(NATO Science For Peace and Security Series B - Physics and Biophysics) Plamen Petkov, Dumitru Tsiulyanu, Cyril Popov, Wilhelm Kulisch - Advanced N

NATO Science for Peace and Security Series - B:
Physics and Biophysics
Advanced Nanotechnologies
for Detection and Defence
against CBRN Agents
Edited by
Plamen Petkov
Dumitru Tsiulyanu
Cyril Popov
Wilhelm Kulisch
AB 3
Advanced Nanotechnologies for Detection
and Defence against CBRN Agents
NATO Science for Peace and Security Series
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Series B: Physics and Biophysics

Advanced Nanotechnologies for
Detection and Defence against
CBRN Agents
edited by
Plamen Petkov
Department of Physics
University of Chemical Technology &
Metallurgy
Sofia, Bulgaria
Dumitru Tsiulyanu
Department of Physics
Technical University of Moldova
Chisinau, Moldova
Cyril Popov
Institute of Nanostructure Technologies and Analytics
University of Kassel
Kassel, Germany
and
Wilhelm Kulisch
Department of Mathematics and Natural Sciences
University of Kassel
Kassel, Germany
Published in Cooperation with NATO Emerging Security Challenges Division

Proceedings of the NATO Advanced Study Institute on
Advanced Nanotechnologies for Detection and Defence
against CBRN Agents
Sozopol, Bulgaria
12–20 September 2017
Library of Congress Control Number: 2018941543
ISBN 978-94-024-1516-2 (PB)

ISBN 978-94-024-1297-0 (HB)
ISBN 978-94-024-1298-7 (eBook)
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Preface
The ever-increasing requirements towards different aspects of security, for example,

in information technology and cyber defence, in biotechnology, in management and
in the early detection and defence against chemical, biological, radiological and
nuclear (CBRN) agents, demand the latest achievements of nanoscience and nano-
technology. Novel functional materials, devices and systems allowing the control of
matter on atomic and molecular levels, that is, at the level of the matter building
blocks, have to face the challenges of the security of the modern society. The
nanostructured materials possess unique mechanical, electrical, optical, magnetic
and biological properties, which are entirely different from those of the conventional
micro- or millimeter-sized materials, due to their distinctive sizes and shapes, and
predominant surface and quantum effects determining their behaviour. In such a
sense, nanomaterials and nanotechnologies have a strong potential to be the main
driving forces in the development of new concepts for security and safety. It
concerns not only the preparation and investigation of smart nanosized materials
for different applications, like quantum dots, nanotubes, graphene, nanowires,
nanoparticles and nanocomposites, but also the combination of their performance
with ICs, micro- and nanooptics, MEMS and NEMS, leading to higher level of
integration and effective processing and transmission. Only the common efforts of
scientists from different fields of research – chemistry, physics, biology, materials
science and engineering – and from different countries can bring the complementary
expertise in the development of reliable conceptions in the defence against CBRN
agents taking the advantages of nanomaterials and nanotechnologies.
The first objective of the NATO ASI on Advanced Nanotechnologies for
Detection and Defence against CBRN Agents held between 12th and 20th
September 2017 in Sozopol, Bulgaria, was to present to the participants the up-to-
date achievements for applications of nanomaterials and nanotechnologies in differ-
ent fields related to the diagnostics and defence against CBRN agents and the future
perspectives and trends. The second objective was the teaching and training of the
participants in the scientific and technological background of nanostructured mate-
rials used in fields, like new generation of advanced sensors and systems for early
v
vi Preface
detection of CBRN agents, efficient defence against these agents and so on. The third
objective addressed the initiation of transborder and interdisciplinary collaborations
between young scientists towards the implementation of the recent nanotechnolog-
ical achievements to meet the emerging security challenges. The overall objective of
the ASI was the transfer of competence in the nanomaterials and nanotechnological
advances in different fields of security and networking between young scientists
from NATO and partner countries in order to meet one of the key priorities of the
NATO Science for Peace and Security Programme.
The ASI covered topics connected with the recent achievements in different fields
of security related to defence against CBRN agents taking the advantages of
nanotechnology and nanomaterials. The lectures were given by outstanding scien-
tists from universities and research institutes who are experts in nanoscience-related
security fields. Eleven thematic seminars on specific topics, not covered by the
lectures, were also included in the programme. Three open-air poster sessions were
held in the afternoons, during which the participants could present their results,
established closer contacts and discussed in less formal atmosphere.
Seventy-seven participants from 12 NATO countries (Bulgaria, Canada, Czech
Republic, Germany, Hungary, Italy, Poland, Portugal, Romania, Spain, Turkey and
USA) and 5 partner countries (Egypt, FYR Macedonia, Moldova, Morocco and
Ukraine) ensured that the overall objective of transfer of competence and technology
in the field of nanostructured materials and nanotechnologies was reached on a high
level. Such events contribute to the scientific collaborations in these advanced fields
of research between NATO and partner countries as well as to the promotion of
nanoscience and nanotechnology in the partner countries. The latter objective was
successfully reached by the participation of 25 scientists from partner countries.
About half of 77 attendees were female reflecting the increased role of the women in
these fields of research.
The ASI demonstrated once again the commitment of NATO to the peace and the
security by facilitating the scientific dialog and cooperation, which was the major
outcome of the meeting. It revealed that the top-leading fields of civil science are
currently playing and will play also in the future a strategic role to address all
emerging security challenges. Furthermore, the ASI exhibited the strength and
effectiveness of modern science as a tool for international dialogue and supported
the exchange of information and ideas on the recent development of nanoscience and
nanotechnology directed to different security challenges. This major message of the
event attracted the media, which covered the event in newspapers, on information
web pages and on the TV.
We, the members of the Organizing Committee, would like to thank the NATO
Science Committee for the financial support for the organisation of the ASI. The
local organisation and the publicity of the ASI in the media were actively supported
by Mr. Panayot Reyzi, Mayor of Sozopol, whom we gratefully acknowledge.
Preface vii
Group photo of NATO Advanced Study Institute on Advanced Nanotechnologies for Detection and
Defence against CBRN Agents
Sofia, Bulgaria Plamen Petkov

Chisinau, Moldova Dumitru Tsiulyanu
Kassel, Germany Cyril Popov
Kassel, Germany Wilhelm Kulisch
November 2017
Contents
Part I General Topics

1 Roadmapping the Future in Defense and Security: Innovations
in Technology Using Multidisciplinary Convergence . . . . . . . . . . . . 3
Ashok Vaseashta
Part II Material Preparation and Processing

2 Crystalline Thin Layers of BaTiO3 for Gas Sensors
Prepared by PLD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Tomáš Kocourek, Miroslav Jelínek, Václav Studnička,
and Jan Drahokoupil
3 A Comparative Study of the Morphology of Y-Type Hexaferrite
Powders Obtained by Sol-Gel Auto-Combustion and
Ultrasonic Co-precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Borislava Georgieva, Svetoslav Kolev, Chavdar Ghelev,
Tatyana Koutzarova, Daniela Kovacheva, Benedicte Vertruyen,
and Raphael Closset
4 2D Hybrid Si-, Ti-Nanocomposites for Optoelectronic
Devices Manufactured by the Sol-Gel Method . . . . . . . . . . . . . . . . . 37
G. M. Telbiz, E. Leonenko, G. Gulbinas, and P. Manoryk
5 Surface Plasmon Resonance Band of Ion-Synthesized Ag
Nanoparticles in High Dose Ag:PMMA Nanocomposite Films . . . . . 43
T. S. Kavetskyy, M. M. Kravtsiv, G. M. Telbiz, V. I. Nuzhdin,
V. F. Valeev, and A. L. Stepanov
ix
x Contents
6 Formation of a Periodic Structure in a Chalcogenide Film

Substrate by Silver Ion Implantation . . . . . . . . . . . . . . . . . . . . . . . . 49
T. S. Kavetskyy, K. V. Zubrytska, A. V. Stronski, L. I. Pan’kiv,
P. Petkov, V. I. Nuzhdin, V. F. Valeev, A. M. Rogov, Y. N. Osin,
A. S. Morozova, and A. L. Stepanov
7 Optical Band Gap and Carbon Clusters in PMMA
Nanocomposite Films Formed by Ion Implantation:
Boron, Helium, and Xenon Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
M. Trzciński, T. S. Kavetskyy, and A. L. Stepanov
Part III Structural and Optical Characterization

8 Preparation and Characterization of SERS Substrates
of Different Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
I. Rigó, M. Veres, L. Himics, T. Váczi, and P. Fürjes
9 Synthesis of UV Sensitive Rare Earth Doped Materials . . . . . . . . . . 69
Irena Kostova and Dan Tonchev
10 Characterization of Nickel-Cobaltite Spinel Prepared
by Different Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
D. Nicheva, V. Boev, P. Petkov, G. Avdeev, and T. Petkova
11 Structure and Thermal Behaviour of Lithium Sodium
Sulphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Z. Slavkova, O. Kostadinova, G. Avdeev, and T. Petkova
12 Influence of Modification on the Structure and Physical
Properties of Arsenic Trisulfide. A Short Review . . . . . . . . . . . . . . 95
Oleksandr Paiuk
Part IV Electrical Characterization

13 Time Domain Versus Frequency Domain in the
Characterization of Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
L. C. Costa
14 The Measurement of Thermally Stimulated Depolarization
and Polarization Currents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
M. P. F. Graça and P. R. Prezas
15 Iron Concentration Effect on the Microwave Dielectric
Properties of BiNbO4 Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
S. Devesa, M. P. Graça, and L. C. Costa
Contents xi
16 Dielectric Analysis of Phosphate-Borate Glass-Ceramics

Doped with Alkali Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
B. M. G. Melo, M. A. Valente, and M. P. F. Graça
17 Electrical and Magnetic Properties of Yttrium Ferrites . . . . . . . . . . 165
S. Soreto Teixeira, A. J. M. Sales, M. P. F. Graça, M. A. Valente,
and L. C. Costa
Part V Materials: Graphene, Nanotubes and Nanodiamonds

18 Nanostructured Carbon Materials: Synthesis and Applications . . . . 177
Alejandro Ansón-Casaos, Enrique Garcia-Bordeje, Ana M. Benito,
and Wolfgang K. Maser
19 Quantum Information Technology and Sensing Based
on Color Centers in Diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Nina Felgen, Alexander Schmidt, Boris Naydenov, Fedor Jelezko,
Johann Peter Reithmaier, and Cyril Popov
20 Experimental Study of Spectral Parameters of Silicon-Vacancy
Centers in MWCVD Nanodiamond Films Important
for Sensing Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
L. Himics, M. Veres, S. Tóth, I. Rigó, and M. Koós
21 Electrochemical Synthesis of PANI/Graphene Nanocomposites
Aimed for Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
Aleksandar Petrovski, Perica Paunović, Anita Grozdanov,
Aleksandar T. Dimitrov, Gennaro Gentile, and Maurizio Avella
22 Preparation of Metallic and Semiconducting SWCNT
Inks by a Simple Chromatographic Method:
A Two-Parameter Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
Ana Santidrian, Nekane Lozano, Ana M. Benito, Wolfgang K. Maser,
and Alejandro Anson-Casaos
Part VI Materials: Nanowires and Fibers

23 Loaded Nanofibers: Force Protection, Filtration,
Decontamination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Ashok Vaseashta and Nimet Karagülle-Bölgen
24 Nanocomposites of Electrospun Polymeric Materials
As Protective Textiles Against Chemical and Biological
Hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Nimet Bölgen and Ashok Vaseashta
xii Contents
Part VII Materials: Nanocomposites

25 Temperature Effect on the Dielectric Response of Carbon
Nanotubes Particles Filled Polyester Polymer Composites . . . . . . . . 261
Z. Samir, S. Boukheir, Y. El Merabet, M. P. F. Graça, M. E. Achour,
and L. C. Costa
26 Nanosized Ferrite Materials for Absorption of and Protection
from MW Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
Svetoslav Kolev and Tatyana Koutzarova
27 Dielectric Relaxation in Biocomposites Based on Olive
Pomace Grains . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
L. Kreit, Z. Samir, I. Bouknaitir, A. Triki, M. E. Achour, L. C. Costa,
A. Kallel, A. Oueriagli, and M. Mabrouki
28 Green Synthesis of Silver Nanoparticles and Their Application
in Thin Polymer Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
Zhana Petkova, Irena Kostova, and Ginka Antova
29 Synthesis of Iron Oxide Nanoparticles Modified with Silanes
and Their Heating Ability in Alternating Magnetic Fields . . . . . . . . 299
L. Storozhuk and N. Iukhymenko
Part VIII Materials: Glasses and Polymers

30 Ureasil-Based Polymer Matrices As Sensitive Layers for
the Construction of Amperometric Biosensors . . . . . . . . . . . . . . . . . 309
T. S. Kavetskyy, O. Smutok, M. Gonchar, O. Šauša, Y. Kukhazh,
H. Švajdlenková, T. Petkova, V. Boev, and V. Ilcheva
31 Impedance Characterization of Gas Sensitive Chalcogenide
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
Dumitru Tsiulyanu, Marina Ciobanu, and Olga Mocreac
32 Swelling Behavior of Organic-Inorganic Ureasil-Based
Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
T. S. Kavetskyy, H. Švajdlenková, Y. Kukhazh, O. Šauša,
K. Čechová, I. Mat’ko, N. Hoivanovych, O. Dytso, T. Petkova,
V. Boev, and V. Ilcheva
33 Synthesis and Characterization of Organically Modified Silicates
Obtained by Co-condensation of Two Organic – Inorganic
Ureasilicate Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
V. Ilcheva, V. Boev, D. Tatchev, G. Avdeev, G. Zamfirova,
V. Gaydarov, V. Lilova, and T. Petkova
Contents xiii
34 Sr-Substituted Barium Titanate Glass Ceramics from Oxide

Glasses As Potential Material for Sensor Preparation . . . . . . . . . . . 349
Ruzha Harizanova, Liliya Vladislavova, Christian Bocker,
Georgi Avdeev, and Christian Rüssel
35 BaO/SrO/ZnO/SiO2 Glass System: Influence of Different
Nucleation Agents: Bulk Versus Surface Crystallisation . . . . . . . . . 361
Liliya Vladislavova, Christian Thieme, Tilman Zscheckel,
Christian Patzig, Thomas Höche, and Christian Rüssel
36 Bismuth-Titanate Bi2Ti2O7 Crystallization in the
Bi2O3/TiO2/SiO2/Nd2O3 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
Stanislav Slavov and Zheng Jiao
Part IX Applications: Sensors and Detectors

37 Application of Sm Oxide Doped Oxyfluoride Glasses for
the Development of Extrinsic Fibre Optical X-Ray Sensors . . . . . . . 375
T. Eftimov, D. Tonchev, I. Kostova, G. Patronov, and T. Pashova
38 MWCNT/PANI Screen Printed Electrodes for Gas Sensors . . . . . . 389
Gorazd Chepishevski, Aleksandar Petrovski, Anita Grozdanov,
Perica Paunović, Aleksandar Dimitrov, Gennaro Gentile,
and Maurizio Avella
39 Synthesis of RGO/SiO2 and Ag/RGO/SiO2 Nanocomposites
and Study of Their Sensitivity Towards Humidity . . . . . . . . . . . . . . 397
A. S. A. Shalaby, Sh. Safwat-Mansour, Ahmed S. Afify, M. Hassan,
and A. Staneva
40 Preparation of Nanoporous Hybrid Materials with Bridged
Tetra Sulfide Functional Groups and Determination of Their
Sensing Characteristics Towards Relative Humidity . . . . . . . . . . . . 407
M. Abdallah, N. Velikova, Y. Ivanova, Ahmed S. Afify, M. Ataalla,
and M. Hassan
41 Humidity Sensing Properties of Tungsten Based Glass
Crystalline Materials in the WO3-ZnO-La2O3-Al2O3 System . . . . . . 417
M. Ataalla, Ahmed S. Afify, M. Hassan, A. M. Adam, M. Milanova,
and Iskra Piroeva
42 Green Synthesis of Silver Nanoparticles Using Lantana Camara
Leaf Extract and Their Use as Mercury(II) Ion Sensor . . . . . . . . . . 427
Didem Demir, Nimet Bölgen, and Ashok Vaseashta
43 Highly Ordered AAO Layers for Various Sensor Applications . . . . 435
S. Kozhukharov, Ch. Girginov, and O. Kostadinova
xiv Contents
44 Individual Bi2O3-Functionalized ZnO Microwire for

Hydrogen Gas Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Vasile Postica, Oleg Lupan, Jorit Gröttrup, and Rainer Adelung
Part X Applications: Water Treatment, Environment and Health

45 Improvement of the Catalytic Activity of Pt through Synergetic
Interaction with Co . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
Perica Paunović, Orce Popovski, Prashant Khadke, Ulrike Krewer,
Goran Načevski, Anita Grozdanov, and Aleksandar T. Dimitrov
46 Antibacterial Coatings for Biomedical Applications . . . . . . . . . . . . 467
P. Písařík, M. Jelínek, J. Remsa, and J. Mikšovský
47 Identification and Evolution of Biocatalysts of Interest . . . . . . . . . . 477
Ioannis V. Pavlidis
48 Self-Organized Magnetic Nanoparticles in Plant Systems:
ESR Detection and Perspectives for Biomedical Applications . . . . . 487
T. S. Kavetskyy, R. I. Khalilov, O. O. Voloshanska,
L. M. Kropyvnytska, T. M. Beyba, V. A. Serezhenkov,
A. N. Nasibova, A. Akbarzadeh, and S. Ya. Voloshanska
49 Nanoparticle Based Decontamination of Bacteria/Pathogens . . . . . . 493
N. Enaki, T. Paslari, E. Starodub, S. Bizgan, C. Ristoscu,
I. N. Mihailescu, and A. Vaseashta
50 Development of Nanostructured Materials with CBRN
Agents Sensing Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
A. Stoilova, A. Georgiev, D. Nazarova, L. Nedelchev, D. Dimov,
and P. Petkov
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
Part I
General Topics
Chapter 1
Roadmapping the Future in Defense
and Security: Innovations in Technology
Using Multidisciplinary Convergence
Ashok Vaseashta
Abstract Setting priorities in a complex defence environment requires technology

assessment, data driven decision support tools, foresight, and roadmapping the
future pathways. There are several procedures to deliver a balanced, yet strategic
assessment. This report posits roadmapping of revolutionary scientific break-
throughs based on advanced sciences convergence (ASC) in multidisciplinary envi-
ronments and data analytics platforms. Innovations lead to mapping technology
roadmaps which are cautiously formulated based on extensive research, expert
elicitation and networking approaches to project “future scenarios” realistically
and epistemologically. Such roadmaps enable the development of transformative
tools and methodologies that fill fundamental knowledge gaps. Synergy arising from
converging technologies and research methodologies will leverage emerging and
potentially transformative studies. A “framework by design” of emerging scientific
and technological advances and trends is developed through a systematic and
strategic planning process to deepen the understanding of current, future, and
varying challenges and opportunities and create fully integrated solution pathways
to address current and future global issues. Through a systematic introduction of
ASC, the methodology exploits future-oriented analytical methodologies, including
heuristics, data-mining, scientometrics, modelling and simulation, and scenario
development to provide solutions and their potential for integrated, novel and
unconventional manifestations.
Keywords Data analytics · Convergence · Roadmap · Defence · Security
A. Vaseashta (*)
Institute for Advanced Sciences Convergence, and Int’l Clean Water Institute, Herndon, VA,
USA
NJCU – State University of New Jersey, NJ, USA
e-mail: [email protected]; [email protected]
© Springer Science+Business Media B.V., part of Springer Nature 2018 3

P. Petkov et al. (eds.), Advanced Nanotechnologies for Detection and Defence
against CBRN Agents, NATO Science for Peace and Security Series B: Physics and
Biophysics, https://doi.org/10.1007/978-94-024-1298-7_1
4 A. Vaseashta
1.1 Introduction
In a conventional defence scenario, the outcome can be predicted by estimating the

quantity of the opposing forces and/or by their quality. In the current asymmetric
environment, the assumption is not valid. To gain a tactical advantage over the
adversaries, it is critical to assess capability, develop scenario planning, learn gaps in
capabilities and develop technological capabilities to bridge such gaps. The study
presented here outlines systematic and forward-looking methodologies on intelligent
ways to support policy makers by using decision support tools, developed using
comprehensive analysis. The methodology offers a plausible “designed” future
based on sound decisions involving the latest technologies, social dynamics, and
foresight that support investment recommendations and implementation of policies
that will have significant benefit to the public at large.
Employing emerging scientific and technological advances and trends, a “frame-
work by design” is developed through a systematic and strategic foresight process to
extend the understanding of current, future, and varying challenges and opportuni-
ties. Technology assessment and data analytics provide fully integrated solution
pathways, or roadmaps, to address current and future global issues. Through a
systematic introduction of the advanced sciences convergence (ASC), the method-
ology exploits future-oriented data analytical methodologies, including heuristics,
data-mining, scientometrics, modelling and simulation, and scenario development to
provide novel solutions in support of the mission. The synergy arising from the
convergence of multiple disciplines offers boundless potential for transformational,
revolutionary, and embryonic opportunities.
For sake of clarity and continuity, it is instructive to define key terminologies.
Predictive analytics is an area of statistics that deals with extracting information
from data and using it to predict trends and behaviour patterns. Often the unknown
event of interest is in the future, but predictive analytics can be applied to any type of
unknown whether it is in the present or future. Technology assessment is a
scientific, interactive, and communicative process that aims to contribute to the
formation of public and political opinion on societal aspects of science and technol-
ogy. Roadmapping is creating and delivering strategy and innovation by strategic
alignment and dialogue between functions. The power of roadmapping lies in its
flexibility, which can provide clarity and alignment of specific needs at all levels,
including functional, organization-wide and even collaboration between organiza-
tions. Advanced Sciences Convergence (ASC) is to understand how advances in
different disciplines, and focusing on diverse and discrete problems and applications,
can coalesce into an integrated system to solve a seemingly intractable problem.
ASC in research methodologies transforms the way research is conducted by
overcoming specific barriers or filling existing knowledge gaps.
Moore’s law has made the storage and analysis of data scalable, creating oppor-
tunities for fine-grained data analytics. New data gathering tools have fostered
1 Roadmapping Technologies 5
precise and customized data management and analysis practical. Multidisciplinary

convergence and data analytics have exceptionally high potential for transforming
the way state-of-the-art information is gathered, analysed, and leveraged to enable
future advances and applications. The idea of “Converging Technologies” in con-
junction with data analytics has considerably influenced scientific and social think-
ing about technological innovation space.
The objective of this investigation was aimed at the use of ASC methodologies to
develop automated data mining tools and decision support tools. Three of such
decision support tools were developed, viz. automated data analysis, mining and
surveillance (ADAMS™), technology foresight and road-mapping (TechFARM™)
and New and Emerging Science and Technology Trends and Surveillance
(NESTTS™) to provide additional knowledge and databases; they are described in
the next section. The objective of such data mining tools is learning technological
capabilities and gaps, to provide tactical advantage. A brief overview of these
decision support tools is provided later in this contribution.
1.2 Advanced Sciences Convergence and Foresight

Modality
Recent advances in science and technology (S&T) have provided the means to study,
recognise, control, and even “change by design” transitional characteristics between
isolated atoms and molecules, and bulk materials. Various novel materials with
remarkable and desired properties have recently been fabricated [1]. Such innova-
tions have occurred in multidisciplinary environments. These advances in conjunc-
tion with advances in biotechnology, information technology, cognitive sciences,
genetics, and artificial intelligence are employed to develop future-oriented analyt-
ical methodologies to provide systematic recognition and evaluation of new or
existing S&T solutions and their potential for integrated, novel and/or unconven-
tional approaches to solve new challenges.
The procedure of ASC occurs at the intersection of multiple fields and by
persistent monitoring of new and emerging S&T developments. Its outcomes can
be described in terms of desired actions or qualities of the eventual system. Multiple
approaches, some of which may be high-yield and high-risk research, can be pursued
simultaneously to create integral components of the system. Several convergence
models employing nanotechnology, biotechnology, information technology, cogni-
tive sciences; along with other fields such as artificial intelligence, genetics and
robotics, are evaluated by the scientific community. Innovations occur, in part due to
due to reduced dimensionality of nanomaterials, producing unique characteristics
[2]. Figure 1.1a maps intersecting trajectories of different disciplines, Fig. 1.1b
shows a projection metaphor to show emergence of new and unique applications [3].
6 A. Vaseashta
Fig. 1.1 (a) Intersecting trajectories of different disciplines; (b) projection metaphor showing the
emergence of new and unique applications [3]
1.3 Foresight Innovation Pathways Methodology: Data

Mining and Predictive Analytics
During the last decade alone, new digital learning technologies have fundamentally
altered the practice of conducting research, articulating the path forward for future
investments. Notwithstanding this tremendous progress, the synergy arising from
ASC offers boundless potential for transformational, revolutionary, and embryonic
opportunities. Convergence in research methodologies provide far-sightedness by
highlighting the options and existing knowledge gaps. New data gathering tools
have fostered precise and customized data management and analysis practices.
To provide strategic assessment of revolutionary scientific breakthroughs in
multidisciplinary environments, several data analytics algorithms and their relative
applicability are used in literature which are listed in Table 1.1. The objective of an
independent investigation was to develop automated data mining tools – such as
automated data analysis, mining and surveillance (ADAMS™), technology foresight
and road-mapping (TechFARM™) and New and Emerging Science and Technology
Trends and Surveillance (NESTTS™) to provide an independent confirmation. A set
of specific methodologies used to develop such decision support tools along with
specific tools used for this investigation, is briefly described here. It should be noted
that such data mining tools, in addition to providing technological capabilities, also
unveil technological gaps, allowing us to focus on gaps to achieve desired
capabilities.
To explore this modality, a multi-dimensional futures-oriented methodology that
identifies and manages emerging and/or disruptive S&T trends has been articulated.
The TechFARM™ methodology consists of team brainstorming, expert elicitations,
and creating concept maps of potential solution paths. The recommended system
evolves through three stages, as shown in Fig. 1.2; it can be described as follows.
Stage I: Define topic and review current situation. The preliminary activity begins
with extensive environmental scanning coupled with bibliometrics of scientific
publications, news and media, books, interviews, and conferences. An assessment
of the strengths and weaknesses of the internal capabilities, as well as the threats and
opportunities of the external environment, is critical to explore uncertainties rather
than repressing them. Stage II: Identify change drivers and select critical drivers.
This stage includes strengths and weaknesses of internal capabilities, as well as
threats and opportunities of the external environment that cannot be ignored. A
comprehensive and systematic assessment, including identification of strategic
trends, critical drivers and uncertainties, possible shocks and scenario building,
provides legitimacy to the envisioned ideal system. Stage III: Synthesis and recom-
mendation. Specific methods used to develop roadmaps are listed in Table 1.2.
The primary objective of the trend forecasting is to monitor a field of activity to be
able to plan the variations that will occur in short or long term. The trend monitoring
through competitive intelligence is collecting data. Even more it is watching the
environment persistently. When trend monitoring is done, those data must be
analysed so that the environment is perfectly known, to be able to forecast the
8 A. Vaseashta
Table 1.1 Data analytic tools developed and scope [3]

Rating
Method Applicability environment 1–10a
Multiple regression When two or more independent factors are involved. Widely 8
analysis used for intermediate term forecasting. Assesses which factors
to include; can be used to develop alternate models
Nonlinear Used for non-linear relationships between variables. Frequently 7
regression used when time is the independent variable
Trend analysis Uses linear and nonlinear regression with time as the explana- 9
tory variable. Used to determine patterns over time
Moving average Forecasts future values based on a weighted average of past 7
analysis values. Easy to update due to simple averages
Weighted moving Widely used where repeated forecasts are required. Uses 8
averages methods like sum-of-the-digits and trend adjustment methods.
Very powerful and economical
Adaptive filtering Used for moving averages, this includes a method of learning 7
from past errors. Responds to changes in the relative impor-
tance of trend, seasonal, and random factors
Exponential A moving average form of time series forecasting. Used with 7
smoothing seasonal patterns, relatively easy to adjust for past errors. Sev-
eral different forms are used, depending on presence of trend or
cyclical variations. Used to prepare follow-on forecasts and
where many forecasts must be prepared
Hodrick-Prescott Uses filter mechanism to obtain a long-term trend component in 6
filter a time series. Reduces a given series into stationary and
non-stationary components such that the sum of squares of the
series from the non-stationary component is minimal, with a
penalty on changes to the derivatives of the non-stationary
component
Multi criteria deci- Used for providing decision support with numerous and 6
sion analysis sometimes conflicting evaluations. Provides a compromise in
conflicting data. Used for risk assessment and forecasting
COTS modeling and Modeling describes a situation through a series of equations. 7
simulation Allows testing of impact of changes in various factors other-
wise time-consuming to construct. Requires user programming
or purchase of packages such as SIMSCRIPT. Powerful in
developing and testing strategies not otherwise evident
Certainty models Used to predict only the most likely outcome. Used as “what if” 6
analysis – often done with computer-based spreadsheets
Probabilistic models Use Monte Carlo simulation techniques to deal with uncer- 7
tainty. Provides a range of possible outcomes for each set of
events
a
Subjective
trends. Early warning and weak signal detection are parts of a trend forecast. This
methodology is used in conjunction with the Thomson Reuters Research Analytics
(TRRA) tools to identify significant trends in sciences and to determine research
Fig. 1.2 (a) Overview of the Delphi expert elicitation process, and (b) TechFARM framework
impact in specific fields of research. Bibliometrics (aka scientometrics) applies

quantitative evaluation of publication and citation data used in research performance
evaluation by different organizations. A series of tools such as InCites, Essential
Science Indicators, ResearcherID, ISI Web of Knowledge, and Web of Science®
would accelerate the process of identifying leading edge advances in different
disciplines [4–7].
10 A. Vaseashta
Table 1.2 Specific methods used for roadmapping using ASC

NBIC convergence – environmental scanning (current trends/monitor weak signals)
Delphi survey method – expert elicitation/expert technical panels
Robust factor analysis and strategic development
Computerized modelling and dynamic simulation
Technology foresight method
Extrapolation method
Scenarios planning
Social networking – monitor trends and methodologies/virtual meetings
Predictive intelligence
1.4 Monitoring, Surveillance, Roadmapping: Metrics

and Indicators
A scientific landscape in conjunction with future studies methodologies would

allow metrics-based projections on the direction and pace of scientific innovation
and a list of plausible scenarios for the probability of success of such technologies.
Explorative methods project future analyses forward from the past or present
situation, identifying the past development and status of a given science or tech-
nology to postulate its future. In contrast, a normative approach traces backward
from a hypothetical future situation to assess likelihood, timing and consequences
of a science or technology, thereby identifying a future desired state and determin-
ing developments and innovations necessary to reach that future. The full potential
of S&T future analysis is realized only where exploratory and normative compo-
nents are combined in an iterative cycle. Technology road-mapping is an important
tool for planning and coordination for governments, organizations, and corpora-
tions. It is a specific technique for technology planning, which fits within a more
general set of planning activities. Because of technology road-mapping, an organi-
zation can make better decisions because it has better information to (a) identify
critical needs, (b) determine the technology alternatives, (c) select the appropriate
technology alternatives, and (d) generate and implement a plan to develop and
deploy appropriate technology alternatives. Technology roadmap (TRM) is driven
by a need, not a solution, and hence must have metrics and indicators. Roadmaps
are usually visionary and thus make it very difficult to develop goals; however,
some of the common metrics and indicators for developing a roadmap are: identi-
fying key problems and the metrics that reflect those outcomes; diagnosing perfor-
mance issues using metrics; identifying deviations, trends and dynamic changes;
preventative and corrective approaches; and goal-setting. The roadmap provided in
this report is guided by most of the tools discussed above and conforms to metrics
and indicators (Table 1.3).
Table 1.3 Data analytic tools developed and scope [8]

TECH FARM Application No.: 85/287,943 – Research and development of new products of
others by providing technology foresight, assessment and forecasting services that apply a future-
oriented approach that exploits analytical methodologies, including heuristics, data-mining,
scientometrics, modeling and simulation, and scenario development to provide systematic rec-
ognition and evaluation of new or existing science and technology solutions for the development
of new products and written reports supplied in connection therewith in International Class 42
NESTTS Application No.: 85/287,940 – Research services, namely, providing, tracking, ana-
lyzing and projecting new and emerging trends to provide awareness and means to mitigate threats
and risks posed by chemical, biological, nuclear, radiological, high-yield explosive materials, and
internet and intranet based communications for governments, non-governmental organizations,
industries, and academic institutions for defense and security applications in International Class
42
ADAMS: Application No. 85/287846 – The mark ADAMS is an interactive tool that utilizes
several data mining tools to analyze, evaluate, and determine emerging S&T trends based on
quality of journals, recognition of individual authors and their international stature recognition,
validation by heuristics, and other scientific databases to provide normalized and scientifically
validated information on emerging trends in science and technologies
Within the framework of the recommendations of data analytics and anticipated

characteristics of loading in nanofibers, a spectrum of potential applications was
mapped and is represented in Fig. 1.3. The scope of applications considered here are
textile for chem.-biological sensing/detection/protection and on-site and
on-demand delivery of drugs from the uniform of soldiers in combat theatre.
Furthermore, the three tools as described above were used to forecast trends in
three specific disciples, viz: nanotechnology, biotechnology, and information tech-
nology (Tables 1.4, 1.5, and 1.6).
1.5 Discussion and Path Forward
Using advanced sciences convergence, three such tools are reported here –
TechFARM™, ADAMS™ and NESTTS™. These tools have been applied for a
specific application – defence and security. Based on a specific set of criteria, the
outcome of expectation can be modified by input datasets. The tools were used to
identify the evolving asymmetric threat. Implementation of effective counter-
measures demands an understanding of transformational emerging sciences, con-
cepts and theories, and their potential applications. Development of integrated
solution paths through a revolutionary approach using ASC, presents unique and
novel opportunities of identifying effective counter-measures to emerging uncon-
ventional threats. While ASC research has much potential in addressing the grand
challenges of this century, we must also take a more proactive approach in devel-
oping ethical research guidelines and engaging social and legislative experts in ASC
research dialogues in the formative years of ASC advancement.
12 A. Vaseashta
Fig. 1.3 (a) Use of nanofibers in information and communications technology; (b) spectrum of
potential applications [9]
Table 1.4 Trends in nanotechnology

Smart materials with nano films/fibers and structures
Integration of functions and structure in membranes, fabrics, fibers, self-powered biomimetic
materials
New environmental leaps in performance: e.g. water filtration and purification, biocidal, biore-
mediation and decontamination
Nano sensor networks, tracking capacities – nano-electro-mechanical systems
Wearable personalized nano sensors with data and communications capabilities
Energy and power efficiencies improvements, battery power management
Smart dust capability for widespread surveillance capability
Computational devices embedded in consumer and commercial goods
Functional, programmable nanostructures for controlled drug delivery, performance of implants
and protheses
New devices, building materials and fabrics that incorporate nano materials based solar power
generation and are climate responsive
Table 1.5 Trends in biotechnology

Control, improvements in living organisms
Bio-sensing at the micro and nano level, micro and nano electromechanical systems
Integration with wireless, RFID (radio frequency identification), photonics-molecular level
cameras
Tissue engineering, artificial organs, implants and protheses
Targeted drug delivery and use of in vitro capacities
Rapid scalable bio-assays for molecule ID, medical diagnosis and forensics
Personalized medicine using large data sets of patient information, disease statistics, gene
sequences and genotypes
Genetically modified insects to counter pathogen carriers
In silico- computer testing and comprehensive modelling for drug characteristics, side effects and
receptor simulation – lab on a chip
Molecular recognition – targeted drug delivery to organs, tumours
Table 1.6 Trends in information technology and ambient intelligence

Progress toward ubiquitous information access and integrative ability
Open source collaborative tools and higher peer- to peer functionality, pervasive social networks
Continued migration towards device and functional convergence
Information based 3D models – disease surveillance
Broader object based nodes and networks, Internet of everything (IoT)
Pervasive sensor networks with powerful, dynamic simulation and modelling
Gaming for personal and organizational decisions, risk abatement and learning
Emerging horizons for faster, exponentially more powerful encryption, quantum information
Sustained information markets growth for surveillance, sensor networks, tracking capacities,
nano-electromechanical systems
Wearable, implantable personalized micro-nano-bio info sensors with data and communications
capabilities
14 A. Vaseashta
References
1. Vaseashta A, Dimova-Malinovska D, Marshall JM (eds) (2005) Nanostructured & advanced

materials. Springer, Dordrecht
2. Vaseashta A (2005) In: Vaseashta A, Dimova-Malinovska D, Marshall JM (eds) Nanostructured
materials based next generation devices and sensors, nanostructured and advanced materials.
Springer, Dordrecht, pp 1–30
3. Vaseashta A (2010) NUARI annual report (FOUO) – Technology Foresight and Road Mapping
(TechFARM), year 1 report of scientific roadmap development – submitted in partial fulfilment
of the Advanced Sciences Convergence Study (ASCS), authorized under Contract W911NF-07-
D-0001. Delivery Order, Scientific Services Program (SSP) Subcontract Agreement – TCN
09003Defense Threat Reduction Agency
4. Nordmann A (2004) The EU-HLEG report: converging technologies – shaping the future of
European societies. http://europa.eu.int/comm/research/conferences/2004/ntw/index_en.html
5. Spence R, Davy B, Dufour P, Lafond R, Leppan W, Woo J (2004) IDRC, biotechnology, and
emerging technologies: a basic primer. http://web.idrc.ca/uploads/user-S/1084840901101_Fore
word.doc
6. Adlakha-Hutcheon G, Khaydarov R, Korenstein R, Varma R, Vaseashta A (2009)
Nanomaterials, nanotechnology: applications, consumer products, and benefits, NATO science
for peace and security series c: environmental security, nanomaterials: risks and benefits
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NATO science for peace and security series b: physics and biophysics, silicon vs. carbon.
Springer, Dordrecht
8. https://www.uspto.gov/ TM: Application Nos.: 85/287943, 85/287940, 85/287846
9. Vaseashta A, Karagulle N (2018) Loaded nanofibers – force protection, filtration, and decon-
tamination. In: Advanced nanotechnologies for detection and defence against CBRN agents.
Springer, Dordrecht, pp 241–252
Part II
Material Preparation and Processing
Chapter 2
Crystalline Thin Layers of BaTiO3 for Gas
Sensors Prepared by PLD
Tomáš Kocourek, Miroslav Jelínek, Václav Studnička, and Jan Drahokoupil
Abstract The synthesis of BaTiO3 thin films for gas detectors was studied. Thin
layers of BaTiO3 (BTO) were deposited by pulsed laser deposition (PLD) on fused
silica and Si (100) substrates using various deposition conditions from a sintered
BaTiO3 target. The energy density of a KrF excimer laser was in the range from 2 to
6 Jcm2. Films were deposited in an O2 ambient in the range from 103 to 10 Pa.
The films were prepared at substrate temperatures ranging from 500 to 980 C.
Polycrystalline BTO was obtained at substrate temperatures above 670 C. With
increasing deposition temperature above 700 C the formation of the unwanted rutile
phase prevented the growth of perovskite ferroelectric BTO. Concurrently, with
decreasing substrate temperature below 670 C, amorphous films were formed. The
layers was characterized by XRD spectroscopy and AFM microscopy. We optimized
the depositions condition of the layers for chemical sensors.
Keywords BaTiO3 · Thin layer · PLD · Crystallinity
2.1 Introduction
Barium titanate (BaTiO3 or BTO) is a ferroelectric ceramic material, showing a

photorefractive effect and piezoelectric properties. It is used in capacitors, electro-
mechanical transducers and nonlinear optics. This titanate is the best-studied arche-
typical oxide ferroelectric material with perovskite-structure Ferroelectric crystals
have long been employed in optical applications owing to their high transparency,
T. Kocourek (*) · M. Jelínek

Institute of Physics of the Czech Academy of Sciences, Prague 8, Czech Republic
Faculty of Biomedical Engineering, Czech Technical University in Prague, Kladno, Czech
Republic
e-mail: [email protected]
V. Studnička · J. Drahokoupil
Institute of Physics of the Czech Academy of Sciences, Prague 8, Czech Republic

18 T. Kocourek et al.
large refraction, and strong linear and nonlinear electro-optic effects in the visible
range [1–4]. Modern and future integrated photonic and optoelectronic applications
require single-crystal-type epitaxial ferroelectric thin films instead of bulk ferroelec-
tric crystals [5–9]. Although there are a number of ferroelectric oxides with large
linear electro-optic coefficients, BaTiO3 has been chosen as the material for thin
film. The high-temperature phase is cubic, which enables the deposition of epitaxial
layers with relative ease. BaTiO3 also occurs in rhombohedral, orthorhombic, and
tetragonal phases.
The aim of our research is the fabrication of layers sensitive to chemical agents
suitable for chemical sensing. To this end, the right deposition conditions for BaTiO3
layers have to be found, with the final application in mind. In this paper we focus on
crystalline structure determination and on the influence of deposition conditions. The
crystalline structure is the main parameter determining the layer properties. Our aim
is not to find the most crystalline sample, but the most responsive crystalline
structure [10–12].
2.2 Experimental
PLD The BaTiO3 films were prepared by PLD, using a KrF excimer laser
(COMPexProTM 205 F, λ ¼ 248 nm, τ ¼ 20 ns), an energy density on the target
of 2, 4, and 6 J/cm2, a pulse repetition rate of 10 Hz, an oxygen pressure from 103
Pa (vacuum) to 10 Pa. Thin layers of BaTiO3 were deposited on fused silica (FS) and
Si (100) substrates. The substrate temperature was between TS ¼ 500 C, and
980 C. The target-substrate distance (DT-S) was also varied (4, 5, 6, and 7 cm).
Morphology The thickness of the layers was measured by an Alpha-step IQ
mechanical profilometer (KLA TENCOR Co.), the layer roughness was examined
by AFM.
XRD We used XRD in two different arrangements and with two sources: with
divergent beam (Bragg Brentano) and with parallel beam configuration. The reason
was to find a wider scale of conditions to determine preferred orientations. The first
one uses a parallel beam geometry, Cu radiation (0.154056 nm), a detector scan with
a stationary sample (rotating around the normal to the surface), and a glazing angle
of incidence (GAOI). The second one uses a Bragg-Brentano geometry with a linear
X’Celerator detector, and Co radiation (λ ¼ 0.178901 nm). The samples were
inclined by 5 from the ideal position to avoid diffraction from the single crystal
substrate. The diffraction patterns were evaluated by Rietveld-like program TOPAS
3 [13–15].
2 Crystalline Thin Layers of BaTiO3 for Gas Sensors Prepared by PLD 19
2.3 Results and Discussion
The influence of the following deposition parameters on BaTiO3 growth was

examined: substrate temperature during the deposition process, oxygen pressure,
laser fluence, and target-substrate distance. The thickness of fabricated layers for
X-ray diffraction and AFM was between 500 and 1000 nm.
XRD The comparison of XRD spectra of layers fabricated at different TS are
displayed in Figs. 2.1, 2.2, 2.3, and 2.4. No significant peaks of BTO are present
Fig. 2.1 XRD BTO spectra for different TS for a constant laser fluence of 2 Jcm2, constant
oxygen pressure of 0.5 Pa, and constant DT-S of 5 cm on FS substrates
Fig. 2.2 XRD BTO spectra for different TS for a constant laser fluence of 2 Jcm2, constant
Fig. 2.3 XRD BTO spectra for different TS for a constant laser fluence of 2 Jcm2, a constant
oxygen pressure of 10 Pa, and constant DT-S of 6 cm on FS substrates
Fig. 2.4 XRD BTO spectra for different TS for a constant laser fluence of 6 Jcm2, a constant
for a laser fluence of 2 Jcm2, an oxygen pressure of 0.5 Pa, DT-S of 5 cm, and for TS
lower than 670 . Peaks attributed to BTO start to appear at TS of 740 C, but
disappear at 780 C and reappear at 980 C, but we found several more peaks that
we were unable to attribute to any know BTO phase (Fig. 2.1).When the oxygen
ambient was decreased to 0.1 Pa and DT-S increased to 6 cm, the amorphous phase at
500 C changes to well crystalline at 700 C. We observe all main peaks, especially
the (100) orientation, which is reported to be critical for functioning sensors [10]
(Fig. 2.2). With increasing pressure (10 Pa) and otherwise constant conditions
(at 700 C) the peaks still appear but their intensity is lower (Fig. 2.3). The same
decrease in peak intensity is observed with the increase of the laser fluence to 6 Jcm2
and DT-S increase to 7 cm. The signal is weak for both temperatures (Fig. 2.4).
The influence of the oxygen pressure on the XRD spectra is displayed in Figs. 2.5,
2.6, and 2.7. We tested pressure values from high vacuum (103 Pa) up to 10 Pa. For
laser fluence of 2 Jcm2, TS of 740 C, and DT-S of 5 cm all layers (103, 0.5, and
5 Pa) were polycrystalline (Fig. 2.5). With decrease of TS to 500 C and an increase
of DT-S to 6 cm the layers were amorphous at 0.1 and 10 Pa (Fig. 2.6).
Well crystalline samples were prepared at TS of 700 C and an oxygen pressure of
0.1 Pa. The layers were textured with a strong (100) peak. At an oxygen pressure of
10 Pa the crystalline content was lower (Fig. 2.7).
Fig. 2.5 XRD BTO spectra for different oxygen pressures, a constant laser fluence of 2 Jcm2, a
constant TS of 740 C, and constant DT-S of 5 cm on FS substrates
The XRD spectra displayed in Figs. 2.8, 2.9, and 2.10 compare different laser
fluences. At TS ¼ 670 C, 0.5 Pa, and DT-S ¼ 5 cm, crystalline layers were obtained
only for a laser fluence of 4 Jcm2 (Fig. 2.8).
At TS 700 C, 0.1 Pa and DT-S ¼ 6 cm all layers are polycrystalline, but the
highest crystalline content was reached for a laser fluence of 2 Jcm2 (Fig. 2.9). For
two best laser fluences BaTiO3 layers were deposited on silicon substrates
(Fig. 2.10), where the highest crystalline content was reached.
Varying DT-S had no significant influence on the crystalline structure for laser
fluences of 2 and 4 Jcm2, at TS of 780 C/670 C and an oxygen pressure of 0.5 Pa.
XRD spectra for DT-S of 4–7 cm are displayed in Figs. 2.11 and 2.12.
From the XRD results optimal deposition conditions can be deduced for BaTiO3
thin layers developed for active detection layer of chemical sensors. The optimal
crystalline structure is preferably oriented in (100) and (200) directions. This orien-
tation was reached for samples fabricated at TS of 700 C, a laser fluence of 2 Jcm2,
an oxygen pressure of 0.1 Pa, and DT-S ¼ 6 cm.
Fig. 2.6 XRD BTO spectra for different oxygen pressures, a constant laser fluence of 2 Jcm2,
Fig. 2.7 XRD BTO spectra for different oxygen pressures, a constant laser fluence of 2 Jcm2,
Fig. 2.8 XRD BTO spectra for different laser fluences at constant TS of 670 C, constant oxygen
pressure of 0.5 Pa, and constant DT-S of 5 cm on FS substrates
Morphology The layer morphology was measured by AFM. The layer roughness
rose with increasing of laser fluence. The characterized samples were fabricated on
Si (100) at TS 700 C, 0.1 Pa, and DT-S of 6 cm. For a laser fluence of 2 Jcm2 the
layers are smooth with occasional droplets of several hundred nanometers
(Fig. 2.13a). For a laser fluence of 4 Jcm2 the surface is rougher with features
around 40 nm (Fig. 2.13c). For the highest laser fluence of 6 Jcm2 the surface
irregularities reached 80 nm (Fig. 2.13b).
Fig. 2.9 XRD BTO spectra for different laser fluences for constant a TS of 700 C, a constant
oxygen pressure of 0.1 Pa, and a constant DT-S of 6 cm on FS substrates
The surface roughness does not pose a problem for chemical sensors based on
electrical resistance change, on the contrary it facilitates higher surface area, which
mean higher sensitivity. For optical measurements methods it would be needed to
prepare smooth and homogeneous layers.
Fig. 2.10 XRD BTO spectra for different laser fluences for a constant TS of 700 C, a constant
oxygen pressure of 0.1 Pa, and a constant DT-S of 6 cm on Si (100) substrates
Fig. 2.11 XRD BTO spectra for different DT-S for a constant laser fluence of 2 Jcm2, a constant
TS of 780 C, and a constant oxygen pressure of 0.5 Pa on FS substrates
Fig. 2.12 XRD BTO spectra for different DT-S for constant laser fluence of 4 Jcm2, a constant TS
of 670 C, and a constant oxygen pressure of 0.5 Pa on FS substrates
2.4 Conclusion
Our results based on XRD and our application [10, 12] indicate that we can
determine the optimal crystalline structure that would be preferably oriented in
(100) and (200). This crystalline structure was reached for samples prepared at TS
of 700 C, a laser fluence of 2 Jcm2, an oxygen ambient of 0.1 Pa, and DT-S of 6 cm.
Generally, better crystalline structures of BaTiO3 were obtained at higher TS on FS
substrates. Si (100) substrates enhanced this even further. The morphology measured
by AFM showed an increase of the roughness with increasing laser fluence. The
higher roughness means a higher surface area which increases the sensitivity. In this
case, it makes sense utilising laser fluence leading to a little deterioration of the
crystalline structure of BaTiO3 thin layers.
80 nm
0 nm
40 µm
40 µm 20 µm
20 µm
0 µm 0 µm
80 nm
0 nm
40 µm
40 µm 20 µm
20 µm
0 µm 0 µm
Fig. 2.13 (a) Surface morphology measured by AFM – laser fluence of 2 Jcm2. (b) Surface
morphology measured by AFM – laser fluence of 6 Jcm2. All samples: TS of 700 C, oxygen
pressure of 0.1 Pa, Si (100) substrates. (c) Surface morphology measured by AFM – laser fluence of
4 Jcm2
80 nm
0 nm
40 µm
40 µm
20 µm
20 µm
0 µm 0 µm
Fig. 2.13 (continued)
Acknowledgments This work has been supported by the Grant Agency of the Czech Republic
(No. GA15-05864S) and the Grant Agency of the Czech Technical University in Prague
(No. SGS16/190/OHK4/2T/17).
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Chapter 3
A Comparative Study of the Morphology
of Y-Type Hexaferrite Powders Obtained by
Sol-Gel Auto-Combustion and Ultrasonic
Co-precipitation
Borislava Georgieva, Svetoslav Kolev, Chavdar Ghelev,

Tatyana Koutzarova, Daniela Kovacheva, Benedicte Vertruyen,
and Raphael Closset
Abstract In recent years, the Y-type hexaferrites have been the object of extensive
research related to studying the magnetoelectric effect in the microwave frequency
range that is typical for these materials and determines their potential use as microwave
absorbers. The morphology of the investigated powders used as fillers in microwave
absorbers considerably affects their properties. We present a study on the influence of
the preparation technique on the morphology of Ba0.5Sr1.5Zn2Fe12O22
and Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 powders. The powders were synthesized by
acetic-acid sol-gel auto-combustion and ultrasonic co-precipitation. The particles of
the samples obtained by ultrasonic co-precipitation had an almost perfect hexagonal
shape typical for hexaferrites. Al-substitution in Ba0.5Sr1.5Zn2Fe12O22
(Ba0.5Sr1.5Zn2Al0.08Fe11.92O22) resulted in lowering the synthesis temperature.
Keywords Magnetoelectrics · Y-type hexaferrites · Al-substitution · Sol-gel auto-

combustion · Ultrasonic co-precipitation
3.1 Introduction
The continuously increasing use of devices operating at microwave

(MW) frequencies in our immediate environment, such as radars and wireless
andmobile communication equipment, has resulted in a substantial increase in the
B. Georgieva (*) · S. Kolev · C. Ghelev · T. Koutzarova

Institute of Electronics, Bulgarian Academy of Sciences, Sofia, Bulgaria
D. Kovacheva
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria
B. Vertruyen · R. Closset
Greenmat, Chemistry Department, University of Liege, Liege, Belgium

32 B. Georgieva et al.
electromagnetic interference. This has led to the growing requirement for the
development of MW absorbing materials reducing the interference, shielding sensi-
tive equipment and minimizing the harmful effects of electromagnetic waves on
biological objects [1]. The M-type hexaferrites have long been used as MW
absorbers. Recently, however, the researchers’ attention turned to the Y-type
hexaferrites, since some of them are also magnetoelectrics, while the magnetoelec-
tric effect in the MW frequency range has been the subject of extensive research
efforts. This effect in the Y-type hexagonal ferrite Ba0.5Sr1.5Zn2Fe12O22 at room
temperature in a low magnetic field (0.1 T) was reported for the first time by Kimura
et al. [2]. Chun et al. [3] reported a large magnetoelectric effect in
Ba0.5Sr1.5Zn2Al0.08Fe11.92O22, which occurs in a much lower magnetic field.
Most of the studies concerning the Y-type hexaferrites focused on their magnetic
and MW properties, which are determined by their microcrystalline structure. The
latter is strongly dependent on the preparation technique and the chemical compo-
sition of the precursor, on the temperature and duration of the particular high-
temperature synthesis, and on the type and degree of substitution. For example, in
our recent studies [4] on M-type barium hexaferrites, we found that the needle-like
Fe2O3 in the precursor leads to incomplete crystallite formation and a
non-uniformity of the particles size in the samples. It was shown in [5] that the
precursor’s type and microstructure substantially affect the Ba2Co2-xZnxFe12O22
formation and, consequently, its magnetic and MW characteristics. In turn, the
precursor’s microstructure is strongly influenced by the method of preparation. On
the other hand, the Y-type hexaferrites are complex oxides, which is reflected in the
large number of difficulties encountered in the preparation of single-phase samples
with homogeneous particles’ size and shape. The process of synthesizing Y-type
hexaferrites always involves the presence of various accompanying magnetic oxides,
the main cause of this being the fact that the temperature interval for Y-phase
synthesis is very narrow. Typically, the Y-type hexaferrite phase synthesis begins
at 900 С and ends at 1200 С [6]. It is, therefore, very important to find methods for
synthesis of Y-type hexaferrite particles with a high degree of homogeneity of size
and shape. Bearing the above in mind, we concentrated our effort on the Y-type
hexaferrites’ microstructure as influenced by the preparation technique. In most of
the published papers, the polycrystalline powder samples have been obtained by sol-
gel auto-combustion, which is a well-known method for synthesis of complex
oxides. We present here a comparative study of the microstructure of
Ba0.5Sr1.5Zn2Fe12O22 synthesized by citric-acid sol-gel auto-combustion and ultra-
sonic co-precipitation.The latter technique can be considered as a modified
co-precipitation, whereby the precursor particles preparation takes place in a liquid
medium under the action of a high-power ultrasound wave causing within a short
period of time the formation, growth and implosive collapse of bubbles generated at
a temperature of 5000 K and a pressure of 800 atm [7, 8].
Besides the preparation technique, another important factor substantially affect-
ing the hexaferrite’s magnetic and MW parameters is the substitution of the magnetic
Fe3+cations with non-magnetic cations. The substitution of iron cations with
3 Comparative Study of the Morphology of Y-Type Hexaferrite Powders 33
aluminum ones in Ba0.5Sr1.5Zn2Fe12O22 results in the appearance of a magnetic

phase transition at 285 K and of a magnetoelectric effect [9]. Our earlier studies on
Al-substituted M-type hexaferrite found that the Al-substitution not only affects the
hexaferrite’s magneto-crystalline structure, but also leads to the formation of very
thin hexagonally-shaped particles [10]. We also discuss here the effect of
Al-substitution in Ba0.5Sr1.5Zn2Fe12O22 on the sample’s microstructure.
3.2 Experiment
The Ba0.5Sr1.5Zn2Fe12O22 and Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 powders were synthe-

sized by citric-acid sol-gel auto-combustion and ultrasonic co-precipitation.
3.2.1 Sol-Gel Auto-combustion
In this case, the corresponding metal nitrates were used as starting materials, and a
citric acid solution was slowly added to the mixed nitrates as a chelator. The citric
acid forms stable complexes with the metal cations and prevents their precipitation in
the solution. The solution was slowly evaporated to form a gel, which was
dehydrated at 120 С to obtain barium-strontium-zinc-iron citrate or barium-stron-
tium-zinc-aluminium-iron citrate. During the dehydration process, the gel turned
into a fluffy mass and was burnt in a self-propagating combustion. The auto-
combustion is accompanied by an oxidation-reduction exothermic reaction, with
the heat released being sufficient to form an oxide mixture. The as-prepared auto-
combusted powders were annealed at 1170 С for 7 h.
3.2.2 Ultrasonic Co-precipitation
This technique consists in dissolving the corresponding metal nitrates in deionized

water and initiating the co-precipitation of metal cations by adding NaOH at
pH ¼ 12. High-power ultrasound was applied for 15 min to assist the
co-precipitation process. The ultrasonic processor used was Sonics, 750 W. The
precursors produced were synthesized at 1170 С for 7 h.
The Ba0.5Sr1.5Zn2Fe12O22 and Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 powders were char-
acterized by X-ray diffraction with Cu-Kα radiation. Scanning electron microscopy
(SEM, Philips ESEM XL30 FEG) was used to determine the size and shape of the
particles and the samples’ morphology.
Fig. 3.1 XRD spectra of the powders obtained by sol-gel auto-combustion (a)
Ba0.5Sr1.5Zn2Fe12O22 and (c) Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 and by ultrasonic co-precipitation (b)
Ba0.5Sr1.5Zn2Fe12O22 and (d) Ba0.5Sr1.5Zn2Al0.08Fe11.92O22
The XRD spectra of all synthesized powders showed the characteristic peaks
corresponding to the Y-type hexaferrite structure as a main phase. The
Ba1.5Sr0.5Zn2Fe12O22 sample obtained by sol-gel auto-combustion contained second
phases of BaFe2O4 and ZnFe2O4 (Fig. 3.1a).
The sample prepared by ultrasonic co-precipitation contained only ZnFe2O4 as a
second phase (Fig. 3.1b). The XRD spectrum of the Ba0.5Sr1.5Zn2Al0.08Fe11.92O22
powder formed by sol-gel auto-combustion showed some impurity of ZnFe2O4
(Fig. 3.1c). Unlike all other samples, in the Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 powder
prepared by ultrasonic co-precipitation the second phase was FeO (wustite)
(Fig. 3.1d).
Figure 3.2 presents the microstructure of the samples. The SEM image (Fig. 3.2a)
of the Ba1.5Sr0.5Zn2Fe12O22 sample obtained by auto-combustion shows that the
particles were of a very non-uniform shape and well-agglomerated to form clusters
of different sizes and shapes.
3 Comparative Study of the Morphology of Y-Type Hexaferrite Powders 35
Fig. 3.2 SEM images of Ba0.5Sr1.5Zn2Fe12O22 obtained by auto-combustion (a) and by ultrasonic
co-precipitation (b)
Fig. 3.3 SEM images of Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 obtained by auto-combustion (a) and by

ultrasonic co-precipitation (b)
In contrast, the particles of the sample obtained by ultrasonic co-precipitation had

the perfect hexagonal shape typical for hexaferrites (Fig. 3.2b), with a size of 1.2 μm
and an average thickness of 168 nm. A three-dimensional grain growth process had
taken place, together with co-growth of the particles; small particles of the second
phase of spinel ZnFe2O4 ferrite were also visible.
As seen in Fig. 3.3a, the Al-substitution in the Ba0.5Sr1.5Zn2Fe12O22 led to a
melting process at 1170 C for the sample obtained by auto-combustion. The
Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 particles show a hexagonal shape. Small ZnFe2O4
particles with an irregular shape are again present. The
Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 powder obtained by ultrasonic co-precipitation
consisted both of particles of various size and shape, and of particles with a
completed hexagonal shape (Fig. 3.3b).
3.4 Conclusions
In conclusion, the Al-substitution reduces the amount of second phases in the case of
auto-combustion. The different techniques of precursor preparation result in differ-
ent second phases in the end-product. The SEM images of the samples’ morphology
demonstrate that the preparation method affects significantly the particles’ shape and
size, with important implications concerning the magnetic and MW absorption
properties of Ba0.5Sr1.5Zn2Fe12O22 and Ba0.5Sr1.5Zn2Al0.08Fe11.92O22.
Acknowledgments B. Georgieva was supported for the synthesis of Ba0.5Sr1.5Zn2Fe12O22 by

Contract DFNP-17-159 funded by the BAS under the Young Scientists and Doctoral Students
Assistance Program 2017. The work was supported in part by the Bulgarian National Science Fund
under contract DN 08/4 “Novel functional ferrites-based magneto-electric structures” and research
agreements between WBI, Belgium, and the Bulgarian Academy of Sciences.
References
1. Xing L, Shun-kang P, Xing Z, Li-chun C (2017) Microwave-absorbing properties of strontium

ferrites prepared via sol-gel method. Cryst Res Technol 52(5):1700057
2. Kimura T, Lawes G, Ramirez AP (2005) Electric polarization rotation in a hexaferrite with
long-wavelength magnetic structures. Phys Rev Lett 94:137201
3. Chun SH, Chai YS, Oh YS, Jaiswal-Nagar D, Ham SY, Kim I, Lee B, Nam DH, Ko K-T, Park
J-H, Chung J-H, Kim KH (2010) Realization of giant magnetoelectricity in helimagnets. Phys
Rev Lett 104:037204
4. Koutzarova T, Kolev S, Grigorov K, Ghelev C, Nedkov I, Ausloos M, Cloots R, Midlarz T,
Zaleski A (2008) Nanosized barium hexaferrite powders obtained by a single microemulsion
technique. Solid State Phenom 140:55–60
5. Kim CM, Na E, Kim I, An SY, Wook Seo J, Hur K, Kim H (2015) The effect of precursor types
on the magnetic properties of Y-type hexaferrite composite. J Appl Phys 117(17A):507
6. Pullar RC (2012) Hexagonal ferrites: a review of the synthesis, properties and applications of
hexaferrite ceramics. Prog Mater Sci 57:1191–1334
7. Manickam S (2011) Sonochemical Synthesis of Oxides and Sulfides. In: Pankaj AM (ed)
Theoretical and experimental sonochemistry involving inorganic systems. Springer, Heidel-
berg, pp 191–211
8. McNamara WB, Didenko YT, Suslick KS (1999) Sonoluminescence temperatures during
multi-bubble cavitation. Nature 401:772–775
9. Georgieva BV, Koutzarova T, Kolev S, Ghelev C, Vertruyen B, Closset R, Cloots R, Zaleski A
(2016) Study of quasi-monophase Y-type hexaferrite Ba0.5 Sr1.5Zn2 Al0.08 Fe11.92 O22 powders.
Bull Chem Comm 48(Special Issue G):141–150
10. Peneva P, Koutzarova T, Kolev S, Ghelev C, Vertruyen B, Henrist C, Closset R, Cloots R,
Zaleski A (2016) Influence of the preparation methods on the structure and magnetic properties
of nanosized Al-substituted barium hexaferrite powders. AIP Conf Proc 1722:220022
Chapter 4
2D Hybrid Si-, Ti-Nanocomposites
for Optoelectronic Devices Manufactured
by the Sol-Gel Method
G. M. Telbiz, E. Leonenko, G. Gulbinas, and P. Manoryk
Abstract Nanoscale hybrid SiO2 and TiO2 films manifest a set of properties
beneficial for use in sensors, dye lasers, amplifiers, switching devices, solar cells,
and OLEDs. With increasing minuteness of these devices, an accurate and homo-
geneous material structure is of primary importance. We studied factors influencing
the characteristics of thin hybrid film which would help to tune the quality of
mesoscale patterned surfaces and to developed a self-assemblying technology
based on the sol-gel method to fabricate of high-quality hybrid nanocomposite
films using network-forming oxides such as silica or titania. The results obtained
are expected to promote the manufacturing of 2D mesoscale surfaces with laser dyes
incorporated into host materials and to open opportunities for simpler configurations
of optoelectronic and sensor device with improved performances.
Keywords Hybrid film · Rhodamine 6G · Sol-gel · Optical spectra · Luminescence
4.1 Introduction
The scientific and technological interest to mesostructured materials is connected to

stable and controlled nanoscale morphologies [1]. These materials would be even
more attractive and useful should it prove possible to dope them with some active
components in order to produce an enhanced absorption or optical nonlinearity. The
main obstacle to the realization of such hybrid materials remains the limited
photostability of the confined dyes inside the solid matrix, the resulting fast degra-
dation of the dye molecules and their luminescent properties [2]. Elaboration of such
materials promises enhanced properties for their applications such as electronic,
G. M. Telbiz · E. Leonenko (*) · P. Manoryk

L.V. Pisarzhevsky Institute of Physical Chemistry National Academy of Sciences of Ukraine,
Kiev, Ukraine
G. Gulbinas
Center for Physical Sciences and Technology, Vilnius, Lithuania

38 G. M. Telbiz et al.
optoelectronic and photovoltaic devices, chemical and biosensors. To this aim, the
chromophore guest should be stable in different environments, small enough to
ensure a good biocompatibility and show high fluorescence yields. Nevertheless,
the preparation conditions might induce interactions between dye molecules causing
their aggregation and hence the quenching of the fluorescence signal. Sometimes
extreme acid or basic conditions could damage the dye causing a loss of the sensing
ability of the dye. The key problem in application hybrid film as photonic materials
is to fix the organic guests into the matrix in order to minimize the self-assembly
aggregation process between individual dye molecules to stabilize the optical prop-
erties of the material. We studied factors strongly influencing the characteristics of
thin hybrid films which would help to tune the quality of surface and bulk, devel-
oping the self-assemblying technology based on the sol-gel method to fabricate
high-quality hybrid nanocomposite films using network-forming oxides such as
silica or titania that allows to variate different types of inclusions [3–5].
Here we present the analysis and comparison of the optical characteristics of dye
molecules self-organized in the bulk of mesostructured silica thin films. Samples
with different concentration of the dye were prepared by the sol–gel method as
homogeneous and transparent films deposited by spin- and dip-coating on the
substrates.
4.2 Experimental
Colored mesostructured SiO2 films were prepared by the template sol–gel technique
using a precursor material composed of matrix tetraethoxysilane or titanium
(IV) butoxide, ethanol, distilled water, HCl and Pluronic P123 (1:8:2:0,5:0,01
molar ratios) and dye. This sol composition has proven to yield good quality SiO2
coatings [6]. The precursors was dissolved in the ethanol using magnetic stirring for
15 min. For preparation of the starting composition, 0,003–0,72 g of Rhodamine 6G
(Rh6G) was dissolved in 10 ml sol. The dye concentration was in the range of 6 104
to 1.5 101 mol/l. This solution was mixed at 60 C for 120 min to form a sol that was
used in all of the following operations. The colored films were obtained on various
substrates (glass, mica, silica) using a hand-made spin coating apparatus and various
rotation speed (1500–2500 min1). A standard procedure of substrate processing
(cleaned in hot chromic mixture), followed by a rinse with distilled water) was adopted
before coating. After that the coatings films were dried at ambient temperature for a
48 h at atmospheric air conditions. The coating thickness measured by atomic force
microscopy (AFM) was 200–800 nm.
The optical (absorption and transmission) spectra were measured at room tem-
perature with a Specord PC 210 spectrophotometer. Steady state photoluminescence
spectra were measured with a Hitachi MPF-4 [7]. The surface relief and thickness of
the films was revealed by AFM using a NanoScope D 300.
4 2D Hybrid Si-, Ti-Nanocomposites for Optoelectronic Devices 39
4.3 Result and Discussion
In designing the films for optical applications, a number of factors need to be taken
into account. Most important is the ability of the film matrix to effectively solubilize
relatively high concentrations of the dye molecules. Such high concentrations are
necessary for the films to exhibit appreciable absorbance, even when their thickness
is only 150–300 nm. Under the assumption that the molecules are not effectively
dispersed within the host matrix, the optical as well as the physical properties of the
films tend to be negatively influenced. For example, broadening of the dye’s
absorption band, loss of its intensity, and a decrease of light transmission through
the film are some of the adverse effects that might result. The method of production
and the optical and physico-chemical quality of the resultant films are the essential
factors to be considered when deciding upon the film composition. Film fabrication
needs to be conducted with relative ease using proven deposition techniques such as
dip-, or spin-coating. This would allow to obtain film containing a variety of dyes
with different concentrations and desired optical properties.
On the Fig. 4.1 compares the absorption spectra of the mesostructured silica and
titanium dioxide thin films. The spectra of the SiO2/P123 and TiO2/P123 films have
absorption maxima at approximately 505, 537 nm and 510, 542 nm, respectively.
The lower wavelength maximum between 505 and 510 nm is known to correspond
to absorption by the H-form of the Rh6G dimer [8, 9]. The main absorption peak,
with a maximum between 530 and 540 nm, corresponds to absorption by the free
R6G monomer. Note that aggregates of Rh6G are known to suppress fluorescent
emission, and are therefore undesirable in the context of amplified spontaneous
emission. The spectra demonstrate that the ratio of dimer to monomer for TiO2 is
significantly lower than for a SiO2 matrix. The results strongly suggest that the
optical properties of the dye molecules in solid matrices depend on the physico-
chemical properties of the matrix (i.e., polarity, refractive index, acidity, etc.), but
also on host-guest interactions, affecting the distribution and orientation of the dye
molecules in the host material, as well as on the dye-dye interactions, responsible for
dye aggregation.
Fig. 4.1 Selected 0,27

absorption spectra of (a)
Rh6G doped P123/SiO2 and A
(b) P123/TiO2 sol-gel films
0,18
a b
0,09
0,00
400 450 500 550 600 650
Wavelenght, (nm)
Fig. 4.2 Selected 1,0

normalized fluorescence I
spectra of (a) Rh6G doped 0,8
P123/SiO2 and (b) P123/
TiO2 sol-gel films
0,6
b a
0,4
0,2
0,0
500 550 600 650 700
Wavelenght, (nm)
Figure 4.2a, b compares the selected fluorescence spectra of Rh6G-doped

mesostructured silica and titanium dioxide thin films measured by excitation at
λex ¼ 480 nm. The spectra had been normalized to the peak emission for clarity.
The fluorescence spectrum of the hybrid SiO2 film (Fig. 4.2a) is broadened, and a
shoulder in the spectrum is observed. The broadening of the band is rather due to the
presence of H-type dimer aggregates, confirmed by the appearance of the shoulder in
the spectrum of this film. Moreover, the appearance of a band with the maximum at
~600 nm can be interpreted as fluorescence of “sandwich”-type aggregates exclu-
sively. This observation is in good accordance with literature data, where broadening
of the emission band is characteristic for the formation of fluorescent aggregates with
“head to tail” geometry. Furthermore, the asymmetric shape of the spectral band is
clearly the result of a high concentration of H- and J- dimers coexisting within the
mesostructured film. Since the H- and J-type aggregates possess exciton states
whose energy levels lie below the monomer S1 state, they can serve to quench the
fluorescence through an energy transfer process.
For Rh6G immersed in the TiO2 matrix (Fig. 4.2b), the spectrum shows that the
emission is broadened which is accompanied by a red shift of the maxima when the
concentration is increased. The spectral broadening can be assigned to increased
re-absorption and subsequent re-emission and at longer wavelengths interpreted as
fluorescence of aggregate with high dye concentration as it was previously attributed
to aggregate fluorescence at elevated RhG6 concentrations in certain solvents
[10, 11]. The occurrence of an FL band at 610 nm in the spectrum was also
associated by other authors [12] to Rh6G aggregates; these low-energy emissions
appear at large dye concentrations. Thus, we have a distribution of dimers,
corresponding to two extreme configurations, which we attribute to sandwich
H-type dimers and head-to tail J-type aggregates.
In the tested regime [13], we had shown the ability of hybrid films for application as
photonic layer in all-optical time-to-space converters. We have recorded the response a
4 2D Hybrid Si-, Ti-Nanocomposites for Optoelectronic Devices 41
dynamic grating in a single-pulse regime. A giant value of the nonlinear optical suscep-
tibility was observed experimentally: χ(3) ¼ 8.6 ∙ 107 esu 8.6 ∙ 1015 m2 V2.
The hybrid sol-gel films (Ti- or Si based) were studied as waveguide laser
medium under transverse optical pumping. The threshold one-mode oscillation for
two different configurations of planar asymmetrical waveguides has been discovered
and investigated. We assumed that gain-narrowing is attributed to amplified spon-
taneous emission which results from the homogeneous distribution of highly doped
dye molecules within the microchannels of the arrays. The pumping threshold values
for the respective (Ti, Si) mesostructured waveguides are different from each other.
In case of a TiO2 matrix, a value of the pumping intensity reduced by almost two
orders compared to a SiO2 matrix is observed.
4.4 Conclusion
The development of a simple sol-gel based method for the production of high quality
inorganic/organic mesostructured SiO2 and TiO2 composite films doped with Rh6G
were studied. The comparison of the concentration dependent evolution of absorp-
tion and emission profiles of both types of matrices reveals the presence of lumi-
nescent aggregates. The observed optical and fluorescence spectra show the ability
of dispersion and controlled aggregation of Rh6G molecules, owing to the time-
delay of their spontaneous transformation and mesoscopic ordering during the
formation of the hybrid sol-gel films. The formation of fluorescent aggregates can
most probably be promoted by the presence of the amphiphilic triblock copolymers
which favor the formation of hybrid micelles and by the excited state of the CT
complex within hybrid micelles between dye and the surrounding Pluronic mole-
cules. Alteration of the optical properties of the films and the exited state dynamic of
Rh6G affected the exiton dynamic of H-type aggregates and makes this film a good
candidate for producing photonic materials for laser action from micron-scaled
devices. Variation of values of refractive index, absorption coefficient and optical
conductivity can be evidence of various spatial organizations of dye molecules
within the body of generated films, subject to method of deposition on substrates.
We demonstrated their possibility for use in modern optoelectronic and optical
devices. It was shown that the unusually spectral-luminescence properties can be
explained by the conditions of spatial organization and controlled self-organization
(aggregation) of dye molecules in the formation process of the hybrid films.
Acknowledgment The authors deeply thank Dr. M. Dvoynenko (Institute of Semiconductor

Physics NASU, Kiev) for kindly help in fluorescence measurements and useful discussions.
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Chapter 5
Surface Plasmon Resonance Band of Ion-
Synthesized Ag Nanoparticles in High Dose
Ag:PMMA Nanocomposite Films
T. S. Kavetskyy, M. M. Kravtsiv, G. M. Telbiz, V. I. Nuzhdin, V. F. Valeev,

and A. L. Stepanov
Abstract Characterization of nanocomposites prepared by Ag ion implantation into

polymethylmethacrylate (PMMA) at different doses (2.5 1016, 1.0 1017, and
1.5 1017 Ag+/cm2) with a constant energy of 30 keV and a current density of
1 μA/cm2 in order to prepare Ag nanoparticles (NPs) was performed by UV-Vis
spectroscopy. For the first time an absorption band at a wavelength of 355 nm for the
highest dose sample was observed experimentally. Changes of size and filling factor
of Ag NPs in the near-surface region of ion-implanted polymers are suggested to
explain this result. However, further verification is needed with more informative
technique such as, for example, slow positron beam spectroscopy to probe near-
surface nanometer size depth profiles.
Keywords Polymers · Ion implantation · Nanocomposite films · Surface plasmon

resonance · Metal nanoparticles · Optical spectroscopy
T. S. Kavetskyy (*)
Drohobych Ivan Franko State Pedagogical University, Drohobych, Ukraine
The John Paul II Catholic University of Lublin, Lublin, Poland
M. M. Kravtsiv
G. M. Telbiz
L.V. Pisarzhevsky Institute of Physical Chemistry National Academy of Sciences of Ukraine,
Kiev, Ukraine
V. I. Nuzhdin · V. F. Valeev
Kazan Physical-Technical Institute of RAS, Kazan, Russian Federation
A. L. Stepanov
Kazan Federal University, Kazan, Russian Federation
Kazan National Research Technological University, Kazan, Russian Federation

44 T. S. Kavetskyy et al.
5.1 Introduction
Understanding how the size, shape, and aggregation state of silver nanoparticles
(NPs) are changed after integration into a target matrix is critical to enhance their
performance in application, including molecular diagnostics, photonics and biomed-
ical devices, and to take advantage of the novel optical properties of these
nanomaterials. In particular, nanocomposites containing noble metal NPs dispersed
in the polymer matrix prepared by high-dose (>1016 ions/cm2) implantation at
low-energy ions (<100 keV) can be used for the construction of plasmonic wave-
guides [1] and diffraction gratings [2]. Typically, form and size of Ag NPs in
optically transparent matrices are related an appearance of a surface plasmon reso-
nance (SPR) band in the visible absorption spectra of the composite. However,
synthesis of Ag NPs by ion implantation in transparent polymer matrices such as
PMMA has been found [1] to be quite unusual. In the present work, characterization
of nanocomposites prepared by Ag ion implantation of PMMA at different doses
was performed by UV-Vis spectroscopy.
5.2 Experimental
Ion implantation into PMMA substrates was performed in vacuum under a pressure
of 105 Torr at room temperature with an ILU-3 ion accelerator [1–5]. 1.2-mm-thick
polymer plates with high optical quality and transparency in a wide spectral range
(400–1000 nm) were used. Ion-implanted PMMA nanocomposites layers (Ag:PMMA)
were fabricated with an energy of 30 keV, an ion current density of 1 μA/cm2 and doses
of 2.5 1016, 1.0 1017, and 1.5 1017 Ag+/cm2 (all doses sufficient for the formation
of Ag NPs [1]). UV-Vis absorption measurements were performed with a
SHIMADZU UV-2700 UV-Vis spectrophotometer.
5.3 Results and discussion
Figure 5.1 shows the absorption spectra for the high-dose Ag:PMMA samples. An
absorption band at λmax ¼ 355 5 nm for the highest dose (1.5 1017 Ag+/cm2)
sample was observed.
Absorption bands below 400 nm were earlier seen in transmission spectra of Ag:
PMMA with dose of 1.0 1017 Ag+/cm2 (but not with dose of 1.5 1017) [2]. It is
assumed that the absorption band at 355 nm for the highest dose sample is due to the
possible changes in size and filling factor of Ag NPs in the near-surface region of
ion-implanted Ag:PMMA in agreement with the basic principles of metal
nanoparticles formation by ion implantation as shown in Fig. 5.2 [1]. In order to
verify this conclusion further research with other proper techniques is needed.
5 Surface Plasmon Resonance Band of Ion-Synthesized Ag Nanoparticles 45
Fig. 5.1 UV-Vis

absorption spectra for the
irradiated Ag:PMMA
samples with different doses
Fig. 5.2 Basic principles of nanoparticles formation by ion implantation
It must be mentioned here that the synthesis of Ag NPs by ion implantation in

PMMA is quite different from that detected for SiO2 glass [6]. So, in PMMA an
unusual weak and very broad SPR band with a maximum at ~500 nm has been
observed for Ag NPs, in contrast to the sharp and narrow SPR band at ~450 nm of
Ag NPs in SiO2. Some plasmonic features in Ag:PMMA have been explained [1, 6]
in the framework of a carbonization of the ion-irradiated polymer and, simulta-
neously, with a formation of carbon-shell Ag-core nanoparticles. Moreover, it has
been concluded that the size of Ag-core NPs increased as the ion dose rises. At the
same time, there are some difficulties to experimentally estimate the NPs sizes
directly from optical absorption for Ag:PMMA [1, 6, 7].
Figure 5.3 shows a schematic presentation of carbon-shell silver-core
nanoparticles with suggested possible changes of size and filling factor of Ag NPs
in the near-surface region of ion-implanted Ag:PMMA for the highest dose sample
(1.5 1017 Ag+/cm2). This assumption should be further confirmed by slow positron
Fig. 5.3 Schematic

presentation of carbon-shell
silver-core nanoparticles
with suggested possible
changes of size and filling
factor for the highest dose
(1.5 1017 Ag+/cm2) Ag:
PMMA
beam spectroscopy (SPBS) as unique technique allowing depth-profiles from tens of

nanometers up to several micrometers. Note, that SPBS has also emerged as a key
experimental tool for understanding high-dose 40 keV boron-ion-implanted
polymethylmethacrylate (B:PMMA) [4, 8] with carbon nanostructures and Ag NPs
loaded poly(dimethylaminoethyl methacrylate) (PDMAEMA) brushes [9, 10]. Also,
the first attempt to find differences between the effects of carbonization and forma-
tion of Ag NPs in high-dose B:PMMA and Ag:PMMA nanocomposites has been
done in [11] by using Doppler broadening SPBS (DB-SPBS).
5.4 Conclusion
Characterization of nanocomposites prepared by 30 keV Ag ion implantation of

PMMA at three doses in order to prepare Ag NPs was performed by UV-Vis
spectroscopy. For the first time an absorption band at 355 nm for the highest dose
sample has been experimentally observed. Possible changes of size and filling factor
of Ag NPs in the near-surface region of ion-implanted Ag:PMMA were in agreement
with the basic principles of metal nanoparticles formation by ion implantation has
been suggested as explanation for this absorption band to be further verified with a
unique technique, for instance slow positron beam spectroscopy to probe near-
surface nanometer-sized depth profiles.
Acknowledgments T.S. Kavetskyy and M.M. Kravtsiv acknowledge the Ministry of Education
and Science of Ukraine (projects Nos. 0116U004737, 0117U007142 (for Young Scientists) and
0117U007143).
5 Surface Plasmon Resonance Band of Ion-Synthesized Ag Nanoparticles 47
References
1. Stepanov AL (2004) Optical properties of metal nanoparticles synthesized in a polymer by ion

implantation: a review. Tech Phys 49:143
2. Galyautdinov MF et al (2016) Formation of a periodic diffractive structure based on poly
(methyl methacrylate) with ion-implanted silver nanoparticles. Tech Phys Lett 42:182
3. Stepanov AL et al (2000) Formation of metal-polymer composites by ion implantation. Phil
Mag B 80:23
4. Kavetskyy T et al (2014) Structural defects and positronium formation in 40 keV B+ -implanted
polymethylmethacrylate. J Phys Chem B 118:4194
5. Stepanov AL et al (2015) Synthesis of porous silicon by ion implantation. Rev Adv Mater Sci
40:155
6. Stepanov AL (2010) Synthesis of silver nanoparticles in dielectric matrix by ion implantation: a
review. Rev Adv Mater Sci 26:1
7. Boldyryeva H et al (2005) High-fluence implantation of negative metal ions into polymers for
surface modification and nanoparticle formation. Surf Coat Technol 196:373
8. Kavetskyy TS, Stepanov AL (2016) In: Monteiro WA (ed) Radiation effects in materials.
InTech, Rijeka, p 287
9. Panzarasa G et al (2016) Positron annihilation spectroscopy: a new frontier for understanding
nanoparticle-loaded polymer brushes. Nanotechnology 27:02LT03
10. Panzarasa G et al (2017) Probing the impact of the initiator layer on grafted-from polymer
brushes: a positron annihilation spectroscopy study. Macromolecules 50:5574
11. Kavetskyy T et al (2017) High-dose boron and silver ion implantation into PMMA probed by
slow positrons: effects of carbonization and formation of metal nanoparticles. J Phys Conf Ser
791:012028
Chapter 6
Formation of a Periodic Structure
in a Chalcogenide Film Substrate by Silver
Ion Implantation
T. S. Kavetskyy, K. V. Zubrytska, A. V. Stronski, L. I. Pan’kiv, P. Petkov,

V. I. Nuzhdin, V. F. Valeev, A. M. Rogov, Y. N. Osin, A. S. Morozova,
and A. L. Stepanov
Abstract Recent results on the fabrication of chalcogenide photonic crystals by

silver ion implantation through a nickel grid mask using (GeSe 5)80B20 chalco-
genide films with a thickness of ~500 nm are reported for the first time.
The periodical structures obtained are characterized by a grating period ~25 μm
and a step height of ~170–200 nm that may find practical use for micro/
nanoelectronics.
Keywords Ion implantation · Chalcogenide glass · Thin film · Photonic crystal
T. S. Kavetskyy (*)
K. V. Zubrytska · L. I. Pan’kiv
A. V. Stronski
V.E. Lashkarev Institute of Semiconductor Physics, National Academy of Sciences of Ukraine,
Kyiv, Ukraine
P. Petkov
Department of Physics, University of Chemical Technology and Metallurgy, Sofia, Bulgaria
V. I. Nuzhdin · V. F. Valeev
A. M. Rogov · Y. N. Osin
A. S. Morozova · A. L. Stepanov

6.1 Introduction
Chalcogenide glasses exhibit a large variety of photoinduced effects which can be

used to obtain different optical elements by means of laser, electron or ion irradiation
[1–3]. Doping of chalcogenide glasses by different elements significantly change
their properties [1–7] with the possibility of surface relief formation using selective
etching [1–3]. Modification of chalcogenide glasses by doping enables the formation
of optical elements with unique properties (e.g., simultaneous formation of surface
and magnetic reliefs) [5]. One frequently used modification tool for chalcogenide
glasses could be ion implantation [2, 3]. Recently, ion implantation was found to be a
powerful tool for the creation of a periodical diffractive structure in silica glass [8],
PMMA [9] and diamond [10]. Actually, a grating was formed in these materials by
implantation with copper, silver, and boron ions through a nickel grid mask with
different square holes of ~20–40 μm. From a practical point of view, such diffraction
gratings could be used in elements of optical communication, for the improvement of
solar cells as well as in biomedical research as active substrates for the registration of
biomolecules through a heterogeneous method in surface-enhanced Raman scatter-
ing (SERS) and surface plasmon resonance (SPR) of metal nanoparticles (in the case
of heterogeneous method in SERS the solution of analyzing biomolecules is placed
onto the surface with SERS-active centers [11]). In the present work, the ion
implantation technique was applied for the formation of a periodic structure in
(GeSe5)80B20 chalcogenide films as substrate using a nickel grid mask with square
holes of ~25 μm.
6.2 Experimental
Chalcogenide glass thin films with a constant ratio Ge:Se ¼ 1:5 and 20 mol.% B were
synthesized by the melt-quenching technique. Starting elements with 5 N purity were
mixed and sealed in evacuated quartz ampoules, heated up to 1200 K for 12 h with
heating rate of 2–3 K min1. The melted samples were quenched in a mixture of ice and
water. Thin film was prepared by a vacuum evaporation of the respective bulk glass in a
standard installation “Hochvacuum” B 30.2. The experimental details of the film
preparation are reported elsewhere [12]. The film thickness was ~500 nm measured
by an optical interference method. Implantation was carried out with Ag+ ions with an
energy of 30 keV, a dose of 8 1016 Ag+/cm2 and a current density of 2 μA/cm2 with
an ILU-3 ion accelerator at the Kazan Physical-Technical Institute of Russian Academy
of Sciences (Russia). The morphology of the formed periodic structure was tested
with scanning electron miscopy (SEM, Merlin, Carl Zeiss). The profile of
the diffraction grating obtained was measured using atomic force microscopy
(AFM, FastScan, Bruker).
6 Formation of a Periodic Structure in a Chalcogenide Film Substrate. . . 51
Figure 6.1 shows the SEM and AFM data obtained for the fabricated sample. The
period of the grating is about 25 μm, step height about 170–200 nm.
The fabrication of submicron chalcogenide glass (As40Se40Te20) photonic crystal
[13] and similar periodic elements [14] using resist-free nanoimprint lithography
was also reported in the literature. Namely, the period of the prepared photonic
crystal structure was 600 nm and the height of the rods in the imprinted structure was
about 150 nm [13]. The observed difference in the period of the photonic crystal
structures is due to the difference in the sizes of the stamp used in nanoimprint
lithography and the square holes in the grid nickel mask used in the ion implantation
technique. If one takes into account the extremely high resolution capability of
chalcogenide inorganic resists [15], ion implantation is promising for fabrication
of different elements with nano- or submicron sizes.
6.4 Conclusion
For the first time a chalcogenide photonic crystal was successfully fabricated by Ag
ion implantation through a nickel grid mask with square holes in a (GeSe5)80B20
chalcogenide film (thickness 500 nm). The results obtained (the period of grating is
about 25 μm, the step height about 170–200 nm) are similar with the literature results
for the fabrication of submicron chalcogenide photonic crystal using thermal
nanoimprint lithography in As40Se40Te20 glass [13] (the period of the prepared
photonic crystal structure is 600 nm and the height of rods in the imprinted structure
is about 150 nm). The observed difference in the period of fabricated photonic
crystal structures is due to the difference in the sizes of the stamp in the case of
the nanoimprint lithography and the square holes in the case of the ion implantation
technique. Thus, the low-energy ion implantation technique, progressively used for
the surface modification of materials and the formation of PMMA nanocomposite
thin films with carbon nanostructures and metal nanoparticles [16–21], oxide mate-
rials with metal nanoparticles [22–24], porous silicon [25, 26] and porous germa-
nium [27], periodic diffractive structure in silica glass [8], PMMA [9] and diamond
[10], could be also used as alternative approach instead of nanoimprint lithography
in the fabrication of photonic crystal structures with certain grating parameters in the
case of chalcogenide glasses.
Fig. 6.1 (a and b) SEM images of the chalcogenide film implanted by 30 keV Ag ions through a
nickel grid mask; (c and d) AFM cross-sections along the lines 1 and 2 shown in (b)
6 Formation of a Periodic Structure in a Chalcogenide Film Substrate. . . 53
Acknowledgments T.S. Kavetskyy and K.V. Zubrytska acknowledge the Ministry of Education
and Science of Ukraine (projects Nos. 0116U004737, 0117U007142 (for Young Scientists) and
0117U007143). A.L. Stepanov thanks for the partial financial support from the Russian Foundation
for Basic Research (project No. 17-08-00780).
References
1. Saito K, Utsugi Y, Yoshikawa A (1988) X-ray lithography with a Ag–Se/Ge–Se inorganic resist
using synchrotron radiation. J Appl Phys 63:565
2. Stronskiin AV, Harman GG, Mach P (eds) (1998) Microelectronic interconnections and
assembly. Springer, Dordrecht, p 263
3. Suzuki T, Hosono H (2002) Ion-beam doping of silver in amorphous As2S3 thin films. J Appl
Phys 92:1821
4. Stronski AV et al (2000) Raman spectra of Ag- and Cu-photo-doped As40S60xSex films. J
Non-Cryst Solids 270:129
5. Stronski A et al (2017) Direct magnetic relief recording using As40S60: Mn–Se nanocomposite
multilayer structures. Nanoscale Res Lett 12:286
6. Stronski A et al (2015) Effect of doping by transitional elements on properties of chalcogenide
glasses. Ceram Int 41:7543
7. Paiuk AP et al (2011) Peculiarities of As–S glass structure doped with ytterbium. Proc SPIE
8306:830617
8. Kavetskyy TS et al (2013) The formation of periodic diffractive plasmonic nanostructures with
implanted copper nanoparticles by local ion etching of silica glass. Tech Phys Lett 39:591
9. Galyautdinov MF et al (2016) Formation of a periodic diffractive structure based on poly(methyl
methacrylate) with ion-implanted silver nanoparticles. Tech Phys Lett 42:182
10. Stepanov AL et al (2017) A diffraction grating created in diamond substrate by boron ion
implantation. Tech Phys Lett 43:104
11. Mamichev DA et al (2012) Optical sensors based on surface plasmon resonance for high-
sensitive biochemical analysis. Mol Med 6:3
12. Petkov P, Parvanov S, Petkova T (2006) Electron transport in amorphous (GeSe5)1x Bx films. J
Optoelectron Adv Mater 8:785
13. Zeng J et al (2017) Fabrication of submicron chalcogenide glass photonic crystal by resist-free
nanoimprint lithography. Appl Phys A Mater Sci Process 123:579
14. Pan WJ et al (2007) Fine embossing of chalcogenide glasses: first time submicron definition of
surface embossed features. J Non-Cryst Solids 353:1302
15. Jain H, Vlcek M (2008) Glasses for lithography. J Non-Cryst Solids 354:1401
16. Kavetskyy TS et al (2014) Structural defects and positronium formation in 40 keV B+-
implanted polymethylmethacrylate. J Phys Chem B 118:4194
17. Kavetskyy T et al (2016) Carbonization in boron-ion-implanted polymethylmethacrylate as
revealed from Raman spectroscopy and electrical measurements. Spectrosc Lett 49:5
18. Kavetskyy T et al (2017) High-dose boron and silver ion implantation into PMMA probed by
slow positrons: effects of carbonization and formation of metal nanoparticles. J Phys Conf Ser
791:012028
19. Trzcinski M, Kavetskyy T, Telbiz G, Stepanov AL (2017) Optical characterization of
nanocomposite polymer formed by ion implantation of boron. J Mater Sci Mater Electron
28:7115
20. Kavetskyy TS, Stepanov AL (2016) In: Monteiro WA (ed) Radiation effects in materials.
InTech, Rijeka, p 287
21. Stepanov AL (2004) Optical properties of metal nanoparticles synthesized in a polymer by ion
implantation: a review. Tech Phys 49:143
22. Stepanov AL (2010) Synthesis of silver nanoparticles in dielectric matrix by ion implantation: a
review. Rev Adv Mater Sci 26:1
23. Stepanov AL (2011) Nonlinear optical properties of implanted metal nanoparticles in various
transparent matrixes: a review. Rev Adv Mater Sci 27:115
24. Stepanov AL et al (2013) Catalytic and biological sensitivity of TiO2 and SiO2 matrices with
silver nanoparticles created by ion implantation: a review. Rev Adv Mater Sci 34:107
25. Stepanov AL et al (2013) New way for synthesis of porous silicon using ion implantation. Adv
Mater – Rapid Commun 7:692
26. Kavetskyy TS, Stepanov AL (2015) In: Petkov P, Tsiulyanu D, Kulisch W, Popov C (eds)
Nanoscience advances in CBRN agents detection, information and energy security. Springer,
Dordrecht, p 35
27. Stepanov AL et al (2017) Synthesis of porous germanium with silver nanoparticles by ion
implantation. Nanotechnol Russ 12:508
Chapter 7
Optical Band Gap and Carbon Clusters
in PMMA Nanocomposite Films Formed by
Ion Implantation: Boron, Helium,
and Xenon Ions
M. Trzciński, T. S. Kavetskyy, and A. L. Stepanov
Abstract The optical band gap and carbon clusters behavior as a function of ion
dose are examined for 40 keV boron, helium, and xenon ion-implanted polymeth-
ylmethacrylate (PMMA) at the same ion doses of 3.13 1015, 6.25 1015,
1.25 1016, and 2.5 1016 ions/cm2. The values of Egopt and Nion are compared
and analyzed. The effect of the ion mass on the carbonization processes in PMMA
nanocomposite films formed by implantation of these ions as revealed from optical
absorption measurements is considered.
Keywords Optical band gap · Carbon clusters · PMMA · Ion implantation
7.1 Introduction
Ion implantation is a powerful tool for structural modification of polymers and

changes of their physico-chemical properties. Investigation of depth profiles of
light and heavy ions implanted into organic polymers [1] has stimulated an increas-
ing interest to new functionalities of modified surface layers with absolutely new
properties. One of the significant changes observed in the physical properties of
ion-implanted polymers is an increasing absorbance in the course of the
M. Trzciński
T. S. Kavetskyy (*)
A. L. Stepanov
Kazan National Research Technological University, Kazan, Russian Federation

56 M. Trzciński et al.
implantation, to be interpreted as the signature on the formation of carbonaceous

clusters [2–4]. Recently, dose dependences of the optical band gap of boron-ion-
implanted layers Egopt,B and the number of carbon atoms in carbonaceous clusters
N in polymethylmethacrylate nanocomposite films formed by boron ion implanta-
tion have been systematically studied [3]. Three regions of ion doses have been
found: (1) 6.25 1014 – 3.13 1015, (2) 3.75 1015 – 6.25 1015, and
(3) 1.25 1016 – 2.5 1016 B+/cm2, showing thresholds in the estimated Egopt,B
and N values as a function of ion dose; consequently, an ion-induced structural
evolution towards the formation of carbon nanostructures within these thresholds
has been suggested [3]. In the present work, the optical band gap and carbon clusters
behavior as a function of ion dose are examined for the 40 keV boron, helium, and
xenon ion-implanted PMMA at ion doses of 3.13 1015–2.5 1016 ions/cm2. The
values of Egopt and N, respectively, are compared and analyzed. The effect of the ion
mass on the carbonization processes in PMMA nanocomposite films formed by
implantation of these ions as revealed from optical absorption measurements is
discussed.
7.2 Experimental
As substrates for ion implantation, optically transparent 1.2-mm-thick PMMA plates

were used. The B+, He+ and Xe+ implantation with an energy of 40 keV, ion doses
ranging from 6.25 1014 to 2.5 1016 ions/cm2, and an ion current density of
<2 μA/cm2 was performed under a pressure of ~105 Torr at room temperature
using the ILU-3 ion accelerator at the Kazan Physical-Technical Institute (KPTI,
Russia). Optical absorption spectra of the pristine PMMA and ion-implanted sam-
ples were measured in the wavelength range of 200–800 nm using an Evolution
220 UV-visible spectrophotometer at room temperature.
Figure 7.1 shows UV-visible absorption spectra and the optical absorption coeffi-
cient α(hν) of implanted samples at different doses and thicknesses d of the
implanted layer. The optical absorption coefficient for pristine and ion-implanted
samples was calculated from the absorption spectra using the relation [5, 6]:
α ¼ 2:303 A=d, ð7:1Þ
where A is the absorption and d the sample thickness. The thickness d of the
implanted layer was predicted by SRIM (stopping and range of ions in matter)
simulations [4]. Note, that the SRIM results were found to be in good agreement
7 Optical Band Gap and Carbon Clusters in PMMA Nanocomposite Films. . . 57
Fig. 7.1 UV-visible absorption spectra (left) and optical absorption coefficient α(hν) of implanted
layers (right) for B:PMMA, He:PMMA, and Xe:PMMA samples at different ion doses and
thicknesses d of the implanted layer as revealed by SRIM simulations [4]
with the experimentally obtained maximum penetration depth of B+ ions into

PMMA by slow positron beam spectroscopy [2]. The optical band gap energies
Egopt for pristine PMMA and the ion-implanted layers Egopt,ion were determined
using Tauc plots as shown in an earlier work [3]. From the optical band gap
58 M. Trzciński et al.
Table 7.1 Optical band gap energy Egopt,ion and number of carbon atoms in carbonaceous clusters
Nion for the implanted layers at different ion doses
Dose, ions/cm2 Egopt,B, eV Egopt,He, eV Egopt,Xe, eV NB NHe NXe
0 4.78 4.84 4.83 – – –
3.13 1015 4.39 4.52 4.81 ~61 ~58 ~50
6.25 1015 4.14 3.98 4.82 ~69 ~74 ~50
1.25 1016 3.90 2.28 4.82 ~77 ~225 ~50
2.50 1016 3.90 1.66 4.82 ~77 ~428 ~50
energy data one may calculate the number of carbon atoms in carbonaceous
clusters N (e.g., N ¼ 60 for buckminsterfullerene C60) using the formula [7, 8]:
Eg opt 34:3 N 1=2 : ð7:2Þ
The estimated Egopt,ion and Nion data for the implanted layers of this study are
collected in Table 7.1. The features of the dose dependence of the boron data have
been reported in [3]. In the present work, the effect of the ion mass on the
carbonization processes in PMMA nanocomposites formed by ion implantation as
revealed from optical absorption measurements was studied. It can clearly be seen
that the He+ implantation into PMMA leads to dramatic changes of Egopt,He and the N
He
in comparison with the B+ implantation, while the effect of Xe+ implantation into
PMMA is negligible. One of the reasons is the significant difference in the penetra-
tion depth for the 40 keV light He and heavy Xe ions of 880 and 90 nm, respectively,
according to SRIM simulations [4]. In order to clarify the results obtained, a
mechanism of ion-irradiation induced processes with low-energy light and heavy
ions should be studied in more detail. Slow positron beam spectroscopy should be
applied for this purpose to extract depth-selective information on defects in the
implanted samples.
7.4 Conclusion
The optical band gap and carbon clusters behavior as a function of the ion dose have
been examined for B:PMMA, He:PMMA, and Xe:PMMA nanocomposite films
formed by ion implantation at the same ion doses and energy. It was established
that He+ implantation into PMMA leads to dramatic changes of the optical band gap
and the number of carbon atoms in carbonaceous clusters NHe in comparison with B+
implantation, while the effect of Xe+ implantation is negligible.
Acknowledgments T.S. Kavetskyy acknowledges the Ministry of Education and Science of

Ukraine (project No. 0116U004737). A.L. Stepanov thanks for the financial support from the
Russian Foundation for Basic Research (project No. 15-48-02525).
7 Optical Band Gap and Carbon Clusters in PMMA Nanocomposite Films. . . 59
References
1. Fink D et al (1985) Distributions of light ions and foil destruction after irradiation of organic
polymers. J Appl Phys 58:668
2. Kavetskyy T et al (2014) Structural defects and positronium formation in 40 keV B+-implanted
polymethylmethacrylate. J Phys Chem B 118:4194
3. Trzcinski M, Kavetskyy T, Telbiz G, Stepanov AL (2017) Optical characterization of
nanocomposite polymer formed by ion implantation of boron. J Mater Sci Mater Electron
28:7115
4. Kavetskyy TS, Stepanov AL (2016) In: Monteiro WA (ed) Radiation effects in materials. InTech,
Rijeka, p 287
5. Arif S et al (2015) Influence of 400 keV carbon ion implantation on structural, optical and
electrical properties of PMMA. Nucl Instr Meth Phys Res B 358:236
6. Zidan HM, El-Khodary A, El-Sayed IA, El-Bohy HI (2010) Optical parameters and absorption
studies of UV-irradiated azo dye-doped PMMA films. J Appl Polym Sci 117:1416
7. Robertson J, O’Reilly EP (1987) Electronic and atomic structure of amorphous carbon. Phys Rev
B 35:2946
8. Fink D et al (1995) Carbonaceous clusters in irradiated polymers as revealed by UV-Vis
spectrometry. Radiat Eff Defects Solids 133:193
Part III
Structural and Optical Characterization
Chapter 8
Preparation and Characterization of SERS
Substrates of Different Morphology
I. Rigó, M. Veres, L. Himics, T. Váczi, and P. Fürjes
Abstract Gold coated patterned silicon substrates of different morphology, pattern

size and period were prepared by photolithography and subsequent etching. Their
performance in surface enhanced Raman scattering (SERS) was tested using an
organic model compound. The highest enhancement was obtained for an array of
inverse pyramids, followed by inverse hemispheres and rounded-edge inverse pyr-
amids. The SERS performance of the substrates was demonstrated with silicon-
carbide nanoparticles.
Keywords Surface enhanced Raman scattering · Raman spectroscopy · SERS

substrates · Photolitography · Etching
8.1 Introduction
Raman spectroscopy is a non-contact and relatively easy material characterization

technique requiring no sample preparation. The Raman scattering process is inher-
ently weak which prohibits its use for the investigation of low concentration
analytes. A number of techniques are known that can increase the Raman sensitivity
including the use of higher excitation energies, utilization of resonant Raman
scattering or surface enhanced Raman scattering (SERS) [1]. The latter promises
single molecule detection [2], and its degree of achievable sensitivity can reach
attomolar (10 18 M) concentrations, as has been observed in many cases [3, 4]. As a
spectroscopic tool SERS has the potential to combine the structural information of
Raman spectroscopy with the sensitivity of fluorescence. During SERS the
I. Rigó (*) · M. Veres · L. Himics · T. Váczi

Wigner Research Centre for Physics, Hungarian Academy of Sciences, Budapest, Hungary
P. Fürjes
Institute of Technical Physics and Materials Science, Centre for Energy Research, HAS,
Budapest, Hungary

64 I. Rigó et al.
scattering takes place in close vicinity of nanostructured metallic surfaces (nanopar-

ticle or some surfaces with a nanoscopic morphology), and the interaction of the
electromagnetic field of photons with the surface plasmons of the metal
nanoparticles results in a gain of the excitation and/or the Raman signal, that can
be several orders of magnitude [5]. The key factor for successful SERS is to find
appropriate SERS-active agents (nanoparticles or substrates) that will provide the
required efficiency for a given excitation wavelength.
In this work SERS active substrates of different size and morphology were
prepared by a lithographic technique from silicon with subsequent gold coating
and tested for their SERS enhancement performance using a highly dissolved
organic solution as a test material.
8.2 Experimental
Polished silicon wafers were used as substrates for the preparation of SERS active
surfaces. Arrays of inverse pyramids, spheres and rounded pyramids were formed
using photolithographic techniques. The silicon surface was coated with an appro-
priate photoresist, in which arrays of rectangular shapes were created with 1 1 and
2 2 μ unit size and 3 μ period. The samples were then etched with isotropic and
anisotropic agents as well as with their mixture, resulting in the formation of arrays
of hemispheres (isotropic etching), inverse pyramids (anisotropic etching) and
rounded inverse pyramids (mixed etching), respectively. Subsequently the substrates
were coated with a 40 nm thick sputtered layer of gold.
The morphology of the structures was characterized using scanning electron
microscopy (SEM) with a Jeol JSM-25 scanning electron microscope. SERS mea-
surements were carried out with a Renishaw 1000 micro-Raman spectrometer
attached to a Leica DM/LM microscope. A 785 nm diode laser served as excitation
source, which was focused into a spot with a diameter of 1 μ. A benzophenone
solution in isopropyl alcohol was used to test the SERS enhancement of the sub-
strates. The same solution was dripped onto each array and the intact silicon
substrate (serving as reference) as well. The Raman measurements were carried
out after the evaporation of the solvent. For another experiment, silicon carbide
nanoparticles were dried on the substrate surface from a water dispersion.
Figure 8.1 shows scanning electron microscopic images of the prepared gold coated
inverse hemispheres, rounded pyramids and pyramids of different size, respectively.
It can be seen that both the 1 and 2 μ unit size structures are of high uniformity. The
different speed of isotropic and anisotropic etchings results in structures of some-
what different size, especially for the 1 μ samples. The slowest etching was observed
8 Preparation and Characterization of SERS Substrates of Different Morphology 65
Fig. 8.1 Scanning electron microscopic images of gold coated arrays of inverse hemispheres
(P1 and P2), rounded pyramids (KP1 and KP2) and pyramids (K1 and K2) with 1 and 2 μ unit size
for the 1 μ unit size inverse pyramids, while on some areas of the silicon surface even
no structures were formed during the treatment process. It can be seen in Fig. 8.1 that
the largest inverse shapes were obtained with the combined application of the two
etchings.
The SERS spectra of the dried benzophenone solution recorded on the samples
are compared on Fig. 8.2. Very weak peaks were observed in the reference spectrum
and in the spectrum recorded on the KP2 substrate. More intense bands and
enhancement of the intensity were seen for all other samples, indicating the effects
of morphology and array unit size on the SERS performance of the gold coated
66 I. Rigó et al.
Fig. 8.2 Comparison of the

P2
SERS spectra recorded on
the different substrates with
RAMAN intensity
a dried solution of the same
concentration. The spectra KP1
are baseline corrected P1
K2
K1
KP2
REF.
500 1000 1500 2000

RAMAN shift, cm-1
Table 8.1 Relative SERS Sample Relative SERS enhancement

enhancement values of the
P1 1420
SERS substrates of different
morphology obtained from P2 760
Raman peak intensity ratios in KP1 740
the SERS and reference KP2 10
spectra K1 730
K2 2610
surfaces. Table 8.1 shows the SERS enhancements calculated from the intensity
ratios of the same peak in the SERS and reference spectra. It can be seen that the
values range between 10 and 2600, and are much lower than the enhancements
reported in the literature. It should be noted, however, that the values in Table does
not reflect the real SERS enhancement. The SERS phenomenon occurs only in the
close vicinity of a metallic surface; however, the samples obtained by drying the
solution constitute not a single molecular layer, but a relatively thick film of material.
For this reason there is a significant non-SERS contribution to the measured spectra
from the part of the samples out of the SERS enhancement region, which is present
in both the SERS and the reference spectra and influences the intensity ratios and
their comparison. Therefore, the SERS enhancements provided in Table 8.1 can be
used only for comparative analysis of the SERS performance of the different sub-
strates. From the six examined samples the K2 substrate has the highest relative
SERS enhancement of 2610, followed by the P1 with an intensity around half of that
of the K2 substrate. The K1, P2 and KP1 surfaces have similar performances, while
only minimal SERS enhancement was observed forthe KP2 sample.The amplifica-
tion of the SERS signal is determined by the plasmonic properties (plasmon reso-
nance wavelength) of the metallic nanostructure and its relation to the wavelengths
of Raman excitation and Raman bands. So the values describing the relative
performance of the SERS substrates are true only for 785 nm excitation.
The SERS enhancement of the K2 substrate showing the highest efficiency was
tested with silicon-carbide nanoparticles prepared from silicon and graphite powder
8 Preparation and Characterization of SERS Substrates of Different Morphology 67
Fig. 8.3 SERS spectra

recorded at different points
RAMAN intensity (a.u.)

of a silicon-carbide
nanocrystal sample dried on
the K2 sample surface from
a water dispersion
600 800 1000 1200 1400 1600 1800 2000

RAMAN shift (cm-1)
precursors using the reactive bonding method [6]. The Raman peaks of this material
were overlapped by the strong photoluminescence background during normal
Raman measurements with 785 nm excitation. However, it was possible to detect
Raman bands after drying the nanoparticles onto the SERS substrate (Fig. 8.3).
Obviously, the interaction of the electromagnetic field of the photons with the
surface plasmons of the nanostructured metal substrate can enhance the
photoluminescence, as well. However, this effect is strongly distance-dependent
and the photoluminescence is quenched near the metal surface [7], where SERS
has the highest efficiency.
SERS spectra recorded at different points of the sample contain several relatively
strong peaks. One group of bands (at 666, 820, 848, 923 and 976 cm 1) can be
assigned to SiC vibrations and indicate the presence of several different polytypes in
the sample [8, 9]. Bands in the 1000–1650 cm 1 region (at 1050, 1085, 1115, 1260,
1383, 1460 and 1615 cm 1) are related to different carbon-carbon vibrations, clearly
showing the presence of carbon impurities in the structure. However, while the
sample was prepared from a graphite precursor, only the 1615 cm 1 peak appearing
in one spectrum resembles the Raman band of nanocrystalline graphite [10]. Being
the most probable source of carbon impurities, Raman spectra show that graphite
transformed into some different carbon structures during the preparation process.
8.4 Conclusions
The performance of gold coated patterned silicon surfaces of different morphology

and size as substrates for surface enhanced Raman scattering was investi-
gated. Among gold coated arrays of inverse pyramids, spheres and rounded pyra-
mids of 1 and 2 μ unit size and 3 μ period the 2 μ sized inverse pyramids showed the
highest SERS amplification with 785 nm excitation. The performance of this
substrate was demonstrated on silicon carbide nanoparticles.
68 I. Rigó et al.
Acknowledgments This work was supported by National Research, Development and Innovation
Fund of Hungary with the NVKP_16-1-2016-0043 grant and the VEKOP-2.3.2-16-2016-00011
grant. Miklós Veres is grateful for the support of the János Bolyai Research Scholarship of the
Hungarian Academy of Sciences.
References
1. Ryder AG (2005) Surface enhanced Raman scattering for narcotic detection and applications to
chemical biology. Curr Opin Chem Biol 9:489–493
2. Le Ru EC, Meyer M, Etchegoin PG (2006) Proof of single-molecule sensitivity in surface
enhanced Raman scattering (SERS) by means of a two-analyte technique. J Phys Chem B
110:1944–1948
3. Etchegoin P, Maher RC, Cohen LF, Hartigan H et al (2003) New limits in ultrasensitive trace
detection by surface enhanced Raman scattering (SERS). Chem Phys Lett 375:84–90
4. Futamata M, Maruyama Y, Ishikawa M (2004) Metal nanostructures with singlemolecule
sensitivity in surface enhanced Raman scattering. Vib Spectrosc 35:121–129
5. Campion A, Kambhampati P (1998) Surface-enhanced Raman scattering. Chem Soc Rev
27:241–250
6. Beke D, Szekrényes Z, Balogh I, Veres M, Fazakas É, Varga LK, Kamarás K, Czigány Z, Gali
A (2011) Silicon carbide quantum dots for bioimaging. Appl Phys Lett 99:213108
7. Acuna GP, Bucher M, Stein IH, Steinhauer C, Kuzyk A, Holzmeister P, Schreiber R, Moroz A,
Stefani FD, Liedl T, Simmel FC, Tinnefeld P (2012) Distance dependence of single-fluorophore
quenching by gold nanoparticles studied on DNA origami. ACS Nano 6:3189–3195
8. Feldman DW, Parker JH Jr Choyke WJ, Patrick L, Phonon dispersion curves by Raman
scattering in SiC, polytypes 3C, 4H, 6H, 15R, and 21R. Phys Rev 173:787 (1968)
9. Wei G, Qin W, Wang G, Sun J, Lin J, Kim R, Zhang D, Zheng K (2008) The synthesis and
ultraviolet photoluminescence of 6H–SiC nanowires by microwave method. J Phys D Appl
Phys 41:235102
10. Ferrari AC, Robertson J (2000) Interpretation of Raman spectra of disordered and amorphous
carbon. Phys Rev B 61:14095
Chapter 9
Synthesis of UV Sensitive Rare Earth Doped
Materials
Irena Kostova and Dan Tonchev
Abstract In this work we report on the synthesis of photoluminescent inorganic

crystalline materials by a hydrothermal process. The synthesis of rare earth doped
and co-doped strontium/barium aluminates was performed in a muffle furnace in air
atmosphere. The prepared powders were excited with an ultraviolet (UV) source and
their emission spectra measured. The PL results show slight fluorescence and strong
visible green phosphorescence under UV light. We also measured the thermal
properties by differential scanning calorimetry (DSC). The structures of synthesized
RE doped materials were studied by XRD analysis. The basic properties of these
materials show potential for different applications. We focused on protection of
security documents. For this reason, we performed additional experiments. We
blended fine grinded phosphorescent powders into different polymer composites
and made successfully thin films from them. The composites were prepared by
polyethylene, polymethyl methacrylate and polystyrene mixed with synthesized
inorganic additives.
Keywords Rare earth · Strontium aluminates · Phosphorescence · Composite

materials
9.1 Introduction
Rare earth (RE) doped materials (crystalline or glassy) are widely used in various
fields. Strontium aluminates are suitable host materials for RE ions such as Eu, Dy
and Tb [1–3]. Strontium aluminate phosphors produce yellow-green, blue-green and
I. Kostova (*)
Departments of Chemical Technology, Plovdiv University “Paisii Hilendarski”, Plovdiv,
Bulgaria
D. Tonchev
University of Saskatchewan, Saskatoon, SK, Canada
University of Plovdiv “Paisij Hilendarski”, Plovdiv, Bulgaria

70 I. Kostova and D. Tonchev
blue hues for excitation wavelengths from 200 to 450 nm, with green emission at
520 nm, blue-green at 505 nm, and blue at 490 nm, depending on the
lanthanide co-doping. The co-doping in this material is usually with Dy and Nd
ions [4, 5]. Due to their luminous properties, easy preparation and chemical dura-
bility, strontium aluminates are excellent additives to different polymers. This is very
important when preparing composite materials. Mishra et al. [6] reported phosphor-
based polymer composites with strontium aluminates phosphors (SrAl2O4: Eu, Dy
and Sr4Al14O25: Eu, Dy) in different organic matrices.
In this article, we report on an experimental study of crystalline powders
co-doped with different lanthanide ions, aiming at correlating their host lattice
structure and chemical composition to the luminescence features. In addition, we
have prepared polymer – inorganic composite materials. For this purpose, phosphor
samples were characterized by X-ray diffraction (XRD), thermal analysis, and
photoluminescence (PL) spectroscopy. This investigation on the optical characteri-
zation of luminous crystalline materials doped with lanthanide ions gives informa-
tion about possible applications such as light-emitting devices, luminescent
pigments, ceramics and composites.
9.2 Materials and Methods

9.2.1 Synthesis of RE Doped Powders
The following raw reagents: SrCO3, SrF2, Al2(SO4)318H2O, CO(NH2)2, Sm2O3,

TbF3, Eu(SO4)38H2O, SmF3 were purchased from Alfa Aesar. The hydrothermal
synthesis was performed by a solid-state reaction from solution and calcined in a
muffle furnace at 500 C. The product was cooled to room temperature and then
removed from the crucible and analyzed.
The resulting crystal powders were prepared by the following chemical
equations:
2AlðOHÞ3ðsÞ ! Al2 O3ðsÞ þ 3H2 OðgÞ
SrCO3ðsÞ ! SrOðsÞ þ CO2ðgÞ
xSrO þ yAl2 O3 ! Srx Al2∗y O3∗yþx
9.2.2 Characterization
DSC was performed with a Thermal Analysis TA Instrument DSC Q100 with an
attached fast air cooling system (FACS) at heating rates of 2 K/min, a period of 60 s
and an amplitude 1.
9 Synthesis of UV Sensitive Rare Earth Doped Materials 71
Table 9.1 Concentration of Phosphor Concentration of RE elements, %

RE elements in the phosphors
Sm Tb Eu
SAO:Sm 0.4
SAO:Tb 0.4
SAO:Eu 0.4
SAO:EuTb 0.2 0.4
SAO:TbSm 0.2 0.4
The aimed stoichiometric compounds were synthesized as follow-
ing: SrAl12O19:Sm (1:6), SrAl4O7:Tb (1:2), Sr4Al14O25:Eu (4:7),
Sr3Al2O6:Sm (3:1), SrAl2O4:Eu (1:1)
6000 Sr4Al14O25
SrAl2O4
5000
4000
3000
2000
1000
0
10 20 30 40 50 60 70 80
Fig. 9.1 XRD analysis of the stoichiometric sample SrAl12O19:Sm (1:6)
Photoluminescence analysis was performed by a SpectroVis Plus spectropho-

tometer in the range 250–1100 nm with different excitation sources in the UV-VIS
range.
The X-ray diffraction measurements were performed in the Institute of General
and Inorganic Chemistry, Bulgarian Academy of Science (BAS). Although the
synthesis aimed at obtaining a clearly defined stoichiometric compounds, the XRD
analysis indicated the presence of different phases.
In Table 9.1 the compositions of the phosphors SrxAl2*yO3*y + x (SAO) doped with
different RE elements are given.
9.3.1 XRD Analysis
The XRD analysis indicates the presence of different phases of polycrystalline

structures as shown on the roentgenograms below (Figs. 9.1 and 9.2).
Al2O3;
6000
Sr4Al14O25
5000 SrAl2O4
4000 SrAl12O19
3000
2000
1000
0
10 20 30 40 50 60 70 80
Fig. 9.2 XRD analysis of the stoichiometric sample Sr4Al14O25:Eu (4:7)
According to the differences of the phase composition of these samples, in their

XRD patterns we can observe a mixture of following crystalline phases: Al2O3;
Sr4Al14O25, SrAl2O4 and SrAl12O19.
9.3.2 Thermal (DSC) Analysis
The themal analysis results are shown in Fig. 9.3a–d. The thermograms are
confirming the results of the XRD analysis that the structure contains two phases –
an amorphous and a polycrystalline one with a low melting point Tm around
120–150 C. This temperature is acceptable for a practical use taking into account
that these materials are going to be dispersed into polymers and desposited as films.
It seems that the amorphous phases of the obtained materials crystallize around
100 C; this is more clear from the thermogram d, However the other materials also
give a hint on this crystallization temperature Tc in the range from 100 to 110 C.
There is also a hint for a glass transition temperature Tg of around 55–75 C but this
is obscured by probably non-reacted sourse materials with low melting points.
9.3.3 Photoluminescence Analysis
Under irradiation with different light sources (UV, white, visible) the obtained
powders exhibited visually detectable phosphorescence for a duration of 4–5 s. It
is possible also to observe a weak fluorescence (not shown). The luminescent
analysis was performed by different LED and laser light sources (excitation wave-
lengths λ ¼ 295, 315, 325, 340, 370, 395 and 405 nm). The resulting spectra are,
given in Figs. 9.4, 9.5, 9.6, and 9.7.
Looking at these spectra it is possible to observe ions peaks typical for rare-earths
(RE). This means that RE elements are successfully doped into the synthesized
luminescent crystals. All materials investigated by photoluminescent
Fig. 9.3 (a–d) Thermograms of phosphours doped with different rare earth elements
Fig. 9.3 (continued)

Fig. 9.4 Luminescent spectra of sample Sr4Al14O25:Eu
Fig. 9.5 Luminescent spectra of sample Sr4Al4O7: Sm
(PL) spectroscopy showed signals in the wavelength range of 450–600 nm. The
most intensive emission was observed when the 405 nm excitation source was used.
At this wavelength the phosphorescence of the synthesized powders is very inten-
sive. This result shows that it is possible to observe both luminescent effects
(fluorescence and phosphorescence) using one excitation source.
In Fig. 9.7 that on joint doping with two materials it is possible to observe the
traces of both doping RE materials. This means that rare earth ions have successfully
doped into the host materials. For all examined compositions emission takes place in
Fig. 9.6 Luminescent spectra of sample SAO: Tb
Fig. 9.7 Luminescent spectra of sample SAO: Eu, Tb
the range 450–600 nm. One can see again that the emission is most intense when the
pumping source works with a wavelength of 405 nm. At this wavelength the
phosphorescence of the powders is strong, which shows that using a single source
it is possible to induce both effects (fluorescence and phosphorescence). In the
co-doped materials bands of both dopant elements are observed.
Fig. 9.8 Procedure of luminescent polymer films preparation
9.3.4 Luminescent Polymer Thin Films
Using the synthesized phosphors polymer films with defined polymer concentration
were prepared. The procedure was performed according to the scheme given in
Fig. 9.8.
Mixtures of polymers and luminescent powders were stirred using an ultrasonic
bath. The resulting dispersions were cast on a glass or polymer (PET) substrate and
left to evaporate the solvent for a day at room temperature. The whole procedure is
given in Fig. 9.8. It has been found that the fillers used are evenly distributed in the
polymer (when the concentration is high).
9.4 Conclusions
Stoichiometric strontium aluminates produced by hydrothermal procedure were

characterized by XRD, thermal and photoluminescent methods. The roentgeno-
grams show the presence of different phases in the powders; low values of Tg and
Tc are seen in the thermograms. We explain this with the synthesis conditions and an
incomplete reaction of the starting components. This actually has a positive effect on
the luminescent properties of the resulting materials compared to the commercial
ones. Namely, we observe a strong phosphorescence with a short time afterglow and
a low fluorescence in the visible spectrum. This combination of both effects is
important for their application for valuable documents protection. In addition, we
have prepared polymer films these synthesized materials. We observed good disper-
sion of the particles in the polymer matrix and the dual (photo-and phosphorescent)
luminescent properties. Moreover, some of the resulting composites are flexible and
with good adhesion to the substrates. Therefore, our studies have shown the possi-
bility of new applications of strontium aluminates as luminophore additives for
polymers and paper substrates.
References
1. Dutczak D, Jüstel T, Ronda C, Meijerink A (2015) Eu(2+) luminescence in strontium aluminates.

Phys Chem Chem Phys 17(23):15236–15249
2. Kim D, Kim H, Kim C (2016) Effect of composition and impurities on the phosphorescence of
green-emitting alkaline earth aluminate phosphor. PLoS One 11(1):e0145434
3. Song H, Chen D (2007) Combustion synthesis and luminescence properties of SrAl2O4:Eu2+, Dy
3+
, Tb3+ phosphor. Luminescence 22(6):554–558
4. Teng Y, Zhou J, Ma Z, Smedskjaer MM, Qiu J (2011) Persistent near infrared phosphorescence
from rare earth ions co-doped strontium aluminate phosphors nanostructured materials, carbon
nanotubes, and fullerenes. J Electrochem Soc 158(2):K17–K19
5. Sun W, Chen Y, Wu L, Jiang Y (2013) Phase composition and luminescent properties of
strontium aluminate long persistence phosphor synthesized by combustion synthesis method
with different Sr/Al ratios. Rare Metals 32(4):414–419
6. Mishra K, Revaprasadu N, Hillie K, Steyn W, Coetsee E, Swart H (2009) Strontium aluminate/
polymer composites: morphology, luminescent properties, and durability. J Appl Polym Sci 112
(6):3347–3354
Chapter 10
Characterization of Nickel-Cobaltite Spinel
Prepared by Different Methods
D. Nicheva, V. Boev, P. Petkov, G. Avdeev, and T. Petkova
Abstract NiCo2O4-spinel has been prepared by three different techniques: The Pechini
method, a hydrothermal method and a precipitation reaction. The obtained samples have
been examined by X-ray diffraction (XRD), differential thermal analysis (DTA) and
scanning electron microscopy (SEM). The results reveal that materials prepared by the
Pechini method possess two phases (Co3O4 and NiO), those obtained by the hydrother-
mal method have phases of NixCo3-xO4. Single-phase NiCo2O4 material is obtained
only by the precipitation reaction. The obtained NiCo2O4 material is nanosized,
exhibiting thermal stability up to 700 C, where thermal decomposition of NiCo2O4
to Co3O4 and NiO takes place. In the region of thermal stability, a linear thermal
expansion of the elementary cell has been observed.
Keywords NiCo2O4 · Spinels
10.1 Introduction
During the last decade oxide spinels of transition metals are subject of fundamental
and applied research due to the expected encouraging properties. Different
approaches are reported for the synthesis of spinel phases like thermal
D. Nicheva (*)
Institute of Electrochemistry and Energy Systems Acad.E.Budevski, Bulgarian Academy of
Sciences, Sofia, Bulgaria
University of Chemical Technology and Metallurgy, Sofia, Bulgaria
V. Boev · T. Petkova
P. Petkov
G. Avdeev
Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria

80 D. Nicheva et al.
decomposition of oxalate precursors [1] and hydrothermal [2–4] and sol-gel methods
[5]. The properties of these oxides are strongly determined by the oxidation states of
the constituent cations and by the distribution of the octahedral and tetrahedral sites
in the spinel structure. The synthesis method can influence both the oxidation state of
the cations and the cation distribution. A study of the influence of the preparation
method on the material behavior is thus of great importance. Nickel cobaltite,
NiCo2O4, is one of the promising metal oxides in the family of cobaltite materials
with the spinel structure AB2O4, where A¼Ni, B¼Co. Generally Ni ions occupy the
octahedral sites in the NiCo2O4 structure; the Co ions are distributed over both
octahedral and tetrahedral sites. The advantages of these oxides are associated with
their activity, availability, low cost, thermodynamic stability, low electrical resis-
tance and environmental friendship [6–8].
The goal of our work was to study different approaches aiming to achieve single-
phase NiCo2O4. We present results on the synthesis of NiCo2O4 by three different
different methods: the Pechini method, a hydrothermal method and precipitation
reaction. We report the thermal behavior and particle size of the obtained materials.
The crystal structure and size distribution can be controlled by adjusting the synthe-
sis route and the molar ratio of the materials.
10.2 Experimental
10.2.1 Preparation
Pechini method: Analytical grade Co(NO3)26H2O and Ni(NO3)26H2O with the

stoichiometric ratio of 2:1 (Co/Ni) were dissolved in ethylene glycol and citric acid
under constant stirring and heated. The obtained mixture was vacuum dried for 2 h.
Finally the obtained product was slowly heated in air up to 350 C.
Hydrothermal synthesis: Nickel nitrate and cobalt nitrate were dissolved in
distilled water under continuously stirring to obtain a homogenous solution. There-
after, aqueous NaOH solution was added dropwise to the solution to reach pH ¼ 11.
The suspension was then transferred in an autoclave and heated at 180 C for 5 h.
The autoclave was naturally cooled to ambient temperature after the process. The
solution was washed in 0.1N HNO3 followed by rinsing in distilled water and
ethanol. The synthesized product was dried at 100 C for 2 h and calcinated at
500 C for 5 h.
Precipitation reaction: Starting materials in precipitation reaction synthesis were
Co(NO3)26H2O and Ni(NO3)26H2O; they were dissolved in NH4OH under con-
stant stirring. The resulting precipitate was filtered and then dried for 2 h. The
obtained product was slowly heated in air to 350 C. The reactions that take place
during the synthesis are:
10 Characterization of Nickel-Cobaltite Spinel Prepared by Different Methods 81
2 NH4 OH þ CoðNO3 Þ2 ! 2 NH4 NO3 þ CoðOHÞ2

2 NH4 OH þ NiðNO3 Þ2 ! 2 NH4 NO3 þ NiðOHÞ2
2 NiðOHÞ2 þ 4 CoðOHÞ2 þ O2 ! 2 NiCo2 O4 þ 6 H2 O
XRD analyses were performed by using a X-ray diffractometer model Philips APD-15.
The data were collected at ambient temperature with a constant step of 0.02 s1 in the
range 2θ ¼ 20–80 at the wavelength λ ¼ 1.54178 Å using a СuКα tube. The high
temperature behavior of the NiCo2O4 sample were examined using a PANalytical –
Empyrean diffractometer with Cu Kα radiation. The instrument is equipped with a
Anton Paar HTK 16N camera. A HighScore Plus software was used to analyze the
X-ray diffraction data. The sample was heated with a rate of 10 /min in the temperature
range 25–900 С. The study was conducted in a platinum crucible.
Thermal analyses of the samples were carried out with a DTA/TG Setaram
Labsys Evo 1600 instrument in air atmosphere. The temperature range of investiga-
tion was between 30 and 900 С using a heating rate of 10 К/min and flow rate of
20 ml/min. The morphology of the material was determined using scanning electron
microscopy (SEM JEOL, JEM-200CX).
10.3.1 X-Ray Diffraction Analysis
In the process of identifying NiCo2O4 we two of the most widely used ICDD (PDF #
731702) and ICSD (24211) databases. The phases existing in the databases were
compared to the cell parameter values of the experimentally obtained phases. Figure 10.1
presents the diffractograms of the samples obtained by the three methods. Using the
Pechini method (Fig. 10.1a) a multi-phase product, i.e. a mixture of Co3O4 and NiO, is
obtained. The amount of Co3O4 is 69 wt%, that of NiO of wt. 31%, determined by the
Rietveld method [9]. The results show that there is no nickel incorporated into the Co3O4
lattice, the oxides exist individually not reacting to each other.
Hydrothermal samples consist of two phases: NixCo3-xO4 spinel with an amount
of 98 wt.% and NiO with 2 wt.% (Fig. 10.1b). The difference with the previously
described synthesis is the inclusion of more nickel atoms in the spinel crystal lattice.
The general chemical formula of the obtained spinel phase is Ni0.93Co2O4.
Co3O4
Fig. 10.1 XRD
Co3O4
Co3O4
diffractograms (a) Pechini Pechini
Co3O4
Co3O4
NiO
method, (b) Hydrothermal a
method, (c) Precitipation
reaction
NixCo3-xO4
NixCo3-xO4
NixCo3-xO4
NixCo3-xO4
NixCo3-xO4
Intensity, a.u.
Hydrothermal
b
NiO
NiCo2O4
NiCo2O4
NiCo2O4
NiCo2O4
NiCo2O4
Precitipation
c
15 20 25 30 35 40 45 50 55 60 65
2Q
A single-phase product is achieved only by means of the precipitation reaction

(Fig. 10.1c). The diffractogram does not show peaks of impurities; the NiCo2O4
obtained is well defined spinel phase with an average crystallite size between
150 and 200 nm, values obtained from the diffractogram. The profile fit of the
experimental diffractogram shows that the NiCo2O4 obtained by the precipitation
reaction has a slightly smaller elementary cell parameter (a ¼ 8.101(1)) compared to
that given in the databases (a ¼ 8.1140). The chemical analysis confirms that the
metal ions are in a stoichiometric ratio, for this reason the difference in the cell
parameter values can only be explained by the presence of oxygen defects.
The thermal behavior of the samples was investigated simultaneously with DTA
and high temperature X-ray analysis. The results from the thermal analysis of the
samples obtained by the Pechini and hydrothermal methods are similar: a low weight
loss at low temperatures and an endothermic peak above 860 C due to the decom-
position the material. In the TG curve of the NiCo2O4 obtained by the precipitation
reaction a weight loss of 0.6% was observed in the temperature range between
40 and 150 C due to the evaporation of adsorbed water. The next weight loss of
approximately 5.6% in the 833–883 C temperature range is accompanied by an
endothermic peak at 866 C which effects serve as an indication of the decomposi-
tion of NiCo2O4 (Fig. 10.2).
The high temperature XRD (HTXRD) structural analysis made on the sample
obtained by the precipitation reaction confirms the DTA data. The NiCo2O4 com-
pound remains stable up to 700 C. Above this temperature changes in the diffrac-
tion picture become visible, and at temperature of 833 C first diffractive peaks of
NiO appear. As the temperature increases the NiO peaks continue to grow
(Fig. 10.3). In the temperature range 25–700 C the NiCo2O4 cell parameter
shows a linear grow as shown in Fig. 10.4.
PECHINI method
102 TG 0.2
100
0.1
98
DTA 0.0
96
94 -0.1
92
-0.2
90
exo
HYDROTHERMAL method
102 TG 4
100 2
Heat flow, mV/mg

Weight loss, %
98 0
96 -2
DTA
94
-4
92
-6
90
PRECIPITATION method
102 0.2
TG
100
0.1
98
DTA 0.0
96
94 -0.1
92
-0.2
90
0 200 400 600 800 1000
o
Temperature, C
Fig. 10.2 TDA/Tg curves of materials obtained from the three methods
10.3.2 Scanning Electron Microscopy
The morphology and particles size distribution of nickel-cobalt oxides studied by

SEM is shown in Fig. 10.5. The sample prepared by the Pechini method possesses a
microstructure composed by spherical particles of several microns distributed among
smaller nanosized particles (Fig. 10.5a).
The material prepared by the hydrothermal method is a mixture of spherical
particles with size of 100 nm and others much bigger of 1–2 μ size (Fig. 10.5b).
SEM images of NiCo2O4 synthesized by the precipitation method demonstrate
nanosized homogeneously distributed particles equal in size and not larger than
200 nm (Fig. 10.5c).
Pt Pt Pt Pt
NiO NiO
o
900 C
o
858 C
o
Intensity, a. u.
833 C
o
700 C
o
500 C
o
400 C
o
300 C
o
200 C
o
100 C
o
25 C
20 40 60 80
2Q, degree
Fig. 10.3 HTXRD spectra of NiCo2O4 obtained by the precipitation reaction. Pt is platinum from
the crrucible
8,20
8,15
Cell parametar
8,10
8,05
8,00
0 100 200 300 400 500 600 700
Temperature
Fig. 10.4 Cell parameter of NiCo2O4 as a function of the temperature

Fig. 10.5 SEM images of materials prepared by different methods. (a) Pechini method. (b)
Hydrothermal method. (c) Precipitation reaction
10.4 Conclusion
The comparison of three approaches for the synthesis of NiCo2O4 shows that the Pechini
method and the hydrothermal method are not suited to obtain pure single-phase NiCo2O4.
Using the precipitation reaction we achieved nanosized single-phase NiCo2O4 thermally
stable up to 700 C. In the temperature range from room temperature up to 700 C the cell
parameter increases regularly revealing that no phase changes occur. Thermal decompo-
sition of NiCo2O4 starts above 700 C.
Acknowledgments PP is deeply grateful to the Bulgarian Scientific Fund for the financial support
under project DUNK-01/3/2009.
References
1. Chinh VD, Trung NQ (2015) Preparation of gold-silver alloy nanoparticles supported on

NiCo2O4 spinel oxides for the treatment of CO in atmosphere. J Nanosci Nanotechnol
15:4403–4408
2. Durrani SK, Asif A, Rehman U, Hussain N, Naveed S (2011) Hydrothermal synthesis and
characterization of nanosized zinc cobaltite spinel ceramic. J Pak Mater Soc 5(1):5–11
3. Singh JP, Singh RN (2000) New active spinel-type MxCo3-xO4 films for electro-catalysis of
oxygen evolution. J New Mater Electrochem Syst 3:131–139
4. Ding R, Qi L, Jia M, Wang H (2013) Hydrothermal and soft-templating synthesis of mesoporous
NiCo2O4 nanomaterials for high-performance electrochemical. Appl Electrochem 43:903–910.
https://doi.org/10.1007/s10800-013-0580-z
5. Guene M, Diagne A, Fall M (2007) Preparation of nickel-cobalt spinel oxides NixCo3-xO4.
Comparison of two physical properties stemming from four different preparation methods and
using carbon paste electrode. Bull Chem Soc Ethiop 21(2):255–262
6. Tjarayil NJ, Raveendran R, Varghese A, Chithra PG (2008) Optical, electrical and structural
studies of nickel-cobalt oxide nanoparticles. Indian J Eng Mater Sci 15:489–496
7. Chang S, Zainal Z, Bantan K, Yusof NA, Wan Yusoff WM, Prabaharan SRS (2012) Surface
morphology and crystallinity of metal oxides in nickel-cobalt binary system. Sains Malays
41(4):465–470
8. Hamdani M, Singh RN, Chartier P (2010) Co3O4 and Co- based spinel oxides bifunctional
oxygen electrodes. Int J Electrochem Sci 5:556–577
9. Rietveld HM (1967) American crystallographic assosiation single-crystal intensity project report.
Acta Crystallogr 22:151–152
Chapter 11
Structure and Thermal Behaviour
of Lithium Sodium Sulphate
Z. Slavkova, O. Kostadinova, G. Avdeev, and T. Petkova
Abstract Lithium sodium sulphate (LNS) has been synthesised by two methods:
mechanical ball milling and melt quenching. The obtained materials have been
studied by means of X-ray diffraction, scanning electron microscopy (SEM),
Infrared spectroscopy and differential scanning calorimetry. The influence of the
synthesis method on the structure and behaviour of the materials will be discussed.
Keywords Lithium sodium sulphate · Nanocomposites · Mechanical ball milling ·

Melt quenching · Infrared absorption spectroscopy · Thermal characterisation
11.1 Introduction
From the protection of our domestic media over the environment, to the control of
industrial processes, gas detection and monitoring is a necessity. Among the widely
used sensors are those based on solid electrolytes [1, 2]. Reliability and performance
of sensor devices are in direct correlation with the used materials and their properties
and behaviour down to the molecular level. In this sense, the study of the physical
and chemical behaviour of materials in the light of the structural organization is a
significant point.
Lithium sodium sulphate (LNS) has been intensively studied both at room and at
higher temperatures [3–5]. It is known that LNS undergoes a first order phase
transition from the beta to the alpha phase at approximately 500–515 C and that
Z. Slavkova (*) · O. Kostadinova · T. Petkova

“Solid State Electrolytes” Section, Institute of Electrochemistry and Energy Systems – BAS,
Sofia, Bulgaria
G. Avdeev

88 Z. Slavkova et al.
the α-phase exhibits a ionic conductivity of about 10 1 S/cm [5, 6]. Some electro-
chemical experiments with LNS as an electrolyte have been performed [7, 8].
In this work two synthesis methods – melt quenching and mechanical ball
milling- are applied to obtain LNS. The goal is to define the material structure and
dependence of the characteristics on the preparation method.
11.2 Experimental
Equimolar ratios of Li2SO4 (Sigma-Aldrich) and Na2SO4 (Alfa Aesar) were used for
both syntheses. A mechanochemically prepared LNS sample was synthesised by
means of a MicroNano Tool’s PBM-2 planetary ball mill. The precursors were
milled for 72 h with a planetary disk velocity of 580 rpm.
The melt-quenched sample was obtained in a Dentamatic 6000-M furnace. The
initial materials were placed in a platinum crucible and heated at 800 C for 2 h.
Thereafter, the melt was rapidly quenched between two pre-cooled copper plates.
X-ray analysis of both samples was accomplished by a Panalytical multifunction
X-ray diffractometer (model: Empyrean), equipped with an Anton Paar accessory for
high temperatures (APHTK-16N) and a 3D PIXcel detector. FT-Infrared absorption
(FTIR) spectra were measured in the middle infrared region (500–4000 cm 1) with
the aid of a diamond ATR-equipped Bruker Tensor 27 FT spectrometer. The spectra
were collected with 64 scans at a resolution of 2 cm 1, referring to air as background
spectrum.
Differential scanning calorimetric investigations (DSC) were conducted by a
Netzsch DSC 404 cell in argon atmosphere in Al2O3 crucibles and in the temperature
range 50–750 C. The heating rate was 10 C/min.
Scanning electron microscopy/EDS measurements were performed with a Bruker
EDS system coupled to a Vega3 TESCAN SEM microscope. Before measurement
the samples were covered with a conductive carbon layer deposited by sputtering.
The XRD analysis reveals that at the synthesis conditions the samples consist of
lithium sodium sulphate and small amounts of not completely reacted Na2SO4
(Fig. 11.1). No visible differences in the diffractograms are observed. The mechan-
ically ball milled sample (MBM) is composed of 91, 6 wt. % β-LNS and 8,4 wt. %
Na2SO4 (Fig. 11.1a), whereas the quenched sample (MQ) possesses a β-LNS content
of 97 wt. % and 3 wt. % of Na2SO4 (Fig. 11.1b). The size of the β-LNS powder
crystallites varies between 70 and 81 nm; the size of the Na2SO4 grain is about
160 nm. Calculations for the bulk material revealed significantly larger β-LNS
crystallites (average 129 nm) and the same size for sodium sulphate. Obviously,
11 Structure and Thermal Behaviour of Lithium Sodium Sulphate 89
* *– b–LNS
o - Na2SO4
Intensity [arbitrary units]
* *
**
MQ
* * *
o o
* * **
o
* o* o ** oo
o
MBM
10 20 30 40 50
2Q [degrees]
Fig. 11.1 XRD of the MBM and MQ samples
mechanical ball milling is a good approach to obtain materials with fine particles and
small crystallites, but on the other hand, melt quenching allows preparation of a
sample in a shorter period of time.
The LiNaSO4 structure has been investigated by several authors [4, 5, 9–13];
however, there are still unclear issues regarding the structural organization and its
influence on the material behaviour. Using the X-ray synchrotron technique, Freiheit
et al. [10] proposed the idea that this salt is composed of SO4 and LiO4 tetrahedra
that form a channel with strong covalent Li-O-S bond, while the Na ions are
positioned inside the channels. Above the phase transition temperature from β to α
phase the sulphate ions rotate and the cations move through the lattice.
Free sulphate ions belong to the Td point group and have nine vibration modes:
the non-degenerate IR-inactive ν1 mode, the triply degenerate IR-active ν3 and ν4
modes, and the doubly degenerate IR-inactive ν2 mode. In sulphate salts the sulphate
anions are perturbed by crystal field effects and by covalent bonding to the cation
through one or more oxygen atoms. Then, the symmetry changes from Td to C3v. As
an effect of the changed coordination of the SO4 ion, the IR-forbidden vibrations ν1
(3A1) and ν2 (6E) are permitted, the degenerate vibrations ν3 (3A1+6E) and ν4 (3A1
+6E) are split, and the fundamental frequencies are shifted. The shifts are determined
by the polarising power of the cations, which in turn are determined by the cationic
radius and charge [13]. Regarding the cationic vibrations, 12 phonon modes (3A1
+3A2+6E) (the so-called external modes) are expected, but and only nine of them
(3A1+6E) are optically active. These external modes are located in the far-IR region
[4, 11]. In most of the structural studies using the IR technique, the authors observe
SO4n4
MQ; MBM SO4n3
0,4
Absorbance units
SO4n1
SO4n2
Li-S-O
0,2
0,0
500 600 700 800 900 1000 1100 1200 1300
-1
Wavenumber, cm
Fig. 11.2 Infrared absorption spectra of a LNS bulk sample (MQ) and a LNS powder (MBM)
only few of the predicted modes. For instance, Sahaya et al. [12] observed two of the
predicted three ν1 modes of the sulphate ion and only three of the expected six ν2
modes. Furthermore, Lv et al. [13] found again only two ν1 and three ν3 modes.
In this study, the ATR FTIR method was used to probe the local environment
which gives more accurate results. Thus, it is possible to observe the three predicted
ν1 vibrations for the SO4 ion. The first two at 971 cm 1, 996 cm 1 (in MQ) are
clearly seen peaks, while the third one, positioned at 1026 cm 1 is seen as a shoulder
(Fig. 11.2). All of them are transverse optical (TO) modes (having a field vector
perpendicular to the direction of propagation of the beam). Up to now, to the best of
our knowledge, only in the work of Zhang et al. [4] scientists were able to observe
the third mode with the aid of a polarisation technique.
IR spectroscopy is a very sensitive vibrational technique that might give infor-
mation not only on the chemical species that constitute the material and the strength
of their bonds. The width of an IR peak is, in much respect, affected by the strength
of the intermolecular interactions, the degree of disorder (e.g. due to inhomogenities)
or strain. Thus, IR absorption can give a wide picture of the intrinsic nature of a
sample. In this investigation, the two spectra bear close resemblance regarding the
positions of the bands which implies similar chemical and structural organisation.
Nevertheless, the melt quenched sample give a more detailed IR spectrum. This
effect may be attributed to strain in the material that results from the synthesis
method (Fig. 11.2).
Additionally, we observed five ν3 vibrations: three with A1 and two with E
symmetry. The symmetric bending modes (ν2) are expected in 470–514 cm 1
MBM
MQ b–a
1,0
Heat flow [mW/mg]
Melting
0,5 1
0,0
0 100 200 300 400 500 600 700 800

0
Temperature [ C]
Fig. 11.3 Thermograms of bulk LNS (MQ) (dashed line) and LNS powder (MBM) (solid curves)
frequency region, so we observe only one band (the one located at 514 cm 1) arising
from symmetric bending vibration with E symmetry. Two of the predicted three ν4
(A1) modes are clearly seen at 655 cm 1 and 664 cm 1, while third that is expected
around 630 cm 1 is under the ν4 E envelope with a maximum at 620 cm 1. In the
spectral range in between 500 and 600 cm 1 a number of relatively low peaks is
observed. They might be attributed to cationic interactions with the SO4 ions [10].
The DSC curves of the MQ and MBM samples show three endothermic peaks.
The small peak (1) in Fig. 11.3 is associated with a phase transition of the Na2SO4
[14]. There is a slight difference in the values marking this transition: in the MQ
sample it begins approximately at 243 C, 11 C lower than for the MBM sample.
The variation is minor and might be attributed to the preparation method.
However, when it comes to the first order phase transition temperature of LNS
(from hexagonal to a body centred cubic cell) there are no outstanding differences in
the temperature values. Both samples exhibit peaks with a maximum at 523 C.
These data are in good agreement with data reported by other authors [5, 6]. The
melting point varies; the bulk material melts at 624 C, the powder material at
618 C. This effect might be due to the difference in the particle size. As was already
discussed, the powder sample has a structure with smaller crystallites which defines
the lower melting temperature of the MBM sample. SEM images of the MBM and
MQ samples reveal completely different morphologies of both samples. The powder
sample (Fig. 11.4) consists of very fine crystallites confirming the data from the
Fig. 11.4 SEM images of MBM (left) and MQ (right) samples with magnification 10.0 k
XRD analysis. The particles are clustered in groups – a result from the synthesis
method. When it comes to the bulk sample the scene is different. A variety of shapes
and sizes of crystals are aligned and frozen during the quenching (Fig. 11.4b).
11.4 Conclusion
The lithium sulphate prepared by two independent methods is composed of 92–97

weight % LiNaSO4 and small amounts of Na2SO4. The structure and the thermal
behaviour of the material are matching irrespective of the preparation method. The
IR study reveals that the two spectra bear close resembles regarding the positions of
the bands which implies similar chemical and structural organisation. The phase
transition and material melting occurs at similar temperatures. The morphology,
however, is very different and depending strongly on the preparation method.
Acknowledgments The research leading to these results has received funding from the Bulgarian
NSF under grant No E02/3. The authors are thankful to the Dr. M. Graca from the University of
Aveiro, Department of Physics for conducting the SEM analyses.
References
1. Moseley PT (1997) Solid state gas sensors. Meas Sci Technol 8(3):223–237
2. Fergus JW (2007) Solid electrolyte based sensors for the measurement of CO and hydrocarbon
gases. Sensors Actuators B 122:683–693
3. Dharmasena G, Frech R (1995) Orientational disorder in lithium sodium sulfate. J Chem Phys
102:6941
4. Zhang M, Putnis A, Salje EKH (2006) Infrared spectroscopy of superionic conductor LiNaSO4:
vibrational modes and thermodynamics. Solid State Ionics 177:37–43
5. Shakhovoy RA, Sarou-Kanian V, Rakhmatullin A, Véron E, Bessada C (2016) High-temper-

ature nuclear magnetic resonance study of phase transition kinetics in LiNaSO4. J Appl Phys
118:243906
6. Pimenta MA, Echegut P, Hauret G, Gervais F (1987) Lattice dynamics of LiNaSO4 above room
temperature studied by infrared spectroscopy. Phase Transit Multinatl J 9(2):185–203
7. Ritchie AG (1994) High temperature electrochemical discharges of lithium-copper oxide cells
using solid electrolytes. Solid State Ionics 70/71:662–665
8. Feng Y, Luo J, Chuang KT (2006) Chemical stability of LiNaSO4 electrolyte during operation
in a H2–O2 fuel cell. J Electrochem Soc 153:A865
9. Morosin B, Smith DL (1967) The crystal structure of lithium sodium sulfate. Acta Cryst 22:906
10. Freiheit H-C, Kroll H, Krane H-G, Kirfel A (1999) High temperature X-ray synchrotron study
on LiNaSO4: anharmonic thermal vibrations and effective atomic potentials, HASYLAB annual
report
11. Teeters D, Frech R (1982) Raman and infrared reflectivity spectra of 6LiNaSO4 and 7LiNaSO4.
J Chem Phys 76(2):799
12. Sahaya Prabaharan SR, Muthusubramanian P, Saravanan R, Mohanlal SK (1992) Growth of
LiNaSO4 single crystals from a solution of stoichiometric pH value. Bull Mater Sci 15:355–362
13. Lv W, Tong Z, Yin Y-M, Yin J, Ma Z-F (2015, July) Novel nano-composites SDC–LiNaSO4 as
functional layer for ITSOFC. Nano-Micro Letters 7(3):268–275
14. Rasmussen SE, Jørgensen JE, Lundtoft B (1996) Structures and phase transitions of Na2SO4. J
Appl Crystallogr 29(1):42–47
Chapter 12
Influence of Modification on the Structure
and Physical Properties of Arsenic
Trisulfide. A Short Review
Oleksandr Paiuk
Abstract This brief review summarizes some results of studies concerning the
effect of modification (doping with amphoteric elements, laser and electron-beam
irradiation) on the physico-structural and optical properties of chalcogenide glasses
and the possibility of using doped arsenic trisulphide to create multilayer composite
structures for the recording of holographic optical elements.
Keywords Chalcogenide glasses · Transition elements · Multilayer nanostructures
12.1 Introduction
Chalcogenide glasses (ChGs) are now being intensively studied as promising mate-
rials for the use as active sensor elements as well as passive constituent parts of
sensor systems. ChGs are widely used due to their unique physical properties, such
as the optical transparency in the infrared range, which allows them to be success-
fully used in various infrared optics devices [1–3], a wide glass formation area and
resistance to corrosive media. The presence of a large variety of photoinduced effects
[4–11] makes it possible to obtain different optical elements by means of laser,
electron or ion irradiation. In addition, the glasses serve as host matrix for doping
with rare-earth elements and transition or other metals [12–15], which alter the
properties of the initial material as a result of structural and electronic transforma-
tions in the glass network [14, 15].
Thus, the combination of the properties mentioned above makes it possible to
develop new functional nanocomposite materials, including hybrid organic-
inorganic media [16] based on chalcogenide glasses and polymers for optical and
optoelectronic applications. In the present review results are summarized which were
O. Paiuk (*)
V.E. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences in Ukraine,
Kyiv, Ukraine

96 O. Paiuk
obtained within the frame of implementation of the FP-7 SECURE R-2I project and
projects N0117U000422 and No.M/95-2017 (reg. number 0117U003395) of the
Ministry of Education and Science of Ukraine concerning modification of chalco-
genide glasses, polymer materials, the creation of composites on their base and
application of such media for the fabrication of optical elements [15, 17–25].
12.2 Chalcogenide Glasses: Characterization

and Properties
Chalcogenide vitreous semiconductors are formed by a combination of one or more

chalcogen elements (S, Se, Te) and other elements from the IV-th, V-th and VI-th
group of the periodical table. Bulk glasses are mostly prepared in sealed vacuumed
quartz ampoules by means of the melt-quenching method. X-ray analysis confirmed
the amorphous nature of the investigated bulk chalcogenide glasses from the As–S
system doped with Mn or Cr. Undoped and doped samples were studied by Raman
spectroscopy, differential scanning calorimetry (DSC), IR spectroscopy, SQUID
magnetometry, positron annihilation spectroscopy, atom force microscopy, and
magnetic force microscopy.
12.2.1 Raman Spectroscopy
Raman spectra of As-S system glasses doped with manganese, chromium or ytterbium
show that doping has a noticeable effect on the glass structure [14, 15, 17, 18]. Raman
spectra of As2S3 glasses are characterized by an intense main band at 346 cm1, which
is associated with symmetric stretching vibrations of As–(S)–As in As(S)3/2 pyramids.
As a result of the Mn, Cr or Yb introduction, an intensity increase of the bands at
192, 227, 236 cm1 is observed, which are associated with internal vibrations of As4S4
structural units containing As–As homopolar bonds, and the band at 365 cm1
corresponding to As-S vibrations in As4S4. On the contrary, band intensity at 496 cm1,
which is characteristic for vibrations of S-S bonds, decreases. Thus, the study of the
glass structure showed that they are microheterogeneous (nanoheterogeneous) and
consist of As(S)3/2 and other molecular structural units (As4S4, S8, Sn), the relative
content of which varies with the concentration level of Mn, Cr or Yb [13, 17, 18].
12.2.2 Differential Scanning Calorimetry
DSC data have shown that with the increase of the Mn content in As2S3 glasses the
glass transition temperature and also the activation energy of the glass transition
12 Structure and Physical Properties of Arsenic Trisulfide 97
decrease [17]. This can be connected with structural changes due to interaction of
Mn with the As2S3 glass matrix which was considered using data of Raman and
X-ray diffraction measurements [15]. It should be noted that this trend persists for
glasses doped with chromium or ytterbium [15, 17, 18].
12.2.3 IR Spectroscopy
The absorption of pure As2S3 glass and those doped with transition metals
differs. The spectral profiles of impurity absorption in the case of chromium
and manganese are similar, but there are some differences in the compositional
features of the main impurity absorption bands [19]. Thus, for glasses doped with
chromium, an insignificant increase in the absorption band intensity of hydroxyl
groups at 3601 cm1 is observed, while for Mn-doped samples this band remains
unchanged. Thus, the concentration changes of OH groups are not the same in
both ChGs systems, and it can be assumed that the OH-impurity complexes are
structurally related to sulfur atoms, the relative content of which varies with
doping level and nature of the element. It should be noted that the intensity of the
vibrational band at 2488 cm1, due to the presence of -S-H complexes, increases
monotonically with increasing chromium admixture and is practically indepen-
dent of the manganese concentration. Such features fully correspond to changes
in the structural compactness of the investigated glasses, the decrease of which
leads to the formation of a “free volume” in glass network and the appearance of
peculiar “micro- or nanopores”. -S-H complexes can be formed on the internal
surfaces of these pores as a result of rapid cooling of the glass melt. On the other
hand, most of the broken S-bonds arise during ChGs formation. Such bonds
become inactive or saturation occurs not only due to the formation of structural
chains of sulfur atoms, but also by binding them to hydrogen atoms. Moreover,
during ChGs synthesis the parallel saturation process of dangling sulfur bonds by
oxygen atoms (band at 1158 cm1, related to the SO2 impurity) occurs, which can
be adsorbed from the atmosphere or formed during high-temperature splitting of
H2O molecules. Formation of As-O bonds (bands at 1048 cm1 and 792 cm1)
and S-S bonds (980 cm1) occurs through the incorporation of SO2 molecules
into the glass network; as a consequence, the As-As bond is broken and the bond
>As–O–S–O–As< is formed. The intensity of the peaks corresponding to As-O
and S-S bonds increases with decreasing intensity of the SO2 band. Note that
these processes are relatively weak, because the structural chains of the glass are
not fully, but only partially closed. They form bridges between neighboring
atoms, fragments and blocks [19].
98 O. Paiuk
12.2.4 Photoluminescence Spectra
Low-temperature photoluminescence spectra for As2S3:Cr glasses with different Cr

contents are in agreement with a model proposed by Tanaka [15, 18]. According to
this model, half-gap photoluminescence arises from the recombination of electrons,
trapped by anti-bonding states of wrong (and strained) bonds at around the mid-gap
Fermi level, and holes in Urbach-edge states at the valence-band top. These wrong
bonds are considered as the most dominant defects in covalent chalcogenide semi-
conductors such as As2S3. Rare-earth luminescence As-S glasses modified by Yb
have two luminescence bands in the near IR range, located near 980 and 1060 nm. In
this case, transitions from the excited state 2F5/2 to the main state 2F7/2 characteristic
for Yb3+ ions are pronounced. The intensity of the photoluminescence increases with
an increase of the ytterbium concentration [14]. In the case of Mn- doped As2S3, two
luminescence peaks are observed, one at approximately 545 nm (2.28 eV) which can
be connected with transitions of Mn2+ ions located near structural defects. The next
peak at 578 nm (2.14 eV) can be associated with radiative transitions of Mn ions
placed near structure defects.
12.2.5 Magnetic Properties
Chalcogenide glasses, in particular As2S3 glasses, are diamagnetics. Introduction of

transitional (Mn, Cr) and rare earth (Yb) impurities changes the magnetic properties
of the investigated chalcogenide glasses [13, 15]. In fields near 6 T, a mass
magnetization dependence M¼M(T) was observed, which is characteristic for para-
magnetics and ferromagnetics in the paramagnetic temperature range and described
by the Curie–Weiss law. A more detailed study of Mn-doped glasses showed that
there is a transition from the paramagnetic to the ferromagnetic state at a temperature
T~14 K. In this case, a difference between M(T) dependences for various cooling
mode disappears in a field B ¼ 0.197 T. It can be assumed that the influence of the
external field on the orientation of the intrinsic magnetic moments of the dopant
atoms on the energy value exceeds the energy of their thermal movement [13, 15].
12.3 Multilayer Nanostructures Based on Doped Arsenic

Trisulfide
Using thin layers of chalcogenide glasses as high-resolution media and selective

etching after exposure, high quality holographic diffraction gratings [6, 9] and other
elements [4, 5, 10] were obtained. Using multilayer nanostructures based on chal-
cogenide glasses as recording media enables to obtain a surface relief directly during
the recording process [26–28]. The development of methods of one-step surface
relief formation is considered as a promising way for the manufacturing of planar

diffractive optical elements. Usually, chalcogenide layers and chalcogenide multi-
layer nanostructures are prepared by thermal vacuum deposition of two materials
(ChGs and Se) [20–28]. The technological processes allow to deposit layers and
structures onto substrate with thicknesses from 0.005 to 3.0 μm and different
geometry. Using of interferometric holographic recording makes it possible to obtain
grating surface reliefs based on multilayer nanostructures, for example, As2S3:Mn
(2 wt.%) – Se and Ge5As37S58–Se with good optical quality of the surface relief
[21, 25]. Besides surface relief formation using mentioned above nanostructures,
As2S3:Mn (2 wt.%)–Se enables to obtain simultaneously also a magnetic relief
[23]. In the case of Ge5As37S58–Se it is possible to realize direct one-step recording
of diffraction gratings by e-beam exposure as well as e-beam pixel recording of other
elements [24, 25].
12.4 Conclusion
• Doping with Mn, Cr or Yb causes a decrease in the glass transition temperature

and leads to a change in the relative concentration of basic and non-stoichiometric
structural elements characteristic for As2S3 and also to the change of luminescent
and magnetic properties.
• IR transmission spectroscopy in the 700–4000 cm1 region showed the existence
of impurity absorption bands of hydroxyl, oxide and carbon-containing groups,
the growth or decrease of which depends on the concentration and nature of the
doping element.
• Nanomultilayered, compositionally modulated ChGs–Se multilayer structures are
perspective for the recording of optical elements using light or e-beam exposure;
simultaneous direct one-step recording of surface and magnetic relief formation
was shown using As40S60:Mn (2 wt.%)–Se nanomultilayer structures.
References
1. Adam J-L, Calvez L, Trolès J, Nazabal V (2015) Chalcogenide glasses for infrared photonics
Int J Appl Glas Sci 6:287
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Zdyrko B, Luzinov I, Novak S, Novak J, Wachtel P, Danto S, Musgraves JD, Richardson K,
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Part IV
Electrical Characterization
Chapter 13
Time Domain Versus Frequency Domain
in the Characterization of Materials
L. C. Costa
Abstract The development of sampling oscilloscopes provided the possibility to

measure dielectric relaxation processes in materials directly in the time domain. This
allows using relaxation models in time. In complex systems, the use of non-Debye
models, such as Kohlrausch-Williams-Watts is common. Simultaneously, the use of
frequency domain measurements is becoming very useful, due to the possibility of
using highly accurate impedancemeters. To obtain a complete characterization of the
dielectric response, a large range of frequencies and temperatures must be used.The
different regimes of the dielectric function can be observed and the dynamics of the
relaxations can be determined, using modelling with different empirical models,
such as Cole-Cole, Cole-Davidson and Havriliak-Negami. In this contribution,
different examples of the use of time and frequency domain measurements are
presented, showing the capability of both techniques.
Keywords Time domain · Frequency domain · Impedance spectroscopy · Dielectric

relaxation
13.1 Introduction
Measurements in the time domain have undergo a remarkable development in the

last years, particularly in the pursuit of relaxation phenomena. The advantage
inherent to this method is that the measurement of time is carried out directly,
without the need to make use of the inverse Fourier transformation. The main
disadvantages imposed by the fact that the measurement is made under broadband
conditions, resulting in the degradation of the signal-to-noise ratio [1]. In the case of
high impedance samples, the use of an electrometer in needed, which can detect
currents on the order of fA. Initially, the sample is subjected to a direct voltage for
L. C. Costa (*)
I3N and Physics Department, University of Aveiro, Aveiro, Portugal

106 L. C. Costa
sufficient time allowing to calculate the d.c. conductivity, and then it is abruptly
turned off in order to study how the current decreases over time [2].
In the frequency domain, the dielectric response of a material is measured
with broadband frequencies from a few mHz to hundreds of GHz [3–5]. To cover
such a wide frequency range, several measurement techniques are required.
In the low frequency range, it is possible to use bridges [6], lock-in amplifiers [7]
and impedance analyzers [8]. Network analyzers are used for the microwave range,
based on the small perturbation theory [9].
Several advantages and limitations can be attributed to these techniques, but
using broadband dielectric spectroscopy to observe the temporal evolution of mate-
rials has a relatively recent origin. In the early years, low frequency measurements
were made using transient current methods [10]. An important improvement was
achieved with the emergence of radio frequency electronic devices in the beginning
of twentieth century, which increased the frequency range of measurement up to
MHz. Finally, in the 1950s, methods including microwave frequencies measure-
ments were developed [11].
In most cases, the electrical measurements are made in a neutral atmosphere using
electrodes in the sample. The general approach is to apply an electrical stimulus and
observe the response of the material. It is assumed that the properties of the
electrode-material system are time-invariant, which is an important demand to the
measurement method [12].
Actually,dielectric spectroscopy can deliver the complex permittivity ε*
(ω) ¼ ε0 (ω)iε00 (ω) or derived quantities related to it. The dielectric modulus [13]
M ¼ ε1, a complex quantity with M*(ω) ¼ M0 (ω) + iM00 (ω) is often used for
conducting materials, where the relaxation can be hidden by the conductivity. The
macroscopic properties, the impedance Z*(ω)¼Z0 (ω)iZ00 (ω) or the admittance
Y ¼ Z1 with Y*(ω) ¼ Y0 (ω) + iY00 (ω) can also define the properties of a material.
The interrelations between these quantities are simple when the shape and size of the
samples are known on which the measurements are made.
13.2 Time Domain
The simplest condition of a relaxation phenomenon was initially described by Debye

[14], based on a physical model that consisted of dipoles immersed in a viscous
medium, with the assumption that they did not interact each other. Under the action
of an electric field, the dipoles were oriented, returning to the equilibrium position
after turning off the field. Then, the depolarization function presents an exponential
decay with time,

t
ΦðtÞ ¼ Φ0 exp ð13:1Þ
τD
13 Time Domain Versus Frequency Domain in the Characterization of Materials 107
where Φ0 is the initial polarization and τD the relaxation time. The depolarization
current is

∂ϕðt Þ t
I ðt Þ ¼ ¼ I 0 exp ð13:2Þ
∂t τD
Linearization of this expression proceeds to
t
ln I ðt Þ ¼ ln I 0 ð13:3Þ
τD
It is known that a large class of physical systems including polymers and glasses
have a comportment for the depolarization function which is not purely exponential.
This behaviour can be described by a stretched exponential function, attributed to
Kohlrausch in the nineteenth century [15] which was subsequently tested and used
empirically by Williams and Watts [16] to study the dielectric relaxation in several
materials. His analytical expression is
β K !
t
ΦðtÞ ¼ Φ0 exp ð13:4Þ
τK
where τk is the relaxation time and βk is an exponent between 0 and 1.

One approach to describe this situation is to postulate a statistical distribution of
relaxation times for the different atoms, molecules, aggregates or other degrees of
liberty. So, assuming that these contributions are additive [17], we can write,
Z 1 t
ΦðtÞ ¼ Φ0 gðτÞ exp dτ ð13:5Þ
0 τ
where the distribution of relaxation times function, g(τ) must obey the normalization
condition
Z 1
gðτÞ dτ ¼ 1 ð13:6Þ
0
In this case, the depolarization current is

βK 1 βK !
∂Φðt Þ t t
IðtÞ ¼ ¼ I0 exp ð13:7Þ
∂t τK τK
where
Φ0 βK
I0 ¼ ð13:8Þ
τK
108 L. C. Costa
Another non-Debye relaxation can be expressed by the Curie-von Schweidler law

[18, 19], where the depolarization current is
I ðtÞ ¼ Ats ð13:9Þ
where A is a constant and 0<s<1.

The linearization of this expression yields
ln I ðt Þ ¼ ln A s ln t ð13:10Þ
From a practical point of view, Eqs. (13.3) and (13.10) can be used to test if
Debye or Curie-von Schweidler models are adequate to fit the experimental results.
It is known that in a large number of materials these models are not acceptable, and
then Kohlrausch-Williams-Watts (KWW) is the most useful representation.
13.3 Frequency Domain
To attain the frequency domain from the time domain, we can use the Fourier
transformation. In the Debye model, that is, corresponding to a single relaxation
time, we can obtain [1],
εs ε1
ε ∗ ð ωÞ ¼ ε 1 þ ð13:11Þ
1 þ iωτD
where ε*(ω) is the complex permittivity ε*(ω)¼ε0 (ω)iε00 (ω),ω ¼ 2πf is the angular
frequency, and ε1 and εs are the dielectric constants at high and low frequencies,
respectively. This equation can be solved for the real and imaginary parts:
εs ε1
ε0 ðωÞ ¼ ε1 þ ð13:12Þ
1 þ ω2 τ D 2
00 ð εs ε1 Þ ω τ D
ε ð ωÞ ¼ ð13:13Þ
1 þ ω2 τ D 2
Figure 13.1 shows typical curves for the real and imaginary parts of the complex
permittivity for the Debye model in semi-logarithmic scale. These curves are
symmetric relative to the relaxation frequency point ω ¼ 1/τD.
From Eqs. (13.12) and (13.13) we can obtain
εs þ ε1 2 00 2 ε ε 2
1
ε 0 ð ωÞ
s
þ ε ð ωÞ ¼ ð13:14Þ
2 2
which is an equation of a circle. Then, in the Cole-Cole representation, that is ε00
versus ε0 , we have a semi-circle with radius (εs ε1)/2and the center in the point
((εs + ε1))/2, 0). Figure 13.2 shows the data of Fig. 13.1 in this representation.
Fig. 13.1 Real and

imaginary parts of the
complex permittivity for the ω=1/τD
Debye model
ε′
ω=1/τD
ε′′
log f (a.u.)
Fig. 13.2 Cole-Cole plot

for the data of Fig. 13.1
ω=1/τD
ε′′
e∞ εs
ε′
For systems where non-Debye relaxation behavior is observed, Eq. (13.11) must
be modified, using the concept of distribution time function, g(τ) [20]
Z 1
gð τ Þ
ε ∗ ð ωÞ ¼ ε 1 þ ð ε s ε 1 Þ dτ ð13:15Þ
0 1 þ iωτ
the real and imaginary parts of the complex permittivity are:

Z 1
gð τ Þ
ε0 ðωÞ ¼ ε1 þ ðεs ε1 Þ dτ ð13:16Þ
1 þ ω2 τ 2
Z 1
0
00 ωτ gðτÞ
ε ð ωÞ ¼ ð ε s ε 1 Þ dτ ð13:17Þ
0 1 þ ω2 τ 2
Then, for non-Debye behavior, one of the most used models is the Cole-Cole
[21], described by
110 L. C. Costa
εs ε1
ε ∗ ð ωÞ ¼ ε 1 þ ð13:18Þ
1 þ ðiωτcc Þ1α
where τcc is the characteristic relaxation time and α a parameter (0<α 1) that leads
to a broadening of the relaxation function. In this case, the curve in the Cole-Cole
plot is also symmetric, as in the Debye case, but the center of the semi-circle is not on
the abscissa, but below it, as shown in Fig. 13.3. The angle of the asymptotes in the
limits of high and low frequency is the same, that is (1-α)π/2.
Another possibility, quite often used in complex materials, is the Cole-Davidson
model [22],
εs ε1
ε ∗ ð ωÞ ¼ ε 1 þ ð13:19Þ
ð1 þ iωτcd Þβ
where again the exponent β reflects the broadening of the relaxation function
(0 < β 1) and τcd the relaxation time. In this case, the curve in the Cole-Cole
plot (ε00 versus ε0 ) is no longer symmetric, as we can see in Fig. 13.4. In the low
frequency regime, the asymptote has an angle of π/2, in the high frequency regime
the angle is βπ/2.
An even more general model function was introduced by Havriliak and Negami
[23], which is a combination of Cole-Cole and Cole-Davidson functions:
Fig. 13.3 Cole-Cole model, 3

showing the symmetry
Cole-Cole
2
ω
ε′′
(1-α)π/2 (1-α)π/2
0
0 1 2 3 4
ε′
Fig. 13.4 Cole-Davidson 3

model, showing the
asymmetry Cole-Davidson
2 ω
ε′′
1
βπ/2 π/2
0
0 1 2 3 4
ε′
εs ε1
ε ∗ ð ωÞ ¼ ε 1 þ β ð13:20Þ
1 þ ðiωτhn Þ1α
The particular case of α ¼ 0 and β ¼ 1 leads to the Debye relaxation.
13.4 Global Characteristics of Relaxation
One phenomenon that has been studied in detail in recent years is the emergence of
more than one relaxing mechanism in the same physical system. It has been detected
in microemulsions [24], viscous liquids [25], polymers [26] and glasses [27].
Conventionally, these processes are denominated as primary or α relaxation and
secondary or β relaxation, each with its own characteristics. Thus, the α processes
typically have high temperature-dependent relaxation times and are found at lower
frequencies than that one recognized as secondary relaxations. Normally, Vogel-
Fucher-Tamman (VFT) function describes the relaxation dependence on tempera-
ture accurately [28]. The secondary relaxations have a lesser variation with temper-
ature and are described by the Arrhenius equation [29].
Figure 13.5 shows the dielectric losses ε00 ,as a function of frequency at constant
temperature for a composite, styrene-b-isoprene-b-styrene copolymer with ferrites
particles, and the best fit, where three relaxation processes are present [30]. In the
low frequency region, a first α relaxation is visible (α1), the corresponding β
-1
1x10
-2
8x10
-2
6x10
e" -2
4x10
-2
2x10
a2 b2 a1
0
-1 0 1 2 3 4 5 6
10 10 10 10 10 10 10 10
Frequency (Hz)
Fig. 13.5 Dielectric loss curve and best fit, showing three relaxation processes for a composite with
8% of lithium ferrite particles at constant temperature (Reprinted with permission from [30]. © 2014
AIP publishing)
112 L. C. Costa
relaxation appears at higher frequencies (β1). In the high frequency region, a new α
relaxation is detectable (α2), the corresponding β relaxation is out of the frequency
window of the measurement.
The relaxation map for this material is shown in Fig. 13.6, where the differences
between the α and the β relaxation processes become clear, with the Vogel-Fucher-
Tamman function and the Arrhenius type behaviors for the two types of relaxations
observed.
13.5 Procedures to Fit the Experimental Data
To fit the experimental data points in the time domain to a Kohlrausch-Williams-

Watts (KWW)function (Eq. 13.4), it is absolutely crucial to use algorithms based on
well-known methods, and especially to take a special care when defining the initial
values of the parameters to be determined. With three degrees of freedom as in this
function, obtaining correct final values strongly depends on the initial values intro-
duced as a starting point for the fit.
The depolarizing current, as the derivative of the polarization function, is, for
KWW function
12
10
8
a1
6
-LogtMáx
2
a2 b2
0
Tg2 Tg1
-2
2,5 3,0 3,5 4,0 4,5 5,0
-1
1000/T (K )
Fig. 13.6 Relaxation map for a composite with 8% of lithium ferrite particles. Tg1 and Tg2 are the
glass transitions of the components of the copolymer, polyisoprene and polystyrene (Reprinted with
permission from [30]. © 2014 AIP publishing)
βK 1 β K !
∂φðt Þ t t
IðtÞ ¼ ¼ I0 exp ð13:21Þ
∂t τK τK
Φ0 β K
with I0 ¼ ð13:22Þ
τK
Manipulating Eq. (13.21), we can obtain [31]
∂ ln IðtÞ
¼ ðβK 1Þ βK ðt=τK Þ ð13:23Þ
∂ ln t
Regarding this equation, the logarithmic derivative takes the value -1 exactly
for t¼τK independent of the values of I0 and βK. This value of τk is a good starting
point as the initial value to be inserted into the numeric fitting process. In Fig. 13.7
we can observe the ∂ln I(t)/∂ln t versus t graph for a lead borate glass, where the
point (t, 1) allows to estimate the initial value of τK.
The next step is to calculate a first approximate value of βK. We can look at what
happens when t>>τK, that is, in the long-time regime. Here, the following approach
is valid:
βK !
t
IðtÞ ¼ I0 exp ð13:24Þ
τK
and we can obtain
Fig. 13.7 ∂ln I(t)/∂ln t versus t graphic for a lead borate glass [7]
114 L. C. Costa

∂ ln I ðt Þ
ln ¼ ln βK τK 1βK ðβK 1Þ ln t ð13:25Þ
∂t
From this equation, having already the value of τK, we can calculate βK..With the
initial values of these parameters, it is accurately possible to fit the data with the
KWW function.
In frequency domain we can also obtain the relaxation parameters, using some
mathematical manipulation.For the Cole-Davidson mode, which is frequently used
to fit experimental data in several materials, we can use a similar strategy. First, we
calculate the approximate values of those parameters from the asymptotic values of
the data, and then use them as a starting point for the numerical fit [32].
For ωτcd >> 1, we can expand the Cole-Davidson Eq. (13.19) [33],
ε0 ε1 h
00 ¼ cot g βπ=2 Þ þ 1 þ cot g2 ðβ π=
2 Þ β ðωτcd Þ1 ð13:26Þ
ε
In the high limit frequency, this expression becomes
ε0 ε1
¼ cot gðβ π=2 Þ ð13:27Þ
ε00
Then, the calculus of the exponent β is easy, as seen in Fig. 13.8.
The expansion in the low frequency region becomes
10
6
e´´
0
6 8 10 12 14
e´
Fig. 13.8 ε00 versus ε0 for a lead borate glass at aconstant temperature. The angle of the tangent to
the curve with the abscissa in the high frequency region is βπ/2

0 1þβ
ε ¼ εs 2π ε00 ðωτcd Þ þ Ο ðωτcd Þ4 ð13:28Þ
2
where O(ωτcd) represents the terms higher than order three. Since in the low
frequencies region these terms are negligible, the graph of ε0 versus (ε00 ω) is a
straight line with a slope proportional to τcd, as seen in Fig. 13.9. Since we have
already a value of β, it is possible to estimate a value for τcd.
13.6 Case Study
Time and frequency domain electrical measurements were madethe glass system
xGd2O3PbO2B2O3.The depolarization current for a glass with x ¼ 0.00 at constant
temperature T ¼ 330 K is shown in Fig. 13.10. The scales ln I(t) versus t and versus
ln t were used, in order to check the possibility of using Debye or Curie-von
Schweidler models (Eqs. 13.3 and 13.10), as discussed previously.
It is clear that none of these models is adequate, as no straight lines are obtained in
this graphic. Therefore, the Kohlrausch-Williams-Watts approach (KWW) was used
to fit the data in the entire x range (0.00<x<0.20).
As can be seen, the values for the relaxation time must be high, corresponding to a
low frequency relaxation.
In Fig. 13.11 the calculated relaxation parameters of the KWW function Φ0, τK, βK
are shown for several concentrations of gadolinium oxide at constant temperature
T ¼ 150 K; in Fig. 13.12 we can observe the same parameters as a function of
temperature for x ¼ 0.07.
9,5
e´
9,0
8 8 8 8 8
0 1x10 2x10 3x10 4x10 5x10
e´´w
Fig. 13.9 ε0 versus (ε00 ω) for a lead borate glass at aconstant temperature in the low frequency
region
116 L. C. Costa
ln t
0 2 4 6
-12 -12
2x10 2x10
ln I (A)
ln I (A)
-12 -12
1x10 1x10
0 0
-20 0 20 40 60 80 100 120 140 160 180 200

t (s)
Fig. 13.10 ln I(t) versus t and versus ln t, for the base glass PbO2B2O3, at a constant temperature
Fig. 13.11 Relaxation 0.4

parameters of the KWW βK
function, as a function of the
gadolinium oxide content in Φ0(u.a.)
0.3
the lead borate matrix at
aconstant temperature 20
τK (s)
T ¼ 150 K
40
30
10
0.00 0.07 0.10 0.20

x
It can be verified that the βK parameter is nearly independent of the concentration

while increasing progressively with temperature. This parameter can be interpreted
as a measure of the distribution of relaxation times [34]; in this case, it would mean
that with increase of the temperature the distribution function g(τ) would become
less wide. It can also be understood as a measure of coupling between the relaxing
units and the system [35]; thus the coupling decreases with the temperature since βK
increases. The initial polarization increases with temperature in a quasi-linear way,
Fig. 13.12 Relaxation

parameters of the KWW 0.5
function as a function βK
temperature for x ¼ 0.07
Φ0(u.a.)
0.3
τK (s) 100
40
60
30
20
100 200 300 330
T(K)
18
16
14
12
e´
10
-2 -1 0 1 2 3 4 5 6 7 8 9
10 10 10 10 10 10 10 10 10 10 10 10
frequency (Hz)
Fig. 13.13 Real part of the complex permittivity for the base glass at constant T ¼ 300 K
till a critical concentration xc ¼ 0.07, from which on it is practically constant. The

relaxation time is thermally activated, and it is observed that the activation energy
does not depend on the doping concentration; therefore this low frequency relaxation
process is characteristic of the lead borate glass.
The frequency domain measurements covered a large range of frequencies and
temperatures. Figure 13.13 shows the real part of the complex permittivity for the
base glass at constant T ¼ 300 K.
The presence of two relaxation processes, separated by about nine decades is
clear. The low frequency one corresponds to that one observed in the time domain.
118 L. C. Costa
Table 13.1 Relaxation x τcd (ns) β

parameters using the Cole-
0.00 0.90 0.89
Davidson model at constant
temperature T ¼ 300 K for the 0.01 0.92 0.88
high frequency process 0.03 0.94 0.87
0.05 0.96 0.86
0.07 0.96 0.85
0.10 0.97 0.85
0.20 0.99 0.84
For the analysis in the frequency domain, the Cole-Davidson model was used, as
confirmed by observing Fig. 13.8, for the high frequency relaxation process. The
calculated relaxation parameters are presented in Table 13.1.
We must note the increase in the relaxation time with the concentration, while the
β parameter reveals a very slight decrease, but close to 1, which means that this
process is close to Debye.
13.7 Conclusions
Time and frequency domain can be used to characterize electrically materials.

Mathematically they are connected by the Fourier transformation.In the time
domain, the Debye-like type is not very common, and then Kohlrausch-Williams-
Watts or Curie-von Schweidler models can be used.In the frequency domain, Debye,
Cole-Cole, Cole-Davidson or Havriliak-Negami are the used models. In our case
study, relaxation processes were studied in both domains, for a lead borate glass
doped with gadolinium oxide. Kohlrausch-Williams-Watts and Cole-Davidson
model fits correctly the experimental data.
References
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2. Daniel V (1967) Dielectric relaxation. Academic, London
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Fitzgerald JJ (eds) Dielectric spectroscopy of polymeric materials. American Chemical Society,
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Wiley, New York
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Chapter 14
The Measurement of Thermally Stimulated
Depolarization and Polarization Currents
M. P. F. Graça and P. R. Prezas
Abstract The measurement of thermally stimulated depolarization currents, a tech-

nique usually known by its initials (TSDC), has contributed substantially to the
knowledge and understanding of charge storage and charge decay processes in
several types of electret materials, i.e., materials that can have electrical polarization
arising from kinetically trapped charges. The polarization of these materials may
increase the magnitude of the applied electric field, until the point of dielectric
breakdown. A similar, and sometimes complementary, technique consists in the
measurement of thermally stimulated polarization currents (TSPC). This
contribution discusses experimental and theoretical considerations regarding both
techniques. Additionally, it also includes a case study regarding LiNbO3 glass-
ceramics, synthesized by the melt-quenching process.
Keywords TSDC · TSPC · LiNbO3 · Glasses · Glass-ceramics
14.1 Introduction
The measurement of thermally stimulated depolarization and polarization currents,

TSDC and TSPC, respectively, are part of a broad group of thermally stimulated
experimental techniques, where a given physical property of the material is studied
as a function of the temperature. In the cases of TSDC and TSPC the property in
analysis, i.e., the electric current, is strictly related to dipolar polarization/depolari-
zation and spatial charge detrapping/decay processes activated by both the temper-
ature and the applied electric field.
The designation TSDC does not coincide with the appearance of this technique in
the scientific community, which occurred in 1964 when it was introduced by Bucci
and collaborators [1]. The technique was introduced under the designation ionic
M. P. F. Graça (*) · P. R. Prezas


122 M. P. F. Graça and P. R. Prezas
thermoconductivity ITC, because it would be applied in the analysis of ion related

processes such as dipolar relaxation, among others. The terminology TSDC was
posteriorly adopted to include materials where both ionic and electronic charges
yield a significant contribution to the magnitude of the polarization and the respec-
tive depolarization or polarization currents [2]. TSDC and TSPC have found a
substantial amount of applications in the study of the electrical properties of glasses,
glass-ceramics, and polymers [3, 4]. However, since the charge transport and
trapping processes are not only essential for electrets, they have also found signif-
icant applications in the characterization of materials applied as thin films, such as
photoconductors and electro-optic devices [5]. Additionally, features such as the
very high sensitivity (capable of detecting small contributions to the polarization,
due to dipole densities on the order of 1015 dipoles per cubic centimeter) and the
resolving power contributed to the popularization of these techniques. Furthermore,
the theoretical description and following mathematical formulation of the different
processes contributing to the depolarization currents are already well established.
The present contribution is divided into two main sections: the first deals with the
theoretical and experimental characteristics of both techniques, while the second will
contain a case study regarding TSDC measurements on LiNbO3 and NaNbO3
containing glasses and glass-ceramics, synthesized by melt-quenching and sol-gel
processes.
14.2 Background
14.2.1 TSDC: Thermally Stimulated Depolarization Currents
The experimental details and steps of the TSDC technique are directly related to the
fact that when heating up a solid dielectric material which is electrically polarized
through the application of an external dc electric field, the relaxation time of the
sample’s polarizable components will be small enough so that the polarization
reaches its saturation condition in a short period.If the electric field is kept applied
while the sample temperature is decreased down to a temperature low enough so that
the relaxation times are very high, the polarization can be considered as “frozen”. At
this point, it will remain “frozen” even after the removal of the electric field, since the
thermal energy is not high enough to activate the return of the charge carriers to their
equilibrium positions. If the temperature of the sample is again increased, there will
be a gradual release of the trapped charges, originating a depolarization current.
This process, represented schematically in Fig. 14.1, is based on the execution of
the following experimental steps [6, 7]:
1. Application to the sample (with appropriate electrodes), at a polarization temper-
ature Tp, of an electric dc field Ep during a period tp high enough so that the
polarization reaches its saturation condition.
14 The Measurement of TSDC and TSPC 123
Fig. 14.1 Scheme of a

typical TSDC experiment
[9]
2. The sample is cooled, preferably with a high cooling rate while keeping the field
Ep applied, down to a temperature T0 where the dipolar motions can be regarded
as negligible.
3. Ep is removed, and the sample is short-circuited (SC step in Fig. 14.1) for a few
minutes to release weakly bonded charges.
4. The sample is connected to a very sensible electrometer (currents as low as 1015
A may be detected) and warmed up with a constant heating rate β. The depolar-
ization current is measured as function of the temperature. The origin of this
current is the relaxation of the charge carriers.
Figure 14.1 also depicts the behavior of the charge current Ic and the current
discharge Id. As expected, the charge current increases during the time of Ep
application, reaching a saturation condition. During the SC step, a discharge current
can be detected, related tothe release of weakly bonded charges. Subsequently, the
depolarization processes will be detected as currents in the Id versus
temperature plot.
As the most significant advantages of this technique, we highlight [3, 8]:
1. In materials with multiple relaxation processes, each process should originate a
separated TSDC current peak.
2. It does not require an applied external electric field during the measurements,
decreasing by this way the electric conduction effects.
3. Allows making quantitative measurements of: impurities concentration; molecu-
lar movements; characterization of macromolecular states; local environment
characterization; chemical degradation; structural anisotropy.
As main disadvantages of this technique, the high sensibility and resolution
required for the data acquisition system can be stated.
Taking into account the discussed experimental procedure, it is clear that all
TSDC measurements will need some mandatory equipment. The list contains a
furnace or cryostat, depending on the temperature range to analyze, a temperature
controller capable of controlling a linear variation of the temperature as a function of
time, with high-precision, a stable dc power supply for the electrical polarization and
a sensible electrometer. Depending on the sample or type of measurement intended,
a vacuum container and the possibility of controlling the atmosphere may be
desirable. In conclusion, Fig. 14.2 shows a general setup for a TSDC measurement,
with all the equipment that was referred to.
14.2.2 TSDC: Physical Processes and Mathematical

Formulation
It is known that different processes can contribute to the measured depolarization

current of a given sample. Among theseprocesses, the followingcan be highlighted:
Fig. 14.2 General experimental setup for a TSDC experiment [10]

the reorientation of electric dipoles (dipolar polarization), the movement of trapped

electric charges, i.e., space charge detrapping, the displacement of the electronic
cloud within an atom or ion (induced electronic polarization) or the ionic displace-
ment within a molecule (induced dipolar polarization), the formation of defect
dipolar polarization, etc. [2, 10].
The analytical expressions describing the depolarization current are usually
applied in materials where ionic processes dominate the response, i.e., the electronic
response can be considered negligible. In such a case, two formulations are most
commonly used, for dipolar reorientation and space charge detrapping processes,
respectively. For a depolarization current peak originated from dipolar reorientation,
and a first order process, the dependence of the current density on the temperature [J
(T)] is given by Eq. 14.1 [2, 10, 11]:
Z T
P0 Ea 1
J ðT Þ ¼ exp exp exp τðT ÞdðT Þ ð14:1Þ
τ0 kB T β T0
where P0 is the equilibrium polarization (basically, the sample’s polarization before

starting the measurement), τ0 is a pre-exponential factor that can be interpreted as the
relaxation time when the temperature tends to infinite, Ea is the activation energy for
dipole relaxation/reorientation, kB is Boltzmann constant, β the heating rate and
τ(T) the characteristic relaxation time. For dipolar reorientation, Eq. (14.1) can be
modified to include an analytical expression describing the dependency of P0 on the
electric dipole density N, the individual dipole moment p, the electric field Ep, and
the polarization temperature Tp, yielding the following expression [2, 10, 11]:
Z T
Np2 E p Ea 1
J ðT Þ ¼ exp exp exp τðT 0 Þd ðT 0 Þ ð14:2Þ
3kB T p τ0 kB T β T0
Equation 14.2 is usually labeled as Bucci-Fieschi theory, describing a depolari-

zation current peak due to a dipolar reorientation process.
On the other hand, to describe a peak originating from spatial charge detrapping,
the Bucci-Fieschi can be still applied to describe the depolarization of space charge,
assuming that all the trapped charges have approximately the same mobility. In this
case, the equilibrium polarization P0 is given by (14.3) [12]:

Ea qLE p qLE p
P0 ¼ 2qLvNt p exp sinh ¼ PSC sinh ð14:3Þ
kB T 2kB T p 2kB T p
where q is the ionic charge, L is the ionic jump length, v is the jump frequency, N is
the density of trapped charge, tp is the polarization time (as shown in Fig. 14.1) and
Ea is the activation energy required for detrapping the charge carriers.
The mathematical treatment of Eq. (14.2) is not trivial, the main problem being
the fact that the integration leads to an infinite series converging to infinite. There-
fore, some approximations are needed to be considered. One of these approxima-
tions is particularly useful for the activation energy calculation: the initial rise
method, introduced by Garlick and Gibson [13], is based on the fact that the integral
is negligible for temperatures lower than the peak temperature. Therefore, the
equation can be simplified, and the activation energy can be evaluated through an
Arrhenius dependency, as expressed in (14.4) [13] (where A is a constant):

Ea
J ðT Þ ¼ Aexp ð14:4Þ
kB T
14.2.3 TSPC: Thermally Stimulated Polarization Currents
The measurement of thermally stimulated polarization currents (TSPC) is a coun-

terpart of TSDC, and also often regarded as an inverse of TSDC. TSPC involves the
measurement of the current that flows through a solid dielectric material subjected to
a dc electric field as the material temperature is increased with a linear rate, from
some low-temperature T0 [6]. Therefore, in TSPC there is no necessity to polarize
the material previously.
Figure 14.3 shows a scheme of a typical TSPC measurement. Initially, small and
current contributions may be detected due to induced dipolar and electronic polar-
ization. These induced polarizations are typically those that respond faster to an
applied electric field, due to the small distances of displacement and also, in case of
the induced electronic polarization, due to the low mass of electrons. Subsequently,
as temperature linearly increases, the alignment of the dipoles or other processes will
be detected as currents peaks in a current versus temperature representation [14]. The
Fig. 14.3 Scheme of a

typical TSPC experiment.
The background current
JB(t) and a dipolar
contribution to the
polarization current, JD(t),
are also represented
reason behind the fact of TSCP being regarded as an inverse of TSDC is that while in
TSDC the current peaks are caused by the depolarization processes, in TSPC they
are due to thepolarization. It is also visible in Fig. 14.3 that a background current
JB(t) is detected, which is also characteristic in TSDC measurements. JD(t) represents
the dipolar contribution of the measured current. About the additional/complemen-
tary information that TSPC can provide, the possibility is highlighted to distinguish
the physical process behind dipolar depolarization processes observed in TSDC
spectra. While depolarization peaks related to dipolar reorientation will be centered
at about the same temperature in both TSDC and TSPC spectra, but with opposite
direction, processes related to vacancies and impurities diffusion will be detected as
an exponential rise of the current in the TSPC spectrum. Figure 14.4 shows this
behavior for a BaF2:Tb3+ single crystal [15]. While the first process at about 195 K is
caused by the reorientation of F-Tb3+ dipoles, the second at around 340 K is assigned
to the diffusion of fluoride vacancies, therefore it is detected as an exponential rise of
the current. It is to be noted that the mathematical formulas for both techniques is
essentially the same, i.e., the formulations discussed in the TSDC section are the
same for both techniques, the only difference being that Tp has to be replaced by a
variable temperature T.
The equipment required for TSPC measurements is essentially the same as described
for TSDC. However, one of the reasons that explain the fact of TSDC being the most
popular technique is that the signal to noise ratio in a current measurement is markedly
better if the current is measured without an applied electric field.
Fig. 14.4 Recorder plots of

TSPC (above) and TSDC
(below, designated as ITC –
ionic thermo-conductivity)
measurements performed
with a BaF2:Tb3+ single
crystal [15]
14.3 Case Study: Glass and Glass-Ceramics with LiNbO3
Glass refers to one of the oldest known materials of mankind. It is defined, according
to ASTM C-169-92, as a inorganic product obtained by rapid cooling of a melt, to
conditions of rigidity, without crystallization. This definition is, however, too
restrictive as it only applies to glasses prepared by the fusion method. A broader
definition was proposed by A. Paul [16]: glasses possess the elastic behavior
characteristic of the crystalline state and the viscous behavior of the liquid state.
The most common properties of vials are transparency to visible radiation, mechan-
ical stability, inactivity at the biological level and electrical insulation. However, due
to the possibility of controlling the microstructure either by altering the initial
composition or by application of heat treatments, controlling the nucleation and
crystallization process [17, 18], the properties of a glass can be modified.
The initial chemical composition is a controllable factor that allows to mold some of
the properties of the glass. In any glass, the units that define its structure can be divided
into three categories, according to their structural function: network former,; modifier,
and intermediate units. The network formers are those units which, that without addition
of other components can form glass, such as SiO2, B2O3, P2O5 and GeO2. The network
modifier do not form glass structures but are often combined with a former. Examples of
modifying elements are the alkali elements (Li, Na, K, etc.) and the alkaline earth metals
(Mg, Ca, etc.). The intermediate species are elements that can either have the role of the
network former or the modifier (Al, Nb, etc.).
The formation of glass ceramics, for example by heat treatment of the base glass, is
technologically advantageous for monocrystals and sintered ceramics. It gives the
possibility to control their properties (optical, electrical, mechanical, chemical, etc.) by
the volumetric fraction of the active phase dispersed in the matrix [19]. For example, to
maintain optical transparency, the nucleation and crystal growth process require high
control; it is achieved when the size of the crystals dispersed in the glass matrix is not
high enough to cause light scattering. However, for most electrical applications it is
necessary that the crystals are of sufficient size to have, for example, a ferroelectric
response. This commitment is not easy to meet. Another condition which can maintain
the optical transparency of a ceramic glass is a small difference between the refractive
indexes of crystals and glass matrix. If this difference is insignificant, it allows,
regardless of the size of the crystals, to maintain the optical transparency of the ceramic
glass [20]. Thus, in recent years there has been a growing interest in the preparation,
characterization and technological implementation of glass and ceramics. However, it is
important to note that in general the electrical and optical properties of ceramic glasses
are not as good as those of monocrystals. This is because ceramics show at least two
distinct phases, a crystalline (considered the active phase) and anamorphous (support).
The electrical polarization of the crystals inserted in a glassy matrix is hampered due to
the low value of the dielectric constant of the glassy phase [21, 22]. On the other hand, as
the growth processes of monocrystals have a high economic cost, they are now judged
deprecated forceramic glasses. Some of these also have the advantage of being dense
materials with no porosity [23].
Different processes can achieve crystalline growth with preferred orientation, for
example: mechanical deformation; thermodynamic control; kinetic control (induced
electrochemical nucleation) [18]. In glasses, the use of thermodynamic control is the
most common process. However, control of crystallization with the desired crystal-
line phase is usually difficult as crystallization is a complex process and affected by
various factors such as composition, surface conditions, and heat treatment
profiles [24].
Ceramic glasses containing ferroelectric crystals are a class of materials with high
technological interest as ferroelectric crystals present a structural anisotropy that
results in the formation of electric dipoles and consequently a spontaneous electrical
polarization [20, 25, 26]. A large part of the ferroelectric materials is in the form of
crystalline ceramics. The scientific and technological development of
photonicsrequires new materials that with characteristics such as optical transpar-
ency and also optical activity to be used as amplifiers in communication systems,
energy, instrumentation, etc. In this way, the preparation, and the structural, electri-
cal and optical characterization of ceramic glasses with ferroelectric properties is of
great importance for possible technological applications.
Of the various ferroelectric materials, lithium niobate (LiNbO3), synthesized for
the first time in 1949 by Matthias and Remeika [25], has attracted more attention
from many researchers because of its excellent piezoelectric, electroacoustic, pyro-
electric and photorefractive properties. In the late 1960s, due to the appearance and
development of optical fiber applications, several research centers, namely the Bell
Laboratories [27], studied in detail the structural characteristics and properties of
LiNbO3 crystals, especially their electro-optical properties [28].
The fact that LiNbO3 monocrystals prepared by the usual growth techniques are a
challenging and expensive task, arose the scientific interest in the structural, optical
and electrical study of glass-ceramics containing LiNbO3 crystals, due to the possi-
ble technological applications that can be of interest.
A significant amount of research work in the field of the preparation and crystal-
lization of glass-ceramics containing LiNbO3, by melting quenching exists. In 1980,
Prasad et al. [29] published a study on the preparation of ceramic glasses from the
SiO2-Li2O-Nb2O5 system. The choice of SiO2 as a network former was due to the
fact that it does not contain cations that could alter the crystalline structure of
LiNbO3. SiO2 satisfies this condition due to the reduced atomic radius and
coordination number. Obtaining crystals without crystalline phases is achieved for
a molar amount of SiO2 between 32% and 39%, using the same molar amount of
Li2O and Nb2O5.
The vitreous glass-forming region of the system (SiO2-Al2O3)-Li2O-Nb2O5,
using the melt-quenching method, was presented by Todorovic et al. [30]. They
found that ifthe molar ratio [Nb2O5]/[SiO2] >1 and the molar amount of [Li2O] >25% is,
transparent and homogeneous glasses can be obtained. The application of thermal
treatments to the base glass allowed the crystallization of LiNbO3 particles with a
size of 150–350 nm, maintaining transparency. These glass-ceramics have a
refractive index of 1.84–1.93 and a dielectric constant of 155–185, measured at
1 kHz and room temperature. They observed that an increase in temperature and/or
thermal treatment time leads to an increase in particle size and consequent opacity of
the samples.
14.4 Glass and Glass-Ceramics Preparation (Composition

60SiO2-30Li2O-10Nb2O5 mol%)
The melt-quenching method was used to prepare transparent glasses of the ternary
system SiO2-Li2O-Nb2O5. The high-purity (>99.9%) raw materials used were sili-
con oxide (SiO2-BDH), lithium carbonate (Li2CO3-Merck) and niobium pentoxide
(Nb2O5-Merck). The preparation of the base glass followed the procedure outlined in
Fig. 14.5.The calcination step aimed to remove the CO2 present in Li2CO3, thus
obtaining Li2O. The last step, the re-baking of the glass, carried out soon after the
melt has been poured into the molds, has the objective of minimizing the tensions of
the glass network to avoid rupture. The parameters temperature and time of calci-
nation, temperature, melting time and temperature, and time of heat treatment
(annealing) are characteristic of each system.
The base glasses were subjected to heat treatments after the annealing step to
obtain ceramic glass with the crystalline phase LiNbO3. Figure 14.6 represents the
schematic of the thermal treatment profile used, which was carried out in a horizontal
tubular furnace. The value of the threshold temperature parameter Tp is determined
based on information about the glass thermal behavior.
It is important to note that prior to the heat treatment, it was necessary to polish
each sample to place them with a thickness of approximately 1 mm and with the
opposite surfaces as parallel as possible. Figure 14.7 shows the macroscopic appear-
ance of the base sample and the samples heat-treated at 600 and 650 C. It was
observed that with increasing the treatment temperature the samples became in the
first phase translucent and for treatments at 700 C opaque.
Figure 14.8 shows the macroscopic appearance of the base glass in the presence
of an external electric field. From the analysis of the macroscopic results, there is a
Fig. 14.5 Scheme for the Weighting of starting materials

preparation of base glass by ¯
the melt-quenching method
Mixture of all materials in a planetary ball mill
system for 1 hour at 300 rpm
¯
Calcination of the mixture at 700 ºC for 24 h
¯
Melting process (1300-1450 ºC for 1 h)
¯
The melt is quenched into stainless steel molds
¯
Annealing process
maximum electric field value that can be applied without modifying or even
destroying the glass network. It is also noted that the presence of the electric field
causes to the surface in contact with the negative electrode to have a different
appearance from that which was with contact with the positive one, i.e., on the
surface which was in contact with the positive electrode a white “film”is formed.
In Figs. 14.9, 14.10, and 14.11 TSDC spectra of the base glass and thermally at
600 and 650 C treated samples, respectively, are shown. For a better visualization of the
spectra, an enlargement of the low-temperature range is presented in each figure. All
samples were polarized at 350 K for 10 min, applying an electric field of 50 kV/m.
Fig. 14.6 Scheme of the
Temperature (°C)
heat treatment process Tp
75 °C\h
300 °C\h
4h
Time (h)
Fig. 14.7 Photographs of the base glass and thermally treated samples at 600 and 650 C (smaller
scale range ¼ 1 mm)
Fig. 14.8 Photographs of the base glass after thermal cycle in the presence of an external electric
field (smaller scale range ¼ 1 mm)
Fig. 14.9 Depolarization current as a function of the measuring temperature, for the base glass. For
better visualization the inset figure shows the depolarization current at low temperatures
Fig. 14.10 Depolarization current as a function of the measuring temperature for the glass treated
at 600 C. For better visualization the inset figure shows the depolarization current at low
temperatures
Fig. 14.11 Depolarization current as a function of the measuring temperature for the glass treated
at 650 C. For better visualization the inset figure shows the depolarization current at low T
The base glass only shows a peak of thermally active depolarization current,
whereas the samples thermally treated possess two peaks, one at temperatures below
~230 K and the second at temperatures greater than 290 K. The characteristics of
these peaks are listed in Tables 14.1, 14.2, and 14.3. It is observed that the
temperature of the current peak in the low and high-temperature zones moves to
lower temperatures with increasing heat treatment temperature. The absolute current
value of both peaks also decreases from the base glass to the sample treated at
650 C.
The activation energy Ea for each peak, calculated using the initial rise method is
registered in the following tables. For the depolarization current peak at low tem-
peratures P1, a maximum of Ea is observed for the sample treated at 600 C. In the
high temperature zone, where the second peak P2 is detected, there is a decrease of
the correspondent Ea from the sample treated at 600 to the one at 650 C. The
relaxation time τ, associated with P1, decreases from the base glass to the sample
treated at 600 C, but increases for the sample treated at 650 C. For the depolari-
zation peak P2, the relaxation time decreases with the increase of the thermal
treatment temperature.
The TSDC results of this 60SiO2-30Li2O-10Nb2O5 %mol glass composition
revealed the presence of two depolarization current peaks P1 and P2 in the thermally
treated samples and only one depolarization peak in the base glass (P1). The first
peak P1 is due to localized free-ion motions within the glass network. These motions
give rise to a dipole orientation formed by the ion structurally inserted in the glass
network (Li+ and/or Nb5+) and the non-bridge oxygen (NBO-) ion to which it is
attached [31, 32]. It should be noted that in this situation the ion structurally inserted
Table 14.1 Peak temperature Tp, peak current i(Tp), activation energy Ea, thepre-exponential
parameter τ0and the relaxation time τ, calculated for the depolarization current peak P1, for the
base glass and samples heat-treated at 600 and 650 C
Sample TP1 [K] i(TP1) (1010) [A] Ea [kJ/mol] τ0 (P1) (102) [s] τ (P1) (103) [s]
Base 232.3 4.134 31.574 0.198 4.159 0.065 2.132
600 221.4 2.243 44.123 0.265 1.262 0.025 1.385
650 203.7 0.138 31.259 0.151 2.626 0.049 1.659
Table 14.2 Peak temperature Tp, peak current i(Tp), activation energy Ea,the pre-exponential
parameter τ0 and the relaxation time τ, calculated for the depolarization current peak P2, for the
samples heat-treated at 600 and 650 C
Sample TP1 [K] i(TP1) (1010) [A] Ea [kJ/mol] τ0 (P1) (102) [s] τ (P1) (103) [s]
600 352.3 17.883 84.081 0.959 1.044 0.014 1.841
650 261.4 0.948 50.569 1.843 1.646 0.027 1.685
Table 14.3 Parameters of the data adjustment through the Arrhenius equation on the high-
temperature measurement zone. ln(A) represents the logarithm of the pre-exponential factor, and
Ea is the activation energy for the base glass and samples thermally treated at 600 and 650 C
Sample ln(A) [A] Ea [kJ/mol]
Base 22,928 115,775 0,637
600 16,609 108,232 0,936
650 3621 80,431 0,605
in the glass network, is not in the most favorable energetical position. According to
Agarwal et al. [33], the application of an electric field results in an ion transfer
towards the field thus creating electrical heterogeneity, i.e., electrical dipoles. With
increasing temperature, these ions tend to return to their initial position thus creating
a depolarization current that will give rise to the low-temperature peak P1. The
activation energy, associated with the origin of the electrical dipoles formed by the
ions structurally inserted in the glass network, basically consists of the energy
required for the movement of those ions to different positions within the structural
“void” in which it is located. It can be seen that the valuesobtained for the activation
energy associated with P1 are lower than the values obtained for the dc process
[34, 35] but close to those obtained for the ac conductivity [34, 35] which suggests a
possible relation. Thus, the decrease in peak current P1 with the increase in the heat
treatment temperature is due to the reduction in the number of dipoles related to the
decline in the number of ions structurally inserted in the glass network. The
characteristic temperature of the current peak corresponds to the transition
temperature from the non-equilibrium freezing state of the ions to the steady state,
analogous to that occurring in the glasses with the glass transition temperature
[36]. The temperature shift of the TSDC peak P1 with increasing heat treatment
temperature can be justified based on the results of Agarwal [33] that associates it to
the decrease in the number of network modifier ions.
In this type of glass containing alkaline ions a second depolarization peak can be
detected, centered at higher temperatures and attributed to the dipolar depolarization
coming from the movements of the electric charge transport units in limited paths,
which result from the presence of micro-heterogeneities in the glass [33]. According
to Hong, these movements are essentially associated with the jumps of the ions
structurally inserted in the network, which is within the structural void in which they
jump between different positions. Thus, the dipole formed between these ions and
the non-bridging oxygen ion closest to each “free” ion, should present an activation
energy higher than that associated with P1. This motion is usually associated with a
dc conductivity, giving rise to space-charge polarization. However, Agarwal et al.
contend that this process must have an activation energy lower than the dc activation
energy, which in this case is not verified [34, 35]. Thus, based on the values of the
activation energy, the peak P2 is not assigned to space-charge depolarization but
rather to the depolarization of the interfacial dipoles formed between the sample
surface and the electrode. The decrease in the temperature at which peak P2 occurs
with the rise of the heat treatment temperature may be related to the observed
reduction in the dielectric loss factor [34, 35], which should indicate an increase in
the number of dipoles. It is suggested that the presence of this current peak in the
base glass sample should be detectable at temperatures above 400 K (maximum
measurement limit). In addition to the P2peak and with increasing temperature, an
increase in current is observed in all samples. This current, usually referred to as
background current, was adjusted by an Arrhenius expression to obtain the activa-
tion energy of this thermally activated process. It decreases with increasing heat
treatment temperature indicating a greater mobility of the charge carriers in this
temperature range.
Concerning the relaxation times, assuming that the value of τ calculated for each
peak of depolarization current corresponds to the mean value of the relaxation times
distribution, it is verified that the value of τ for P1 (Table 14.1), displays a maximum
for the base sample. We believe that this maximum may be associatedwith the fact
that this sample has the highest number of ions structurally inserted in the network
and, therefore, a broader distribution of relaxation times. The increase of τ related
with P1 from the sample treated at 600 to the sample treated at 650 C, is related to
the presence of LiNbO3 crystals whose dipoles are difficult to depolarize resulting in
a longer relaxation time. The decrease in the value of τ related toP2, with the increase
of the thermal treatment temperature, suggests that the dipoles that give rise to this
depolarization are not linked to the presence of LiNbO3 crystallites. Knowing that
the density ratio between these crystals and the glass matrix increases and also that
these crystals are difficult to depolarize, the relaxation time would otherwise greater
than τP1. Thus, this relaxation time τP2 should, as indicated, be associated with the
depolarization produced by interfacial sample-electrode dipoles. The decrease in τP2
with increasing heat treatment temperature is due to the decrease in the activation
energy, which will facilitate the mobility and the return to equilibrium positions.
14.5 Conclusions
This contribution shows the principles of the thermally stimulated depolarization

current method. The advantages and disadvantages are discussed; and present an
example of the application of this electrical characterization technique applied to a
glass and glass-ceramic samples is presented. The TSDC results of the 60SiO2-
30Li2O-10Nb2O5 glass composition, with and without heat-treatments reveal the
presence of at least two thermally stimulated depolarization mechanisms. The
depolarization peak current detected at lower temperatures (<250 K) is due to the
depolarization of the dipoles associated with ions structurally inserted in a glass
network. The second peak of depolarization, centered at temperatures >250 K, is due
to the dipolar depolarization from the movements of the electric charge transport
units in limited paths. The presence of depolarization current peaks at temperatures
higher than the second peak should be associated with dipoles formed between the
sample surface and the electrodes.
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Chapter 15
Iron Concentration Effect
on the Microwave Dielectric Properties
of BiNbO4 Ceramics
S. Devesa, M. P. Graça, and L. C. Costa
Abstract Ceramic dielectrics based on bismuth are recognized as materials with

low sintering temperature and have been studied for different applications in the
microelectronic area. Since 1992, when Kagata reported the microwave dielectric
properties of bismuth niobate (BiNbO4), various attempts have been undertaken to
improve the microwave dielectric properties of this ceramic material. Besides the
addition of different oxides, such as CuO, ZnO, V2O5, PbO, Bi2O3 and Fe2O3,
several researchers tried to improve bismuth niobate properties by adding lantha-
nides. In this work, (Bi1-xFex)NbO4 (0.00 1.00) samples were prepared using
the sol-gel method. The fine particles were pressed into cylinders and heat-treated at
specific temperatures. Single phase samples of BiNbO4 (x ¼ 0.00) and FeNbO4
(x ¼ 1.00) were then used as precursors for (Bi1-xFex)NbO4, prepared by the solid
state reaction method. The microwave dielectric characterization of the samples was
performed using the small perturbation method, and related to their structure. With
the sol-gel method the substitution of bismuth by iron was successful, since two
non-stoichiometric phases, Bi1.34Fe0.66Nb1.34O6.35 and Bi1.721Fe1.056Nb1.134O7,
were obtained. Moreover, the inclusion of iron inhibited the formation of low and
high temperature triclinic bismuth niobate. With the solid state technique, the
substitution of bismuth by iron was not achieved; it was observed that the dielectric
constant decreases with the increase of the FeNbO4 phase and that the dielectric
losses follow the opposite trend.
Keywords Bismuth niobate · Sol-gel · Solid state · Microwaves · Dielectric

properties
S. Devesa (*) · M. P. Graça · L. C. Costa


140 S. Devesa et al.
15.1 Introduction
Microwave dielectric materials are a key factor at the present time, with a wide range
of applications from terrestrial to satellite communication systems. In fact, with the
widespread use of mobile phones operating in the microwave frequency regime, the
research and development of dielectric materials that allow device miniaturization
has been one of the biggest challenges in contemporary materials science [1–4].
In order to meet the specifications of current and future systems, enhanced
dielectric materials are required. In fact, dielectric oxide ceramics have contributed
to one significant change in the microwave wireless communication industry by
reducing the size and cost of filters, oscillators and antenna components in applica-
tions ranging from cellular phones to global positioning systems. However, the
constant need for miniaturization can be considered as an incentive for the devel-
opment of more sophisticated materials to perform the same or improved functions
with decreased size and weight [4–6]. The requirements that a ceramic material must
fulfill to be used in microwave frequency range are a high dielectric constant ε0 , low
dielectric losses (tg δ ¼ ε00 /ε0 ), and a low temperature resonance frequency coeffi-
cient τt [7, 8].
In 1992, Kagata reported the microwave dielectric properties of bismuth niobate
(BiNbO4) improved with the addition of CuO and V2O5 [9]. After this first attempt,
several researchers tried to improve the properties of bismuth niobate with the
addition of other oxides, ZnO [7], PbO, Bi2O3 [10], and Fe2O3 [11]. Furthermore,
the addition of lanthanides was also considered in numerous studies. (Bi1-xRx)NbO4
compositions were developed and studied, where R represents different lanthanides,
such as Ce, Nd, Dy, Er, La, Sm, Ta, Gd, La and Eu [12–17].
The measurement of the dielectric properties is essential for the characterization
of these materials, aiming at the different potential applications. In fact, knowing the
properties of a material is important to predict the system performance [4]. Several
methods have been developed to study the dielectric properties of materials;
according to the literature, the most accurate measurements at high frequency can
be performed using the resonant cavity method [4, 18].
The relation between the structural characteristics and the dielectric properties
should also be considered. Since BiNbO4 exists in two polymorphs, orthorhombic
(α) and triclinic (β) [19–22], the influence of the phase transitions on the dielectric
properties of this material is likewise important [19].
In addition, there are other important parameters that require improvement, such
as the density, since dense BiNbO4 ceramics are difficult to obtain [5, 20]. The solid-
state reaction has been the most common method to process bismuth niobate
[21, 23–26]. The powders prepared by this method have a high crystallinity, but
not always in pure and homogeneous phases, because some metastable phases are
obtained under the same conditions [16]. This method may also cause other prob-
lems such as large grain growth, segregation of components and loss of stoichiom-
etry due to the volatilization of bismuth at high temperature [25, 27]. More recently,
15 Iron Concentration Effect in the Microwave Dielectric Properties of BiNbO4 141
the application of wet-chemical techniques such as co-precipitation, alkoxide and

citrate sol-gel and the flux-method lead to interesting results [27].
In particular, the sol-gel method through the citrate route is considered a simple
way to obtain stable precursors and stoichiometric fine powders. This method is
considered promising for achieving high homogeneity, since the formation of citrate
complexes allows to mix the component cations in an atomic scale, thus they can
immediately react with each other at relatively low temperatures [7, 25–27].
In this work, (Bi1-xFex)NbO4 (0.00 1.00) samples were prepared using the
sol-gel method through the citrate route. The fine particles were pressed into
cylinders and heat-treated at four different temperatures between 500 and 1200 C.
Single phase samples of BiNbO4 (x ¼ 0.00) and FeNbO4 (x ¼ 1.00) were then used
as precursors of (Bi1-xFex)NbO4, prepared by the solid-state reaction method.The
microwave dielectric characterization of (Bi1-xFex)NbO4 (x ¼ 0.25, 0.50 and 0.75)
samples obtained with the two methods was performed using the small perturbation
theory, and related with their structure.
15.2 Experimental
15.2.1 Samples Preparation
The first process applied for the (Bi1-xFex)NbO4 samples preparation was the sol-gel
method through the citrate route. The starting materials, bismuth nitrate (Bi
(NO3)35H2O), niobium chloride (NbCl5) and iron nitrate (Fe(NO3)9H2O), were
reagent-grade powders, supplied by Mateck and Merk. A suspension containing
stoichiometric amounts of the starting materials was previously prepared in a minor
amount of hydrogen peroxide (3% V/V) and dispersed in a mixture of citric acid and
ethylene glycol (supplied by Sigma-Aldrich) which performed as chelating agent
and reaction medium. The obtained mixtures were stirred to promote the solubility,
until clear colloidal suspensions were obtained. Finally, the prepared solutions were
dried to evaporate the solvent: the solution with x ¼ 0.00 was dried at 400 C for
48 h; the solutions with 0.25< <0.75 were dried at 300 C for 60 h; the solution
with x ¼ 1.0 was dried at 300 C for 24 h. Subsequently, the obtained powders were
thermally analysed by differential thermal analysis (DTA), performed in a Lynseis
Apparatus type L92/095 in the temperature range of 20–1200 C, with a heating rate
of 5 C/min for the sample with x ¼ 0.00 and 10 C/min for the remaining samples,
using Al2O3 as reference. Finally, the dry powders were pressed into cylinders and
heat-treated according to the DTA results at temperatures between 500 and 1200 C,
using a dwell time of 4 h, with a heating rate of 5 C/min. The flow chart for the
preparation of the samples by the sol-gel method is shown in Fig. 15.1.
For comparison, samples of (Bi1-xFex)NbO4 with 0.25< <0.75 were also
prepared by the solid -state reaction method. In this case, the precursors were the
Fig. 15.1 Flow chart for the sol-gel method
pure single phases that were previously obtained with the sol-gel method. Ortho-
rhombic bismuth niobate and iron niobate were mixed in stoichiometric quantities
with a minor amount of ethanol in a planetary ball mill at 500 rpm. After being
milled for 5 h, the powders were calcined at 300 C for 5 h and heat-treated at
700 C, using a dwell time of 4 h and a heating rate of 5 C/min. This procedure was
repeated, but with triclinic bismuth niobate, also sintered previously by the sol-gel
method. The flow chart for the preparation of the samples by the solid state reaction
method is shown in Fig. 15.2.
15.2.2 Material Characterization
The structural characterization was performed using X-ray diffraction (XRD). The
patterns were obtained on a X’Pert MPD Philips diffractometer (CuKα radiation,
λ ¼ 1.54060 Å) at 45 kV and 40 mA with a curved graphite monochromator, an
automatic divergence slit (irradiated length 20.00 mm), a progressive receiving slit
(height 0.05 mm), and a flat plane sample holder in a Bragg-Brentano parafocusing
optic configuration. Intensity data were collected by the step counting method (step
0.02 in 1 s), in the 2θ angle range from 10 to 60 for the samples prepared by the
sol-gel method and from 10 to 80 for those obtained with the solid-state reaction.
The ceramics bulk density was measured using the Archimedes method in
reference to water. The measurement of the complex permittivity was made using
Fig. 15.2 Flow chart for the solid-state reaction method
the small perturbation theory, with a cavity operating in the TE105 mode at a resonant
frequency of 2.7 GHz. These measurements were made using a HP 8753D coupled
to the cavity resonator.
For a given cavity and a regular sample shape and well-defined dimensions, it
is possible to determine the permittivity of the material. It can be calculated
through the changes in the resonant frequency Δf and of the inverse of the quality
factor Δ(1/Q) of the resonant cavity, when introducing a sample in the cavity,
where the electric field is maximal [28, 29].The shift Δf can be related to the real
part of the complex permittivity ε0 , whereas the change Δ(1/Q) can be related to
the imaginary part ε00 . Considering only the first order electric field perturbation
caused by the sample [28–31], we obtain
Δf V
ε0 ¼ K þ1 ð15:1Þ
f0 v

K 1 V
ε00 ¼ Δ ð15:2Þ
2 Q v
where K is a constant related to the depolarization factor, which depends upon the
geometric parameters, v and V are the volumes of the sample and the cavity,
respectively, and f0 is the resonance frequency of the cavity. Using a sample of
known dielectric constant, in our case polytetrafluorethylene (PTFE), we can deter-
mine the constant K.
Fig. 15.3 X-ray diffraction patterns of (Bi1-xFex)NbO4 samples for x ¼ 0.00, heat-treated (HT) at
850 and 1050 C, and x ¼ 1.00 treated at 1200 C
15.3.1 Structural Characterization
The details of the differential thermal analysis performed with the samples prepared
by the sol-gel method were already reported in previous works [8, 27, 32]; the heat
treatments were performed in agreement with these results. Figure 15.3 shows the
X-ray diffraction patterns of (Bi1-xFex)NbO4 samples for x ¼ 0.00, treated at 850 and
1050 C, and for x ¼ 1.00 for the sample treated at 1200 C, consistent with the
standard ICDD codes 04-010-6365, 04-013-6357 and 04-009-5798, respectively
[33–35].
For x ¼ 0.00, after the treatment of the samples at 850 C, the X-ray diffraction
pattern shows the formation of pure orthorhombic BiNbO4 and, with a further
temperature increase, this phase is totally converted to triclinic BiNbO4. These
results are consistent with the literature reports, since the transition of low temper-
ature β-BiNbO4 to α-BiNbO4 occurs between 600 and 750 C, with the opposite, and
supposed irreversible, transition occurring at 1020/1050 C [36, 37]. For the samples
with x ¼ 1.00, the formation of monoclinic FeNbO4, occurred even at the lowest
heat-treatment temperature, nonetheless, the single phase was obtained only at
1200 C.
The samples with 0.25 0.75, produced by sol-gel were also characterized
using X-ray diffraction. The phases α-BiNbO4 and FeNbO4 were present, as
expected. However, the absence of β-BiNbO4 in the samples treated at 1100 C was
unexpected, since the transition from α-BiNbO4 to β-BiNbO4 occurs according to
previous works at 1020/1050 C [36, 37], and was observed in the sample with
x ¼ 0.00 at 1043 C. This means that the presence of iron inhibits the formation of
high temperature β-BiNbO4. Two non-stoichiometric phases, namely
Bi1.34Fe0.66Nb1.34O6.35 and Bi1.721Fe1.056Nb1.134O7 were found, where the substitu-
tion of Bi3+ by Fe3+ ions was successful. The identification of the crystalline phases
of (Bi1-xFex)NbO4 samples obtained with the sol-gel method is presented in
Table 15.1.
Figure 15.4 shows the X-ray diffraction patterns of (Bi1-xFex)NbO4 samples
prepared by the solid-state reaction method. As one can see, only the starting
materials were identified, this is, the substitution of Bi3+ for Fe3+ ions was not
successful. Furthermore, the possible transformation from high temperature
β-BiNbO4 to α-BiNbO4 in bulk samples, first reported by Zhou et al. [21] in 2007,
was also not observed.
The bulk density values of (Bi1-xFex)NbO4 ceramics, prepared by the sol-gel
method, for 0.25 0.75 were obtained in a previous work [27] and are shown in
Table 15.2. For each of the x values, the bulk density increases when the treatment
temperature increases for 650 C, decreases for the treatment at 800 C, reaching a
minimum value, and increases again. Irrespective of the heat treatment, the samples
with higher bulk density are the ones with x ¼ 0.50.
Considering the samples obtained with the solid-state reaction method, one can see in
Fig. 15.5 that the increase of FeNbO4 promotes a decrease of the bulk density. This
result is in agreement with the literature, since the theoretical density of FeNbO4 ceramic
is 5.40 g/cm3 [38], lower than the theoretical densities of α-BiNbO4 (7.345 g/cm3) and
β-BiNbO4 (7.5 g/cm3) ceramics [13, 14]. Comparing these values with the ones obtained
with the sol-gel method, it is perceptible that with the solid-state reaction method it is
possible a better densification at lower temperatures.
15.3.2 Dielectric Properties
Figure 15.6 presents the measured transmission of 2.7 GHz cavity, the cavity with
the sample holder, and the sample holder filled with either PTFE or with the samples
prepared from orthorhombic bismuth niobate using the solid-state reaction method.
A shift in the resonant frequency of the cavity Δf, is observed.
Since this shift Δf can be related to the real part of the complex permittivity ε0 , it
isto be expected that the sample with x ¼ 0.75 presents the lowest ε0 , followed by the
sample with x ¼ 0.50 and finally the sample with x ¼ 0.25. This prediction will be
confirmed later.
Figure 15.7 shows the real (a) and the imaginary (b) parts of the complex
permittivity at 2.7 GHz as function of x for the samples prepared by the solid-state
reaction method. The dielectric constant decreases with the increase of the FeNbO4
content. The experimental data also suggests that the decrease of the bulk density is
146
Table 15.1 Crystalline phases of (Bi1-xFex)NbO4 samples obtained with the sol-gel method
HT ( C) x ¼ 0.00 x ¼ 0.25 x ¼ 0.50 x ¼ 0.75 x ¼ 1.00
500 Bi2O3 Bi1.34Fe0.66Nb1.34O6.35 Bi1.34Fe0.66Nb1.34O6.35 Bi15NbO25 FeNbO4
Fe2O3 Fe2O3
BiOCl Fe0.33Nb0.67O2
α-BiNbO4
β-BiNbO4
650 BiOCl α-BiNbO4 α-BiNbO4 FeNbO4 FeNbO4
α-BiNbO4 Bi1.34Fe0.66Nb1.34O6.35 Bi1.34Fe0.66Nb1.34O6.35 Bi2O3 Fe2O3
β-BiNbO4
800 – α-BiNbO4 Bi1.721Fe1.056Nb1.134O7 FeNbO4
FeNbO4 FeNbO4 Bi2O3
Bi2O3
850 α-BiNbO4 – – – FeNbO4
Fe2O3
1000 – – – – FeNbO4
Fe2O3
1050 β-BiNbO4 – – – –
1100 – Bi1.721Fe1.056Nb1.134O7 Bi1.721Fe1.056Nb1.134O7 FeNbO4 –
BiFeO3 FeNbO4 Bi15NbO25
1150 β-BiNbO4 – – – –
Bi3.54Nb7.09O22.7
1200 – – – – FeNbO4
S. Devesa et al.
Fig. 15.4 X-ray diffraction patters of the prepared samples with (a) α-BiNbO4 [25α75F – 25% of
α-BiNbO4 and 75% of FeNbO4; 50α50F – 50% of α-BiNbO4 and 50% of FeNbO4; 75α25F – 75%
of α-BiNbO4 and 25% of FeNbO4] and (b) β-BiNbO4 [25β75F – 25% of β-BiNbO4 and 75% of
FeNbO4; 50β50F – 50% of β-BiNbO4 and 50% of FeNbO4; 75β25F – 75% of β-BiNbO4 and 25%
of FeNbO4] as starting material
Table 15.2 Bulk density in x HT 500 HT 650 HT 800 HT 1100

g/cm3 of (Bi1-xFex)NbO4
0.25 3.9 4.1 2.9 5.1
samples obtained with the
sol-gel method 0.50 4.0 4.3 3.4 5.3
0.75 2.8 3.5 2.7 5.0
Fig. 15.5 Bulk density of

(Bi1-xFex)NbO4 samples
obtained with the solid state
reaction method
decisive for the decrease of the dielectric constant. Comparing the ε0 values of the
samples with orthorhombic and triclinic bismuth niobate, one can see that this
constant is higher in the samples with α-BiNbO4, except for x ¼ 0.75. This possibly
means that the increase of FeNbO4 (and consequently, the decrease of the bulk
density), overlaps the effect of the crystal structure. The dielectric constant of (Bi1-
Fig. 15.6 Transmission of

the unperturbed and
perturbed 2.7 GHz cavity,
for the samples prepared by
the solid-state reaction
method, using α-BiNbO4 as
precursor. The lower panel
shows the results enlarged
Fig. 15.7 Calculated ε0 (a) and ε00 (b) of (Bi1-xFex)NbO4 samples prepared by the solid state
reaction method
xFex)NbO4 ceramics, prepared by the sol-gel method, for 0.25 0.75, were
obtained in a previous work [27] and are shown in Table 15.3.
Figure 15.7b shows that the imaginary part of the complex permittivity increases
with the increase of FeNbO4. Confronting this data with the experimental density,
we can see opposite trends, that is, the ε00 values increase with the decrease of the
bulk density. Comparing the ε00 values of the samples with orthorhombic and triclinic
bismuth niobate, one can also see that this constant is higher in the samples with
α-BiNbO4, except when x ¼ 0.75. We can assume, once again, that the increase of
FeNbO4 (and consequently, the decrease of the bulk density), overlaps the effect of
the crystal structure.
15
Table 15.3 Calculated ε0 and ε00 , for the different samples, at room temperature
Sol-gel method Solid state reaction method
HT 700 HT 700
HT 500 HT 650 HT 800 HT 1100 α-BNO þ FNO β-BNO þ FNO
x ε0 ε00 ε0 ε00 ε0 ε00 ε0 ε00 ε0 ε00 ε0 ε00
0.25 4.24 0.08 3.74 0.06 3.65 0.07 10.7 0.22 5.52 0.19 5.36 0.10
0.50 3.81 0.09 3.81 0.09 5.59 0.15 11.2 0.35 5.49 0.27 5.07 0.15
0.75 2.83 0.08 2.37 0.03 3.57 0.15 15.9 2.59 4.37 0.27 4.93 0.30
Iron Concentration Effect in the Microwave Dielectric Properties of BiNbO4
149
The imaginary part of the complex permittivity of (Bi1-xFex)NbO4 ceramics,

prepared by the sol-gel method, for 0.25 0.75, were also presented in a
previous work [27] and are shown in Table 15.3.
Comparing the two methods, one can see that the highest ε0 and ε00 values were
obtained with the sol-gel method, in the samples treated at 1100 C. Nonetheless,
considering treatment temperatures compatible with low temperature co-fired
ceramics, the solid-state reaction method led, in general, to higher dielectric con-
stants and higher losses.
15.4 Conclusion
In the samples prepared by the sol-gel method the substitution of Bi3+ by Fe3+ ions
occurred successfully, with the formation of two non-stoichiometric phases, while in
the solid-state reaction method, only the starting materials were present.
Comparing the bulk density values of the samples obtained with the two methods,
it is perceptible that with the solid state reaction a better densification at lower
temperatures is possible.
Considering the ε0 and ε00 values of the samples with orthorhombic and triclinic
bismuth niobate, obtained with the solid state reaction method, one can conclude that
these parameters are higher in the samples with α-BiNbO4, except when x is
maximum.
Considering treatment temperatures compatible with low temperature co-fired
ceramics, the solid state reaction method led, in general, to higher dielectric con-
stants and higher losses.
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Chapter 16
Dielectric Analysis of Phosphate-Borate
Glass-Ceramics Doped with Alkali Oxides
B. M. G. Melo, M. A. Valente, and M. P. F. Graça
Abstract The synthesis of dielectric materials with high-energy density is funda-

mental for capacitors in power electronics and pulsed power applications. Ceramic
materials have been broadly used for capacitors due to their high dielectric constant.
However, they have some disadvantages such as a low breakdown strength and a
high remanent polarization, which limits their application in high-voltage devices.
The development of glass-ceramics with high dielectric constant and high
breakdown strength can be a promising solution for applications in high-voltage
and impulse power systems. In the present work, functional glasses with the molar
composition 20.7P2O5–17.2Nb2O5–13.8WO3–34.5A2O–13.8B2O3 where A¼Li, Na,
and K were prepared by the melt quenching technique. The base glasses were heat-
treated in air at 800 C for 4 h, which led to the formation of glass-ceramics. The
present work studies the ac conductivity and dielectric properties in the 200–650 K
temperature range of the glass doped with K2O. Impedance spectroscopy was used
in the frequency range 100 Hz to 1 MHz in order to characterize electrically the
glass.
Keywords Glass-ceramics · Glass · Dielectric constant · Impedance spectroscopy ·

Ac conductivity · Electrical characterization · Dielectric relaxation
16.1 Introduction
The formation of glass-ceramics has significant advantages when compared with

single crystals and ceramics because the optical, electrical, mechanical and chemical
properties can be controlled/tuned by the volume fraction of the active crystalline
phase dispersed in the amorphous matrix [1–3]. For this reason, there is a large
interest in the preparation, characterization and technological application of glass
B. M. G. Melo (*) · M. A. Valente · M. P. F. Graça

I3N and Physics Department, Aveiro University, Aveiro, Portugal

154 B. M. G. Melo et al.
and glass-ceramics as substitutes for single crystal materials [1, 2]. Glass-ceramics
with nanosized crystalline particles dispersed in the amorphous matrix are promising
materials since the properties of the materials depend on their specific surface area.
Although the electrical properties of the single crystals are usually better than those
of glass-ceramic material as the amorphous phase generally has a low dielectric
constant, glass-ceramics become an appealing alternative since the growth of single
crystals is expensive [1–3]. Currently, ceramic dielectrics are widely used for
capacitors due to their high dielectric constant. Nevertheless, their application as
high-voltage devices is limited by their high remanent polarization, along with
residual pores and irregular grains in their structure which restrict the increase of
breakdown strength [4, 5]. However, glass-ceramics combine the advantages of
glass and ceramic phases, high breakdown strength and dielectric constant [4–7].
In our recent work [3], we discussed the changes induced by a heat-treatment in
air at 800 C on the structural, electrical and dielectric properties of the glass system
20.7P2O5–17.2Nb2O5–13.8WO3–34.5A2O–13.8B2O3 where A¼Li, Na, and K. The
present work studies and expands the dielectric properties of the K2O containing
sample over a broader range of temperature (200–650 K).
16.2 Experimental
Functional glasses with the desired molar composition were prepared by the melt
quenching technique, using high purity (>99%) P2O5, Nb2O5, WO3, A2CO3 and
B2O3 in powder form. The experimental conditions used for the synthesis of these
glasses can be found in [3]. For the formation of glass-ceramics, the as-grown
glasses were heat-treated in air at 800 C for four hours with a heating rate of
5 C/min. The heat-treatment temperature was chosen according to differential
thermal analysis [8] which revealed an exothermic phenomenon for the as-grown
glasses between 530 and 600 C. The samples discussed in this work will be termed,
A-Li, A-Na, and A-K, according to the alkali oxide included on each glass, Li2O,
Na2O, and K2O, respectively.
X-ray diffraction (XRD) patterns were obtained at room temperature with a
Philips X’Pert MPD diffractometer (CuKα radiation, λ ¼ 1.54056 Å) operating at
45 kV and 40 mA, with a curved graphite monochromator, an automatic divergence
slit, a progressive receiving slit and a flat plane sample holder in a Bragg-Brentano
parafocusing configuration.The acquisition was performed using a scan step of 0.02
in 1 s, in the 2θ angle range of 10–60 . The obtained patterns are shown in Fig. 16.1.
The ac electrical conductivity (σac) of the sample was measured in the tempera-
ture range between 200 and 380 K, using a nitrogen bath cryostat setup and an
Oxford Research IT-C4 controller, and from room temperature up to 650 K in an
electric furnace equipped with a Eurotherm 3508 controller. For these measurements
a Network Analyzer Agilent 4294, operating between 100 Hz and 1 MHz in the
CpRp configuration (capacitance in parallel with resistance) was used. During the
200–400 K measurements, the sample was kept in a helium atmosphere to minimize
16 Dielectric Analysis of Phosphate-Borate Glass-Ceramics Doped with Alkali Oxides 155
KNbWO6
A-K HT @ 800 °C
A-K as-grown
Intensity (arb. units)
o Na2W4O13
# Nb2W3O14 # o A-Na HT @ 800 °C
# # #
o o # o
#o # # # # # # o o
# # o #
A-Na as-grown
· Li6P4W8O32 +
+ A-Li HT @ 800 °C
+ LiNb3O8 ·
+ +
+ + + · ·+ + · + + · +
++ + + + ++
· ++ + + +
Nb26W4O77
Li0.585NbO3
A-Li as-grown
10 15 20 25 30 35 40 45 50 55 60
2q (°)
Fig. 16.1 XRD spectra of the samples (Reprinted with permission from [3]. © 2016 AIP Pulishing)
thermal gradients. Further details about the sample preparation and the mathematical
formalisms used to determine ac conductivity, dielectric constant, dielectric loss, and
loss tangent can be found in [3].
The XRD spectra of the as-grown glasses and heat-treated samples are shown in
Fig. 16.1. Except for the Li2O containing sample, the base glasses show XRD
patterns characteristic for amorphous materials. After the heat-treatment the forma-
tion of crystalline phases was observed for all compositions. Identification and
discussion of the crystalline phases obtained for A-Li and A-Na glasses heat-treated
at 800 C can be found in our recent work [3]. As mentioned before, this contribution
will focus on the results for the K2O containing glass system (A-K).
After the heat-treatment, the A-K sample shows the formation of a single
KNbWO6 phase with a cubic crystal system. The KNbWO6 particles have a
pyrochlore-type structure which possesses useful properties for applications such
as a ionic conductivity (both cations and anions), electrical conductivity, and
magnetic and ferroelectric properties [3, 9, 10]. Additionally, materials based of
KɅWO6 (Ʌ – Nb, Sb, Ta) compounds can be used as catalysts due to their content of
transition metals [9]. To evaluate these potential applications, and to provide further
knowledge about the dielectric properties of glass-ceramic systems with KNbWO6
crystalline particles, the impedance spectroscopy results of the A-K glass heat-
treated at 800 C (A-K glass-ceramic) will be discussed next.
3.0 250 3.5

3.0
Frequency = 2.5 kHz
Frequency = 1 kHz 1000 2.5
3.0
Dielectric constant
2.0
2.5
1000
Tan (d)
200 1.5
100
1.0 2.5
2.0 e' 0.5
Tan (d)
Dielectric constant
Dielectric constant
10 0.0
150 200 250 300 350 400 2.0
Tan (d)
Temperature (K)
Tan (d)
1.5
1.5
100
Frequency = 10 kHz
1.0 100
1.0
0.5 0.5
e' 50
e'
Tan (d)
Tan (d)
10 0.0 0.0
200 250 300 350 400 200 250 300 350 400
(a) (b)
Temperature (K) Temperature (K)
85 1.2 60 0.40
Frequency = 100 kHz
80 Frequency = 1 MHz
0.35
1.0
55
75
0.30
70 0.8
0.25
Dielectric constant
Dielectric constant
50
65
Tan (d)
Tan (d)
0.6 0.20
60
45
0.15
55 0.4
0.10
50
40
0.2 e'
e' 0.05
45 Tan (d) Tan (d)
40 0.0 35 0.00
200 250 300 350 400 200 250 300 350 400
(c) Temperature (K) (d) Temperature (K)
Fig. 16.2 Dielectric constant and loss tangent values of the A-K glass-ceramic as a function of
temperature at (a) 1 kHz; (b) 10 kHz; (c) 100 and (d) 1 MHz. The inset of 2b shows the f ¼ 2.5 kHz
results
Figure 16.2. displays the temperature dependence of the dielectric constant ε0 and
the loss tangent tan(δ) of the A-K glass-ceramic. This figure resumes the results
obtained at different frequencies, namely, 1 kHz, 2.5 kHz, 10 kHz, 100 kHz, and
1 MHz. For all frequencies, the dielectric constant increases with temperature, as
expected. Although at low frequencies (1 kHz and 2.5 kHz) the sample has high ε0
values for glass materials, but those of the loss tangent are also high. For these two
frequencies, we can also see a sharp increase of ε0 above 300 K. This temperature
matches the maximum observed in the loss tangent. This maximum shifts to higher
frequencies with increasing temperature as seen in the inset of 2b. The dielectric
constant (at 300 K and 10 kHz) is 79, which is slightly larger than the value obtained
by Kar and Choudhary [10] in KNbWO6 polycrystalline samples (ε0 ¼ 44 for the
same temperature and frequency). However, the loss tangent value of the studied
sample is also larger, namely 0.62, instead of 0.07 obtained in [10]. The 100 kHz
(Fig. 16.2c), and 1 MHz (Fig. 16.2d) values show that ε0 decreases with frequency,
Fig. 16.3 3D graphics of

the dependence of (a) ε00 and
(b) M00 (b) on frequency and
temperature
which is also the expected behavior. For these frequencies, the loss tangent also
decreases and becomes below 1 in the temperature range examined.
The presence of dielectric relaxations for the A-K glass-ceramic was investigated
using the dielectric loss (ε00 ) and dielectric modulus (M00 ) dependence on both
temperature and frequency. The results are presented in Fig. 16.3. Sometimes the
dielectric relaxation peaks are not visible in the ε00 representation. Therefore, the
complex dielectric modulus (M00 ) formulation is often used to study the dielectric
properties of glasses with a high degree of ionic conductivity since it has the
advantage of minimizing high capacitance effects due to spatial charge accumulation
[3, 11]. However, for this sample it is possible to observe a dielectric relaxation using
both formalisms (permittivity and modulus).
The evolution of a thermally activated relaxation peak, which shifts towards
higher frequencies with increasing temperature is clear for both figures.
Figure 16.3a shows that in the ε00 representation the dielectric relaxation is observ-
able only above 300 K, since below this temperature its peak is centered at a
frequency smaller than 100 Hz and therefore out of the examined frequency window.
However, since the relaxation peak shifts to higher frequencies with the modulus
formalism [12], we can observe the dielectric relaxation at lower temperatures in

Fig. 16.3b. One can also see that both formalisms appear to show a second dielectric
relaxation at lower temperatures (below 250 K), that should be visible at higher
frequencies. This secondary dielectric phenomenon could be the secondary relaxa-
tion, which is faster than the primary and is supposed to originate from
intermolecular motion [11]. We suggest that if we used a frequency range above
1 MHz or if we studied this sample at even lower temperatures (below 200 K), this
second dielectric relaxation could be observable.
Figure 16.4a shows the Nyquist plot in the modulus formalism. The obtained plot
shows a non-Debye behavior, which is typical for amorphous materials [11]. A
Debye-like relaxation behavior is characterized by a single relaxation time. How-
ever, the dielectric relaxation behavior in amorphous materials rarely follows this
simple picture; usually, a distribution of times is found instead [11]. The shape of the
dielectric relaxation (Fig. 16.4a), namely a skewed arc, identifies this as a Cole-
Davidson relaxation type. Figure 16.4b shows the frequency-dependence of the
Fig. 16.4 (a) Nyquist

1.5x10-2
(M*) plot and (b) frequency
354 K
distribution of the imaginary 377 K
part of the dielectric 425 K
modulus, for the A-K glass- 501 K
ceramic 1.0x10-2 556 K
603 K
649 K
M"
5.0x10-3
0.0
0.0 5.0x10-3 1.0x10-2 1.5x10-2

(a)
M'
8x10-3
649 K
556 K
501 K
425 K
6x10-3 377 K
354 K
Temperature
4x10-3
M"
2x10-3
102 103 104 105 106

(b)
Frequency (Hz)
imaginary part of modulus at higher temperatures (room temperature up to 650 K).

Similarly to Fig. 16.3, we can see that the relaxation peak shifts towards higher
frequencies with increasing temperature. However, for temperatures above 501 K,
the relaxation peak shifts to frequencies above 106 Hz, which is outside the fre-
quency window used.
The frequency-dependent conductivity of the A-K glass-ceramic, measured at
different temperatures, can be seen in Fig. 16.5a. Two regimes can be identified
within the measured frequency window: (i) a low-frequency plateau region and (ii) a
high-frequency dispersion region following a power law profile. The plateau region
10-2
AC Conductivity (S/m)
10-3
10-4
354 K 455 K
365 K 603 K
403 K 649 K
10-5
1000 10000 100000 1000000
(a) Frequency (Hz)
Temperature (ºC)
-123 -73 -23 27 77 127 177 227 277 327 377
10-2 High Temperature

Low Temperature
AC Conductivity (S/m)
10-3
1 MHz
-4
10
100 kHz
10-5
10 kHz
10-6
150 200 250 300 350 400 450 500 550 600 650
(b) Temperature (K)
Fig. 16.5 (a) Frequency dependence of σac at several temperatures and (b) temperature dependence
of σac for the A-K glass-ceramic
corresponds to a frequency independent conductivity and can be assigned to the dc

conductivity [11]. The temperature transition point between the nearly frequency
independent and the strong frequency dependence region shifts towards higher
frequencies with increasing temperature. This shift can be related to the dc compo-
nent, which becomes more influent than the ac contribution at higher temperatures
[11]. As observed in Fig. 16.5a, at higher temperatures (650 K) the conductivity
becomes practically frequency independent. At these temperatures, the conductivity
of the sample is over 102 S/m. While the polycrystalline samples prepared in [10]
shown a σac value (at 300 K and 106 Hz) of 5.04 105 S/m, the prepared sample
revealed at the same conditions, a larger conductivity value of 2.62 104 S/m.
Figure 16.5b shows the σac values measured at 10 kHz, 100 kHz and 1 MHz in the
200–650 K temperature range. The conductivity from 200 up to 400 K (Low
Temperature) was measured using the nitrogen bath cryostat setup, while from
room temperature up to 650 K (High Temperature) was used the previously
discussed electric furnace. The first observation we can see is that there is a good
agreement in the experimental values obtained by the two apparatus. For higher
frequencies, and above 350 K, the ac conductivity seems to increase logarithmically.
The behavior of σac evidenced at low temperatures (below 250 K) with increasing
frequency could be related to the second dielectric relaxation previously discussed in
Fig. 16.3 in this temperature range.
The KNbWO6 structures are built up from corner-sharing WO6 octahedra, creat-
ing networks of hexagonal tunnels [13, 14]. Since the univalent cations occupy large
framework voids and are weakly linked to their atoms, they can easily migrate along
the channels within the structure [13, 14].
The ln(σacT) vs. 1000/T dependence can be found in Fig. 16.6a. These results
were measured, once again, with the two setups described above. For the A-K glass-
ceramic, we can identify three temperature regions with a thermally activated
conductivity. As one can see, the activation energy Ea values are different and
increase with temperature. The latter could suggest that, either three different
conduction mechanisms are contributing to the total conductivity, or that the con-
ductivity does not follow the Arrhenius model in this range of temperatures. Another
possible explication could be an increased contribution from the conduction mech-
anism of the KNbWO6 particles when the temperature increases. The Ln(σacT)
vs. 1000/T results for the as-grown A-K glass show that the activation energy
assigned to the dominant conduction process of the base glass, namely, the dipolar
mechanism between the modifier potassium ions and the non-bridging oxygen
anions in their vicinity, is smaller. This could suggest that for the A-K glass-ceramic
the conduction mechanism due to the mobility of K+ in the amorphous matrix
becomes negligible for higher temperatures. Further discussion about the electrical
conductivity of this sample can be found in [3, 8].
Figure 16.6b shows the activation energy values as function of frequency. As one
can see, the activation energy values decrease when the frequency of the applied
electric field increases. This behavior can be explained since, when the frequency is
smaller, the mobile charge carriers travel a longer distance across the glass network
Temperature (ºC)
394 227 127 60 13 -23 -51 -73
3
2 Ea= 48.51 kJ/mol A-K glass-ceramic [f=10 kHz]
Ln(sac´T) [sac measured in S/m at 10 kHz ]
A-K glass-ceramic [f=10 kHz]
1 A-K as-grown glass [f=10 kHz]
0 Ea= 33.04 kJ/mol
-1
-2
-3 Ea= 28.02 kJ/mol
-4
-5
-6
-7
-8 Ea= 24.77 kJ/mol
-9
-10
-11
-12
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
(a) 1000/T (K-1)
Temperature (ºC)
227 127 60 13 -23 -51 -73 -91
0
17.03 kJ/mol
-1
21.74 kJ/mol
-2 28.02 kJ/mol
Ln(sac´T) [sac measured in S/m]
27.93 kJ/mol
1 MHz
-3
-4
-5
100 kHz
-6
-7
-8 10 kHz
Ln(sac´T)
-9 Linear fit 1 kHz
-10
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
(b) 1000/T (K ) -1
Fig. 16.6 (a) Linearization of σac using the Arrhenius equation and (b) analysis of the activation
energy values as a function of frequency
and can go through some conduction channel that requires higher energy for the
migration. On the other hand, for higher frequencies, the charge carriers are excited
with higher energy and oscillate over a shorter distance of the network between
neighboring sites. Hence, they do not have to overcome the highest energetic barriers
to contribute to the conductivity process.
16.4 Conclusions
In the present work, we discussed the ac conductivity and the dielectric properties of
a glass-ceramic system prepared by a heat-treatment in air at 800 C with the
composition 20.7P2O5–17.2Nb2O5–13.8WO3–34.5K2O–13.8B2O3. The XRD pat-
tern of this sample indicate the formation of a single KNbWO6 crystalline phase with
a cubic crystal system.
The dielectric permittivity of the sample is frequency and temperature dependent.
The sample was studied in the 200–650 K temperature range, using two different
apparatus; we found a good agreement between the results obtained from the two
experimental setups. Using both, permittivity and modulus formalisms, a thermally
activated relaxation peak which shifts towards higher frequencies with the increase
of the temperature, was found. The Nyquist plot using the modulus formalism
revealed that this dielectric relaxation is described by a Cole-Davidson model.
In the 200–400 K temperature range, it was found that the activation energy
values decrease when the frequency of the applied electric field increases. The study
of the ac conductivity as a function of frequency for different temperatures showed
that the dc component becomes more influent than the ac contribution for higher
temperatures (above 603 K). Additionally, at higher temperatures (650 K) the ac
conductivity of the sample is over 102 S/m.
References
1. Graça MPF, Valente MA (2011) Glass ceramics with para, anti or ferroelectric active phases,
advances in ceramics – electric and magnetic ceramics, bioceramics, ceramics and environment.
INTECH Open Access Publisher. https://doi.org/10.5772/20854
2. Graça MPF, Ferreira da Silva MG, Valente MA (2008) Structural and electrical characteristics
of LiNbO3 embedded in a 34% SiO2 glass matrix. J Eur Ceram Soc 28(6):1197–1203
3. Melo BMG, Graça MPF, Prezas PR, Valente MA, Almeida AF, Freire FNA, Bih L (2016)
Study of structural, electrical, and dielectric properties of phosphate-borate glasses and glass-
ceramics. J Appl Phys 120(5):051701
4. Li C, Zhang Q, Tang Q, Zhou H, Tan F, Du J (2016) Dielectric and energy storage properties of
BaO-SrO-Na2O-Nb2O5-SiO2 glass–ceramics with different crystallization times. J Electron
Mater 45(6):3025–3029
5. Manoharan MP, Zou C, Furman E, Zhang N, Kushner DI, Zhang S, Murata T, Lanagan MT
(2013) Flexible glass for high temperature energy storage capacitors. Energ Technol 1
(5–6):313–318
6. Zheng H, Pu Y, Liu X, Wan J (2016) Correlation between dielectric properties and crystalli-
zation treatment in potassium sodium niobate glass-ceramics for energy storage application. J
Alloys Compd 674:272–276
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microstructural and dielectric behaviors of barium strontium titanate glass ceramics. J Alloys
Compd 672:52–58
8. Graça MPF, Melo BMG, Prezas PR, Valente MA, Freire FNA, Bih L (2015) Electrical and
dielectric analysis of phosphate based glasses doped with alkali oxides. Mater Des 86(Supple-
ment C):427–435
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spectroscopic studies of the KNbWO6–KSbWO6–KTaWO6 system. Thermochim Acta 506
(1–2):20–27
10. Kar T, Choudhary RNP (2001) Structural dielectric and electrical conducting properties of
KB0 B00 O6 (B0 ¼Nb, Ta; B00 ¼W, Mo) ceramics. J Phys Chem Solids 62(6):1149–1161
11. Melo BMG, Attafi Y, Ben Haj Amara A, Soreto Teixeira S, Costa LC, Valente MA, Graça
MPF. Electrical and dielectric analysis of lithium chloride mixed sodium and lithium phosphate
glasses. Int J Appl Glass Sci
12. Cheng PF, Song J, Li S-T, Wang H (2015) Modulus spectroscopy of grain–grain boundary
binary system. Phys B Condens Matter 459(Supplement C):105–109
13. Mączka M, Ko JH, Włosewicz D, Tomaszewski PE, Kojima S, Hanuza J, Majchrowski A
(2004) Heat capacity and dielectric studies of ferroelectric superionic conductor RbNbWO6.
Solid State Ionics 167(3–4):309–315
14. Chernaya TS, Simonov VI, Muradyan LA (1991) Structural features that cause different ionic
conductivity in RbNbWO and TlNbWO. Butlletí Soc Catalanes Fís Quím Matemàtiques Tecnol
12:427–434
Chapter 17
Electrical and Magnetic Properties
of Yttrium Ferrites
S. Soreto Teixeira, A. J. M. Sales, M. P. F. Graça, M. A. Valente,

and L. C. Costa
Abstract The development of new materials with a high dielectric constant and low
losses is one of the main targets in scientific research for applications. These
properties permit to reduce the size and weight of electronic devices. A potential
candidate for this goal is yttrium ferrite. Powder precursors of yttrium ferrites,
Y3Fe5O12 (YIG) and YFeO3, were prepared by the sol-gel method through the
Pechini route. The powders were heat-treated at 1000, 1300 and 1400 C. The
sample structure was characterized by X-ray diffraction (XRD), the morphology
by scanning electron microscopy (SEM). For all temperatures of the heat-treatment,
the YIG crystalline phase was the predominant and YFeO3 the secondary phase. The
highest percentage of YIG (90%) was obtained in the samples heat-treated at
1400 C. By means of impedance spectroscopy measurements, the dielectric prop-
erties were studied between 100 Hz and 1 MHz, and between 200 and 400 K. The
dielectric constant improves with the growth of the YIG phase, increasing grain size
and decreasing porosity. The highest value of dielectric constant at 1 kHz was
obtained for the sample heat-treated at 1400 C (ε0 ¼ 1750; tan δ ¼ 0.18). The
values of dielectric losses are sufficiently low to use this material in electronic
applications. For all samples, one non-Debye relaxation process was identified; the
relaxation time versus temperature shows an Arrhenius behaviour. Magnetic
measurements (M vs. T and M vs. B) were performed using a vibrating sample
magnetometer (VSM). The dc magnetic susceptibility was recorded under zero field
cooled (ZFC) and field cooled (FC) sequences, with a field of 0.1 T between 7 and
300 K. The results of the magnetic investigations show the presence of a blocking
temperature, TB 50 K for the sample treated at 1000 C and TB 250 K for
samples treated at 1300 and 1400 C, respectively. The saturation magnetization
slightly decreases with the temperature of measurement being of 35 Am2kg1 at
7 K and 25 Am2kg1 at 300 K.
S. Soreto Teixeira (*) · A. J. M. Sales · M. P. F. Graça · M. A. Valente · L. C. Costa


166 S. Soreto Teixeira et al.
Keywords Yttrium ferrites · Impedance spectroscopy · Magnetic properties ·

Dielectric relaxation
17.1 Introduction
Ferrites possess interesting properties with potential industrial applications such as

in electrochromic displays, waste-water cleaning, electrodes in rechargeable batte-
ries and as strong oxidizing agents [1, 2].
The garnet Y3Fe5O12 (YIG) has the general formula 3M2O35Fe2O3, where M is
yttrium. The yttrium cations are of the type M3+ which makes electron hopping
through the material very difficult and the resistivity is extremely high [3]. YIG is a
ferrimagnetic material with interesting dielectric and magnetic properties, such as a
controllable saturation magnetization, low dielectric losses and small linewidth in
ferromagnetic resonance [4]. The magneto-electric effect of YIG is very remarkable
due to the direct interaction between dielectric and magnetic properties [5]. Due to its
interesting magnetic and magneto-optic properties it can be used in the telecommu-
nication area, at very high frequencies and data storage applications [2, 3, 6]. This
material can also be used in electronic devices such as insulators, circulators, trans-
mitters, and transducers of acoustic energy [3].
Several techniques can be used to prepare the crystalline YIG phase. The con-
ventional solid state reaction method uses yttrium and iron oxides. This method
requires high temperatures of sintering; particles with micron size were obtained
[7]. To prepare fine particles (submicron size) at lower temperatures, wet chemical
routes can be used such as sol-gel, co-precipitation or the glycothermal synthesis [7].
On the other hand, YFeO3 belongs to the MFeO3 rare-earth orthoferrite perov-
skites, and has been studied due to its applications in solid-oxide fuel cells [6],
photocatalysis, vehicle catalytic converters [8, 9], optical devices of ultrafast optical
switches, magnetic fields sensors, and magneto-optical current sensors [10]. It is also
a candidate for applications in the field of chemical sensors [11]. The dielectric
properties, high permittivity, and low dielectric losses permits its use in wireless
communication systems. YFeO3 is an antiferromagnetic material with a high Néel
temperature (TN ¼ 640 K) and a high resistivity [12].
The main goal of this work is to correlate the dielectric and magnetic properties
with the structure and morphology of yttrium ferrites, prepared by the Pechini route
at different heat treatment temperatures.
17.2 Experimental
The yttrium ferrite powders were obtained by the sol-gel method, through the
Pechini route which has the advantage that no strong acids/bases or organic com-
pounds are needed, besides being a low-temperature process. In this route, the
17 Electrical and Magnetic Properties of Yttrium Ferrites 167
polymerizable complex is based on the poly-esterification reaction between citric

acid (CA) and ethylene glycol (EG) [13, 14]. In detail, the metal solutions, yttrium
nitrate [Y(NO3)3.6H2O, purity>99%, Aldrich] and iron nitrate [Fe(NO3)3.9H2O,
Mateck], were used as starting materials, citric acid and ethylene glycol as chelating
agents to polymerize the mixture. After the preparation of an aqueous solution of
nitrates, it was mixed with CA to promote the complex formation of the metal ions;
there after EG was added as a dispersant [3].
The suspension contains stoichiometric amounts of each metal, and are charac-
terized by the use of an excess of CA (1:3 molar ratio) with a molar ratio between
CA:EG of 2:3. To promote the solubility, the suspension was stirred for 30 min at
room temperature. The final suspension, after the addition of EG, was mixed for
24 h. To evaporate the solvent, the solution gel was dried at 250 C for 60 h. The
obtained powder was pressed into pellets and heat-treated at 1000, 1300 and 1400 C
(HT1000, HT1300 and HT1400 respectively) for 4 h with a heating rate of 5 C/min.
X-ray diffraction (XRD) patterns were obtained with a Philips X’Pert diffractom-
eter (CuKα radiation, λ ¼ 1.54056 Å) at 40 kV and 30 mA, with a curved graphite
monochromator, an automatic divergence slit (irradiated length 20.00 mm), a pro-
gressive receiving slit (height 0.05 mm) and a flat plane sample holder in a Bragg-
Brentano parafocusing optics configuration. Intensity data were collected by the step
counting method (step 0.02 in 1 s) in the 2θ angle range of 10–60 .
Impedance spectroscopy (IS) was used to analyse the samples in pellet form, with
a thickness of about 1 mm and the opposite surface sides painted with silver paste.
The electrical signal was measured with an impedance analyzer Agilent 4294A.
These measurements were performed in the frequency range from 102 to 106 Hz
from 200 up to 400 K. In order to improve the heat transfer and to homogenize the
temperature, the sample holder was maintained in a helium atmosphere during the
measurements.
The magnetic properties of the samples were measured with a vibrating sample
magnetometer (VSM) from Cryogenics. The magnetic properties as a function of
temperature were acquired in field cooling (FC) and zero field cooling (ZFC) modes,
applying a magnetic field of 0.1 T. The dc magnetic susceptibility as a function of
temperature from 7 to 300 K was acquired in zero field and field cooling. The M vs.
B hysteresis curves were obtained at different measurement temperatures.
The diffractograms of the samples HT1000, HT1300 and HT1400 powders are
shown in Fig. 17.1. In all samples, two crystallographic systems are present: a
cubic (Y3Fe5O12) and an orthorhombic (YFeO3) one with different weight
percentages.
In order to obtain information about the composition of each crystal phase, the
Rietveld refinement of the X-ray data was performed using the DBWS Tools 2.4
Fig. 17.1 XRD patterns of

the samples HT1000,
HT1300 and HT1400
powders
software. The parameter S (Goodness of Fit) has values between 1.17 and 1.37
which indicates a good fit for the refinements of all samples.
The cubic Y3Fe5O12 crystalline phase has the highest weight percentage
(Fig. 17.1) in all samples, with the main diffraction peaks at 2θ 28, 32, 36,
54 and 56 [15]. The presence of a peak at about 2θ ¼ 33 indicates the presence
of the orthorhombic YFeO3 crystal phase [15, 16]. The sample HT1400 presents a
significant increase in the weight percentage of Y3Fe5O12 to 90.38% and a minimum
of 9.62% for YFeO3.
Figure 17.2 presents the samples surface micrographs. In all samples, grains with
similar shapes but different sizes between 2 and 10 μm are perceptible. The grain size
increases and the porosity decrease with the rise of the heat treatment temperature.
From impedance spectroscopy, the measured values of Cp and Rp, allow the
calculation of the real (ε0 ) and imaginary (ε00 ) parts of the complex permittivity [17]:
d
ε0 ¼ C p ð17:1Þ
Aε0
d
ε00 ¼ ð17:2Þ
ωRp Aε0
where d represents the sample thickness, A the area of the electrodes, ε0 the empty
space permittivity and ω the angular frequency. Figure 17.3 shows the dependence
of the real and the imaginary parts of the permittivity with frequency for the sample
HT1400.
In Fig. 17.3, one relaxation process and low losses for sample HT1400 are visible.
As expected, the relaxation frequency increases with temperature. For high
temperatures and low frequencies, the Maxwell-Wagner-Sillars (MWS) effect is
present. According to the literature, this phenomenon can be attributed to the
contribution of YFeO3 phase reaching values of the dielectric constant higher than
Fig. 17.2 SEM micrographs of samples HT1000, HT1300 and HT1400
Fig. 17.3 Dielectric 190-400 K HT1400

constant and dielectric
losses vs frequency 3000
(sampleHT1400)
T
2000
e'
1000
0
102 103 104 105 106
Frequency [Hz]
4
190-400 K HT1400
3 T
tand
102 103 104 105 106

Frequency [Hz]
104 [18]. Nevertheless, also the pure YIG phase can reach values of 1000
[5]. Actually, the influence of the MWS effect is not much pronounced at frequencies
higher than1 kHz and temperatures around room temperature. A comparison at
different temperatures (220, 300 and 330 K) and a frequency of 1 kHz as a function
of the heating treatment is shown in Fig. 17.4.
Fig. 17.4 Dielectric 2100 T= 220 K

constant and dielectric T= 300 K
1800
losses at a frequency T= 330 K
f ¼ 1 kHz 1500
1200
900
e'
150
100
50
0
HT1000 HT1300 HT1400
Heat Treatment [ºC]
3.0
T= 220 K
T= 300 K
2.5 T= 330 K
2.0
Tan d
1.5
1.0
0.5
0.0
HT1000 HT1300 HT1400

Heat Treatment [ºC]
Figure 17.4 allows to conclude that the sample which has the lowest losses and
the highest values of the dielectric constant is HT1400. This fact can be due to the
increases of the grain size and the decreases of porosity (Fig. 17.2) in combination
with the right composition of YIG and YFeO3 crystal phases (Fig. 17.1).
The magnetic measurements were done under ZFC conditions with an applied
magnetic field (B) of 0.1 T, from 7 K up to 300 K. At 300 K, magnetization (M)
versus B measurements were carried out. Then, FC measurements were performed
from 300 K down to 7 K under the magnetic field of 0.1 T. Again, at 7 K, M versus
B measurements were performed. The dependence of the magnetic susceptibility on
the temperature is shown in Fig. 17.5.
The magnetic susceptibility varies with the heat treatment temperature being between
305 Am2kg1 T1 (HT1300; HT1400) and 325 Am2kg1 T1 (HT1000) in the FC
sequences and from 300 Am2kg1 T1 (HT1300; HT1400) to 315 Am2kg1.T1
(HT1000) in the ZFC sequences. A decrease of the magnetic susceptibility with
330
HT1000_FC @ 0.1 T
320
Magnetic Susceptibility [(Am2kg-1)/T] HT1000_ZFC
310
300
290
280
Magnetic Susceptibility [(Am2kg-1)/T]
306 HT1400_FC
270 1300_FC
304
260 HT1400_ZFC
302
250 1300_ZFC
300
240 10 15 20 25 30 35 40 45 50
Temperature [K]
230
0 50 100 150 200 250 300
Temperature [K]
Fig. 17.5 Magnetic susceptibility versus temperature, recorded under field cooled conditions with
an applied magnetic field of 0.1 T between 7 and 300 K
increasing measurement temperature is observed; this behaviour was expected as it is

characteristic for ferrimagnetic materials [19, 20]. It is also visible that with increasing
temperature of the heat treatment, the blocking temperature (TB) also increases being
50 K for sample HT1000 but 250 K for samples HT1300 and HT1400. This fact
may be related to the increasing of the grains size for samples treated at a higher
temperature.
Figure 17.6 shows the magnetization versus the applied magnetic field, measured
at 7 K and 300 K, respectively. At T ¼ 7 K, for sample HT1000 it is visible that the
saturation magnetization (Ms) is not achieved; this can be related to the presence of
the YFeO3 phase, which is antiferromagnetic, and the smaller size of the particles
since this behaviour does not occur for sample HT1300, which has a similar amount
of the YFeO3 phase. For sample HT1400 a saturation magnetization of Ms ¼ 35 Am2
kg1 was obtained which is in agreement with literature data for the YIG phase
[21]. At room temperature, all samples have similar values of the saturation magne-
tization, which is near to that reported in the literature for YIG phase [21] which is
the majority crystal phase in all samples. In relation to the YFeO3 crystal phase and
according to the literature, the magnetization does not saturate in magnetic fields up
to 6 T, showing a magnetization of 4 Am2kg1 at 1.5 T [22] and 3 Am2kg1 at 6 T
[18]. According to our results, at room temperature, the saturation magnetization is
independent of the temperature of the heat treatment. This means that the composi-
tion of YIG and YFeO3 does not interfere in the magnetic hysteresis results.
Magnetization (Am2Kg-1)
Fig. 17.6 Magnetic
hysteresis curves at T ¼ 7 K 60
T= 7K
and T ¼ 300 K 50 HT1000
40
30 HT1300 / HT1400
20
10
0
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
-10
B(T)
-20
-30
-40
-50
-60
Magnetization (Am2kg-1)
30
T=300 K
20 HT1000 / HT1300 / HT1400
10
0
-10 -8 -6 -4 -2 0 2 4 6 8 10
B(T)
-10
-20
-30
17.4 Conclusions
Yttrium ferrites can be obtained by a sol-gel method using iron and yttrium nitrates
as raw materials. Cubic ferrite Y3Fe5O12 (YIG) is predominant in all samples with
the maximum for sample HT1400 (~90%).
One dielectric relaxation process is observed for all samples. The MW effect, due
to interfacial polarization, is also present for high temperatures and low frequencies.
Nevertheless, at frequencies higher than 1 kHz this contribution is not very relevant,
and the dielectric constant is still huge (>1000). The right combination of the YIG
and YFeO3, the structural changes, the increases of the grain size and the decreases
of the porosity combine giant dielectric constants with low losses. As a consequence,
sample HT1400 could be a potential candidate to be used in electronic devices such
as capacitors.
The magnetic susceptibility decreases with the heat treatment temperature. We

obtain typical hysteresis curves; the saturation magnetization slightly decreases with
the measurement temperature as expected. According to the dielectric and magnetic
results, the composition of the YIG and YFeO3 crystal phases, the structural changes
and the increase of the grains size affect the dielectric and magnetic properties of
yttrium ferrites.
References
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material. Mater Res Bull 47:2294–2298
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4. Sánchez RD, Rivas J, Vaqueiro P, Caeiro D (2002) Particle size effects on magnetic properties
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8. Li X, Tang C, Ai M et al (2010) Controllable synthesis of pure-phase rare-earth orthoferrites
hollow spheres with a porous shell and their catalytic performance for the CO þ NO reaction.
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9. Pena MA, Fierro JLG (2001) Chemical structures and performance of perovskites oxides. Chem
Rev 101:1981–2017
10. Shen H, Xu J, Jin M, Jiang G (2012) Influence of manganese on the structure and magnetic
properties of YFeO3 nanocrystal. Ceram Int 38:1473–1477
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properties. J Magn Magn Mater 321:3274–3277
12. Rearick TM, Catchen GL, Adams JM (1993) Combined magnetic-dipole and electric-
quadrupole hyperfine interactions in rare-earth orthoferrite ceramics. Phys Rev B 48:224–238
13. Kuz AP, Abakumov PV (2011) Raman imaging of domains and fine structure of domain walls
in YFeO3 crystals. Tech Phys Lett 37:1058–1061
14. Kuzmenko AP, Abakumov PV, Dobromyslov MB (2012) Domain wall structure of weak
ferromagnets according to Raman. J Magn Magn Mater 324:1262–1264
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Part V
Materials: Graphene, Nanotubes and
Nanodiamonds
Chapter 18
Nanostructured Carbon Materials:
Synthesis and Applications
Alejandro Ansón-Casaos, Enrique Garcia-Bordeje, Ana M. Benito,

and Wolfgang K. Maser
Abstract The family of carbon nanostructures includes a great number of forms

with different properties derived from their reduced dimensionality. In particular,
carbon nanotubes (CNTs) and graphene show special electronic, optical, mechanical
and chemical properties that allow their potential application in new materials and
devices. The real possibilities of pristine CNTs and graphene depend on their
synthetic origin, which can be roughly classified into methods starting from graphite
and chemical vapor deposition (CVD) processes. Applications of CNTs and
graphene encompass electronics, energy devices, multifunctional composites, catal-
ysis and sensors. Their reduced size and weight suggest potential uses in portable,
wearable and mobile equipment with a high added value.
Keywords Nanotube · Graphene · Electronic properties · Energy · Composite ·

Sensor
18.1 Introduction
Carbon nanomaterials have been central in the development of nanoscience and

nanotechnology. The discovery of carbon nanotubes (CNTs) in 1991 [1], and later of
graphene [2], led to a new way of thinking in physics and materials science.
Previously, the synthesis of fullerenes in the 1980s was also a revolution in chem-
istry and materials chemistry [3]. Nowadays, carbon allotropes constitute a family
that is the paradigm of how the reduction of dimensions to the nanoscale leads to
quantum confinement, and thus to new physical properties, starting from electronics
and optics, but also covering thermal, mechanical and chemical properties, and even
fluid dynamics.
A. Ansón-Casaos (*) · E. Garcia-Bordeje · A. M. Benito · W. K. Maser

Instituto de Carboquímica, ICB-CSIC, Zaragoza, Spain

178 A. Ansón-Casaos et al.
Many different methods have been utilized for the synthesis of carbon
nanostructures, particularly in the cases of CNTs and graphene. Fullerenes were
first discovered as the products of experiments in an electric arc discharge reactor
with graphite electrodes. Also CNTs, both multi-walled (MWCNTs) and single-
walled (SWCNTs), were later observed by electron microscopy in an arc-discharge
cathodic deposit. Chemical vapor deposition (CVD) methods have been successfully
applied to the synthesis of CNTs from gaseous carbon precursors; high quality
SWCNTs can be synthesized from graphite by laser ablation methods. Graphene
was first prepared by exfoliation from graphite using an adhesive tape, while the
current methods of production include CVD and liquid phase exfoliation of graphite,
which commonly involves the interesting product known as graphene oxide (GO).
Applications of carbon nanomaterials are being investigated in many fields, some
of them are already commercial, including additives for lithium ion batteries, new
composites as new generation carbon fiber materials, etc. The utilization of carbon
nanostructures opens up a wide field both in device miniaturization and in the
improvement of the properties of bulk materials through their addition in small
amounts.
In this mini-review, the most outstanding types of carbon nanostructures are first
summarized and briefly described. All the nanomaterials mentioned, but especially
CNTs and graphene, are currently the focus of a great number of scientific research
works. The effects of dimensionality reduction are illustrated, specifically with the
example of the optical spectra of SWCNTs. In the next section, the most common
methods for the synthesis of CNTs and graphene are described. Knowledge on the
nanostructures synthetic origin is often of paramount importance, as it limits the
material properties and thus the potential applications. In the final section, the
applications of CNTs and graphene are reviewed, mostly through studies developed
at the Institute of Carbon Chemistry, ICB-CSIC. The applications cover the energy
field, catalysis, polymer composites, inorganic composites, electronic applications,
and sensors.
18.2 The Family of Carbon Nanomaterials
Diamond and graphite are the classical forms of elemental carbon in the solid state;
the crystalline organization of carbon atoms is respectively purely tetrahedral sp3 and
trigonal sp2. The natural appearance of linear acetylenic carbon or carbine, the
allotrope with pure linear sp geometry, is still a topic of discussion. The discovery
of fullerenes in 1985 was one of the greatest hits of physics and chemistry in the last
years of the twentieth century [3]. The existence of fullerenes led to a revision of the
basic concepts in carbon chemistry and general chemistry, since their characteristics
of bonding and symmetry were unknown. In particular, the possibility of synthesiz-
ing closed hollow structures of only carbon atoms would have been unimaginable, as
carbon bonds have to adapt to allow pentagonal rings. In fullerenes, the carbon bond
geometry is between sp2 and sp3; the larger the number of atoms in the structure, the
18 Nanostructured Carbon Materials: Synthesis and Applications 179
nearer to sp2. Soon after the discovery of fullerenes, their chemistry was studied, and
it resulted to be extremely rich. Fullerenes can enclose metal atoms in their inner
cavities, and can be also covered by one or several layers of ordered metal atoms. In
addition, a great number of organic moieties can be bonded to fullerenes, resulting in
new molecules.
MWCNTs were observed in 1991 during an investigation on fullerenes [1], while
the existence of SWCNTs was demonstrated later in 1993 [4, 5]. CNTs are formed
by cylindrical seamless graphene layers, in which carbon atoms present nearly sp2
geometries, and are typically closed at the ends by fullerene-like caps. MWCNTs
have 2–50 concentric layers, an interior diameter of 2–10 nm, an exterior diameter of
15–30 nm, and an interlayer distance of 0.34 nm, which is nearly identical to the
separation between graphene layers in graphite. SWCNTs have diameters of
0.71–3 nm and easily join longitudinally to form bundles. Many different SWCNT
conformations exist depending on the wall helicity. Despite having a great stability,
CNT walls can be functionalized with many chemical groups, similarly to fullerenes.
It can be stated that the discovery and study of CNTs has been central in the
development of nanoscience and nanotechnology. Apart from fullerenes and carbon
nanotubes, other related morphologies have been observed and studied, such as
nanoonions and nanohorns [6, 7].
The idea of isolating a single graphene layer was realized in 2004 through
mechanical exfoliation of graphite with an adhesive tape [2]. A single sp2 carbon
layer is very unstable and tends to fold, stack, or collapse. Therefore, a graphene
layer can be only stabilized either on a solid substrate or in a liquid medium.
Nowadays, graphene materials encompass a great variety of forms including single
sheets on different solid substrates [8], multi-platelet graphene [9], graphene
nanoribbons (GNRs) [10], GO and reduced graphene oxide (RGO) [11, 12]. More
recently, a great interest has been focused on graphene flakes with reduced lateral
dimensions, which are generically called graphene quantum dots (GQDs). Other
new nanomaterials such as carbon dots and nanodiamond complete the large family
of carbon nanostructures [13].
Nanostructured materials are low dimensional structures at the nanoscale. In other
words, at least one of the spatial dimensions is reduced to the nanoscale. In such
conditions, electrons are affected by spatial confinement and thus the electronic
properties of the materials are modified. Whilst diamond and graphite are classical
three dimensional (3D) structures, the thickness of a single graphene layer is <1 nm,
so it is negligible against the lateral sheet dimensions (up to several μm), thus
graphene can be conceptually understood as a 2D nanostructure. The configuration
of carbon atoms at the edges is relevant for the graphene sheet properties, particu-
larly when lateral dimensions are very small, for example in GNRs. In CNTs, the
length/diameter aspect ratio is typically so high that they can be considered 1D.
Several different carbon nanostructures behave as 0D entities or quantum dots,
including fullerenes, GQDs and carbon quantum dots. Finally, classical porous
materials such as activated carbons (ACs) are sometimes considered as fractal
structures with a reduced dimensionality between 2D and 3D. ACs can confine
ordered atoms or molecules in their small pores and can act as molecular sieves.
Fig. 18.1 Optical

absorption spectra in the
visible-near infrared region
for surfactant-stabilized
aqueous suspensions of
different powder materials:
a graphitic soot, b CVD
MWCNTs, c laser-grown
SWCNTs, d arc-discharge
SWCNTs, e CoMoCAT®
SWCNTs, and f HiPco®
SWCNTs. Both CoMoCAT
®
and HiPco® are
commercial products
synthesized by CVD
methods. All suspensions
were diluted in their
respective aqueous media
until reaching 0.4
absorbance units at 850 nm
One of the effects of dimensionality reduction and electronic confinement is the

special optical response of SWCNTs [14–16]. Figure 18.1 shows optical absorption
spectra of four different SWCNT samples compared to a MWCNT sample and a
graphitic material. All the starting powders were dispersed in a surfactant by
ultrasound treatments and centrifugation. The graphitic soot (Fig. 18.1a) absorbs
light in the whole visible range, decreasing towards the infrared. This absorption
profile is typical of carbon materials, in accordance with their black color, and related
to collective electronic excitations along the sides of sp2 domains. Qualitatively
similar spectra are measured for most of the carbon materials including MWCNTs
(Fig. 18.1b), as the single nanotube optical response is hindered by their multi-
layered structure. Apart from the typical spectral background of carbon materials,
SWCNTs present particular absorption features, which are associated to the nano-
tube diameter and conformation. Electron confinement occurs in the so-called 1D
van Hove singularities, and the permitted transitions between those particular elec-
tronic states give rise to the SWCNT absorption spectra. Each SWCNT type should
give quite sharp spectral peaks. However, in typical SWCNT samples, which contain
complex mixtures of many SWCNT types, wide bands are observed as a superpo-
sition of individual peaks (Fig. 18.1c–f). It can be observed that absorption spectra
are indicative of the SWCNT synthetic origin. Also, absorption features are sensitive
to SWCNT purity, functionalization and structural quality [17–19].
Other effects of electronic confinement are SWCNT fluorescence phenomena

[20, 21], the electronic structure of graphene and GNRs, the fluorescence of GQDs,
and so on. Also, many other special properties (optical, mechanical, chemical) are
derived from the particular electronic structure of carbon nanomaterials.
18.3 Synthesis of Carbon Nanotubes and Graphene
The synthesis of CNTs can be performed by different methods, all of them based on
the generation of small reactive molecular carbon units from either graphite or
simple organic gases. Under certain process conditions, often in the presence of
catalyst metal particles, the reactive carbon units combine to yield the cylindrical
structures. Graphite evaporation can be effected in an electric arc reactor or by laser
ablation methods, in which very high temperatures (>5000 ) are locally achieved.
On the other hand, decomposition of organic gases and the subsequent CVD process
to give the nanostructures are performed in reactors at a constant temperature of
around 1000 C or lower.
The electric arc reactor method can be utilized for the synthesis of both fullerenes
and CNTs under slightly different conditions. The graphite anode is evaporated
when a high electrical current is passed in a sub-atmospheric pressure of certain
ionizing gases. Fullerenes appear in the soot that covers the inner reactor walls after a
discontinuous evaporation process without catalysts, and can be separated from the
impurities by extraction in organics, particularly in toluene. MWCNTs were first
observed in the inner part of the cathodic deposit. The yield of the process for the
synthesis of MWCNTs in the arc reactor can be improved just by slight modifica-
tions in the operation conditions for fullerene production [22, 23]. When the graphite
anode contains certain metal catalysts (Fe, Ni, Co), SWCNTs appear in the material
growing around the cathode and in the soot covering the inner reactor wall
[4, 5]. Higher yields of the SWCNT production were achieved with binary metal
catalyst mixtures, in particular Ni/Y [24]. The temperatures between the electrodes
during operation are very high (>5000 ) but decrease very fast towards the reactor
walls, generating strong gradients, so the growing conditions of the nanostructures
are not determined [25]. Arc-discharge CNTs show a high structural quality with a
low number of defects, although the as-synthesized powders contain impurities
(metal catalysts, graphite particles, amorphous carbon) that often have to be removed
by purification post-treatments.
In laser synthesis methods, a graphite target is exposed to a laser beam, which
increases the temperature of the solid until vaporization. From the gas phase, small
carbon units react and can produce nanotubes, which settle on the chamber walls as
soot. The laser source, which can be both pulsed and continuous, is often a YAG or a
CO2 laser [26]. A nearly identical synthesis concept can be developed with a solar
concentrator [27]. The resulting CNTs show high structural qualities, but the prod-
ucts contain impurities, similarly to arc-discharge CNTs.
In CVD methods, a gaseous precursor, typically CO, CH4 or C2H2, acts as the
carbon source, and the CNTs grow on catalyst metal particles. The method provides
a large number of variable parameters, including the carbon source, carrier gas,
temperature, catalyst composition and catalyst preparation [28–32]. The catalyst can
be prepared from metal ion solutions and organometallic complexes, and it can be
inserted in the reactor either as an aerosol or supported on silica, alumina and other
materials. Since catalyst particles can be placed at defined positions on the support, it
is possible to grow CNT forests, nanotubes on AFM cantilever tips and nanotubes
between two electrodes. CVD methods allow the synthesis of many different CNT
types and they are the preferred ones for industrial production.
CVD methods have been also successfully utilized for the synthesis of graphene.
It has been demonstrated that the dimensions of the as-synthesized graphene
domains (1 μm–1 cm) can be on the order of that of highly crystalline graphite
[8]. Graphene is first synthesized on catalyst metal sheets, typically made of copper,
nickel and other metals, then it can be transferred to other supports, usually with a
certain loss in its structural quality. CVD-grown graphene is expected to reach an
industrial demand, particularly in electronic applications [8].
Graphite exfoliation is the other route (top-down) for the synthesis of graphene.
The micromechanical cleavage of graphite through the adhesive-tape method was
utilized for the first experimental description of graphene, and it can be still useful in
laboratory works. Other methodologies such as milling and chemical exfoliation in
the liquid phase are the alternative for industrial applications in functional composite
materials and inks. Physical milling of graphite leads to multi-platelet graphene
materials that might be applied in polymer composites with improved frictional and
mechanical properties [9]. Liquid phase exfoliation has been widely utilized in
laboratory research, and it is usually performed through a modified Hummers
methods that involve a sequence of acid oxidant treatments [12]. Liquid phase
exfoliation is also possible in a surfactant or in organic solvents. A particular case
of liquid phase exfoliation is the preparation of graphene nanoribbons from
MWCNTs by unzipping in acid oxidant media [33, 34]. Small size GQDs can be
also synthesized by chemical oxidation, and by electrochemical cleavage of graphite,
a clean method that is interesting for biological applications.
18.4 Applications of Carbon Nanotubes and Graphene
Applications of carbon nanostructures can be grouped, according to the appearance

of the nanostructure, into those using individual nanostructures, assemblies of
nanostructures, and composite materials [35]. An special mention must be also
made of processes that substantially modify the nanostructure properties, including
functionalization, dispersion in a liquid, etc. [35] In the following, the most direct
classification is followed, which is based on the application field. Several topics are
briefly reviewed, including energy devices, catalysis, light multifunctional polymers,
and sensors.
18.4.1 Energy Devices
Carbon nanomaterials have been integrated in different parts of energy devices,

sometimes as the whole component, but most commonly as additives to other active
materials. Since carbon nanomaterials possess high aspect ratios and good electrical
and thermal conductivities, they can act as wires for electronic transport and heat
dissipation channels in devices such as batteries, electrochemical double layer
capacitors (EDLCs), and solar cells.
CNTs, GO and RGO were soon tested as electrodes for EDLCs, also called
supercapacitors. The powder materials can be compressed in a mold and impreg-
nated with the electrolyte, which easily enters the mesoporous network created by
the randomly oriented aggregated nanostructures. CNTs typically show nearly
rectangular voltammograms, which are characteristic of electrodes with a capacitive
behavior. Arc discharge SWCNTs and thermally oxidized SWCNTs reach capaci-
tance values between 30 and 140 F g 1, showing that an alkaline electrolyte (KOH)
provides higher energy densities, while an acid electrolyte (H2SO4) leads to higher
power densities [36]. The specific capacitance can be improved using aligned CVD
CNTs, which show a higher specific surface area, but still the values remain lower
than those obtained with some microporous activated carbons (ACs). Interestingly, a
high capacitance at high currents and a power density maximum is reached with
certain SWCNT/AC mixtures [37]. High capacitances (231 F g 1) can be also
reached with graphene-based porous electrodes prepared from GO and solid organic
precursors [38]. On the other hand, CNT fillers improve the thermal stability,
potential window, porosity and durability of conducting polymers showing
pseudo-capacitance, such as polypyrrole and polyaniline [39].
Carbon nanotubes and graphene can be integrated in new-generation solar cells as
active layers [40–42], electron acceptors [43], counter electrodes [44], electron
transport layers (ETLs) and hole transport layers (HTLs) [45, 46]. The utilization
of CNTs and graphene as transparent conducting film (TCF) electrodes for indium
tin oxide (ITO) substitution is limited by the requirements of electrical conductivity
and transparency [47]. Recently, a SWCNT synthesis process by aerosol CVD has
provided high quality TCFs for solar cells [48]. A polyanylyne/MWCNT (arc
discharge) composite has been tested as the hole collecting electrode in photovoltaic
textile applications [49].
Storage of gaseous fuels (H2, CH4) and CO2 will probably have a great impor-
tance in the future energy scenario, which is expected to be based on clean renewable
sources. The possibility of using carbon nanomaterials as adsorbents to improve the
storage capacity of pressurized tanks was discussed for years, particularly in the case
of hydrogen. Measurements of hydrogen adsorption in SWCNTs revealed low
storage capacities [50, 51], even if the adsorption was catalyzed by palladium
nanoparticles [52, 53]. Finally, it has been demonstrated that gas capacity (H2,
CH4 and CO2) can be substantially improved in a pressurized storage tank at room
temperature when the tank is filled with AC monoliths, compared to simple
compression [54].
Fuel cells are being widely investigated as a clean solution for powering mobile
devices and vehicles. Carbon nanostructures have been successfully tested as cata-
lyst supports for several chemical reactions that take place in different types of fuel
cells. Arc discharge SWCNTs were used as supports for platinum nanoparticles, and
tested for the oxygen reduction reaction, reaching efficiencies similar to typical
carbon black conducting supports [55]. The Pt/SWCNT catalyst also demonstrated
good activities for the oxidation of methanol and formic acid [56]. The catalyst
efficiencies depend on the metal nanoparticle size and crystalline structure, which is
ultimately influenced by the carbon support characteristics. Macroscopic assemblies
of SWCNTs such as thick films (“buckypapers”) were tested as supports of Pt/Ru
nanoparticles, and the catalyst activity towards methanol oxidation was clearly
dependent on the buckypaper preparation procedure [57].
18.4.2 Catalysis
Apart from the catalytic reactions that take place in fuel cells, carbon nanomaterials
can be utilized in other important chemical reactions. CVD MWCNTs and GO have
been tested as supports of catalytic metal particles with controlled sizes.
Pd/MWCNT hybrids are active in C-C coupling and dehydrogenation reactions
[58], and specially in alkene hydrogenations [59]. Au/MWCNT catalysts have
proved good activities in the selective hydrogenation of nitroaromatic derivatives
[60]. Also, alkene hydrogenation reactions have been selectively catalyzed by
Pd/GO catalysts [61].
1D and 2D nanocarbons are excellent building blocks for 3D architectures with a
developed porosity and catalytic interest. Some examples are monoliths coated with
a layer of CNTs [62], monoliths coated with N-doped CNTs [63], and graphene
aerogels [64]. 3D-structured nanomaterials can be applied as metal nanoparticle
supports or metal-free catalysts. CNTs and N-doped CNTs have been loaded with
Ru nanoparticles for the CO2 reduction with renewable H2 to produce CH4
[65, 66]. Nitrogen- and boron-doped carbon nanofibers (CNFs), and nanodiamond
supported on graphene aerogels have been tested as metal-free catalysts in the
propane dehydrogenation to produce propene [64, 67]. NH3 decomposition to
produce H2 can be catalyzed by metal nanoparticles on CNFs and N-doped CNFs
[68]. Water cleaning applications include the ozonation of organic pollutants on
CNTs and CNFs as metal-free catalysts [69], and the reduction of nitrate and
bromate on CNTs or CNFs as catalyst supports [70].
18.4.3 Multifunctional Materials
Processing issues and applications of CNT and graphene polymer composites have
been reviewed in previous NATO ASIs [71, 72]. The synthetic origin and
functionalization greatly influence the resulting properties of the composite material,

particularly in structural polymers such as polyether ether ketone (PEEK) and
epoxies [73, 74]. Polymer composites are promising light materials for mobile
applications in the aeronautical and automotive industry, since a vehicle weight
reduction leads to important energy savings. In SWCNT/epoxy composites, the
electrical properties and toughness are maximized through the non-covalent
functionalization of the SWNTs with compatibility block copolymers, while the
mechanical and thermal properties are maximized through covalent
functionalization with amine moieties. The improvements in the electrical conduc-
tivity of structural polymers, maintaining their mechanical performance, are typi-
cally great enough for application of the composites in electrostatic charge
dissipation and electromagnetic interference shielding [75]. In addition, it has been
observed that CNTs may act as radical scavengers in polymer systems, protecting the
composite materials against the effects of gamma radiation. More specifically, the
protective effects of arc-discharge SWCNTs, CVD MWCNTs and arc-discharge
MWCNTs have been demonstrated [76–79].
18.4.4 Sensors and Biosensors
The electronic properties, together with the high specific surface area, rich surface
chemistry, optical properties, thermal stability and mechanical robustness allow the
application of CNTs and graphene as sensitive materials. The properties of individ-
ual nanostructures can in part be translated into micro- and macroscopic systems
including thin films, fibres, inks, buckypapers and composite materials, which often
constitute the active part in the sensor system. Applications of sensors based on
carbon nanostructures cover many sectors.
In resistive gas sensors, the resistance of the sensitive material changes upon
exposure to the gas molecules through physical adsorption. For instance, a film of
Pd-functionalized SWCNTs can act as the resistive channel for the reversible
detection of H2 [80, 81], and MWCNT films have been tested for the detection of
NO2 [82]. Also, chemically functionalized SWCNT films experience sensitive
changes upon exposure to explosive components [83], and biologic agent
simulants [84].
Acoustic wave sensors measure the difference in wave propagation from an
emitter to a detector through a tuneable guiding layer. In this type of sensors,
CNTs and GO have been successfully tested as the sensitive layer for the detection
of chemical warfare agents [85].
Semiconducting SWCNTs or SWCNT films can work as channels in field effect
transistors (FETs), and the device response is modified through the adsorption of
molecules on the SWCNT surfaces. Therefore, appropriately designed SWCNT
FETs are sensitive to biological molecules such as different DNA types and anabolic
steroids [86–88].
Another concept for specific biomolecule detection is based on electrochemical

sensing, both by amperometric [10, 89–91], and potentiometric methods [92, 93]. In
a typical device, inks, films or papers of functional carbon nanostructures are
deposited on a glassy carbon electrode for improving the device sensitivity.
Finally, strain sensors have to be considered, which can be utilized for the
detection of pressure and movement. The most direct way for strain sensing is the
use of piezoelectric materials. Other strategies include piezoresistive SWCNT com-
posites, in which the electrical resistance greatly changes upon bending [94, 95]. The
piezoresistive effect is maximized at SWCNT loadings near the electrical percolation
threshold [96].
18.5 Summary and Outlook
Nowadays, the methods for the synthesis of CNTs and graphene are well-stablished,
and good quality materials can be obtained either directly after the synthesis process
or applying purification treatments. Certain types of CNTs and graphene are fabri-
cated in large amounts, allowing their use in industry. Even though improvements in
the synthesis control and purification are still needed, scientific research in CNTs and
graphene has mainly expanded towards the applications, covering a great number of
technological fields. Some of the developed technological products have already
reached the industry, and it is expected that many others will soon be ready for the
market. In the meantime, other new forms of nanostructured carbons are being
described, including GNRs, GQDs, nanocones and carbon dots. In all the cases,
the nanostructure synthetic origin influences the properties and thus determines the
applications. According to their potential, further developments in carbon
nanostructures can be foreseen for the next years.
Acknowledgments The authors thank the organization of the NATO ASI taking place in Sozopol,
Bulgaria from 12/09 to 20/09/2017. This work has been funded by MINECO and European
Regional Development Fund (ENE 2016-79282-C5-1-R), Government of Aragon and European
Social Fund (DGA-ESF-T66 “Grupo Consolidado”).
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Chapter 19
Quantum Information Technology
and Sensing Based on Color Centers
in Diamond
Nina Felgen, Alexander Schmidt, Boris Naydenov, Fedor Jelezko,

Johann Peter Reithmaier, and Cyril Popov
Abstract Diamond is a material with a number of outstanding mechanical, optical,

electrical and chemical properties. In the last decade it has additionally attracted the
attention of scientists due to the promising properties of the color centers in its
crystal lattice which can find applications in quantum information technology or
quantum sensing on a nanometer scale. In this contribution we present the most
prominent color centers in diamond, namely the nitrogen-vacancy (NV) and the
silicon-vacancy (SiV) centers, and the possibilities to create them in diamond. In
order to increase the collection efficiency of the photons emitted by the color centers
they should be incorporated in photonic structures. We demonstrate the fabrication
of nanopillars with diameters down to 50 nm in nanocrystalline diamond (NCD)
films and monocrystalline diamond. In order to reduce the photon scattering from the
rough NCD surfaces we developed a planarization technique which significantly
reduced the surface roughness.
Keywords NV centers · SiV centers · Diamond nanopillars · Surface planarization
19.1 Introduction
Over the past years diamond gained a growing interest as a platform for quantum
information technology (QIT) components and devices, like quantum memories,
quantum repeaters or single photon sources, but also as component for sensing
N. Felgen · A. Schmidt · J. P. Reithmaier · C. Popov (*)

Institute of Nanostructure Technologies and Analytics, University of Kassel, Kassel, Germany
B. Naydenov · F. Jelezko
Institute of Quantum Optics, University of Ulm, Ulm, Germany

194 N. Felgen et al.
applications. These applications are possible due to certain defects in the diamond
lattice based on vacancies and impurity atoms, the so-called color centers. The
advanced applications of these defects is based on their outstanding properties
which include highly stable fluorescence (photo-stability), control of single coherent
spins even at room temperature, sensitivity to magnetic and electric fields at the
nano-scale and many others. Incorporation of these color centers into photonic
structures allows for the control of light – matter interaction.
19.2 Diamond Properties and Synthesis
Diamond as a host material for color centers provides additionally a wide range of
beneficial properties: it is the hardest known natural material, has the highest thermal
conductivity at room temperature, possesses a high optical transparency from the
deep UV to the far IR region, it is a very good electrical insulator which upon doping
can obtain metallic conductivity, is biologically compatible and inert to most
chemicals [1, 2]. Any colors observed in diamond arise from defects such as
impurities, dislocations, vacancies and complexes, creating electronic energy levels
in the bandgap [3].
Synthetic diamond can be distinguished in two groups depending on the synthesis
route. The first one, high pressure high temperature (HPHT) synthesis, was devel-
oped in the 1950s imitating the conditions at which diamond is formed in the earth.
The required pressure of ca. 5 GPa and temperatures of 1300–1700 C make the
method not only time consuming, but also expensive. This can be alleviated by
catalysts. The catalysts used for HPHT synthesis of diamond crystals include alloys
of Fe, Ni, Co, but also elements such as Ti and Al, whereas graphite serves as a
carbon source [4, 5]. Almost at the same time diamond thin film deposition was
realized via chemical vapor deposition (CVD) [6] where a low pressure gas is
activated by plasma, hot filaments, or combustion flames. The CVD process allows
control of the sample size (i.e. the coated area), crystallinity, morphology and doping
[7]. By variation of the process parameters and choice of the substrates all crystalline
forms of diamond can be achieved: mono-, poly-, nano- and ultrananocrystalline
diamond, where many of the superior properties of the monocrystalline bulk dia-
mond are preserved [8].
Diamond films can be grown on a variety of substrates for example Si, glass, W,
Ta and many others after seeding the surface with diamond particles (pre-treatment)
or after bias enhanced nucleation (BEN) [9–12], followed by diamond CVD starting
from the created nucleation sites on the surface. But also diamond itself can serve as
a substrate for homoepitaxy [13]. The most commonly employed carbon precursor
is methane, but also other hydrocarbons, alcohols, etc. can be applied, in all cases
diluted in hydrogen, nitrogen or argon. The major process parameters for diamond
CVD growth are the substrate temperature, the working pressure, the total gas flow,
and the gas phase composition (see for example [14–16]). They determine the
crystallinity of the deposited films. In our experiments nanocrystalline diamond
(NCD) films were deposited via hot filament chemical vapor deposition (HFCVD)
19 Quantum Information Technology and Sensing Based on Color Centers in Diamond 195
Table 19.1 HFCVD Substrate temperature TSub [ C] 850–910

parameters for the growth of
Heater Voltage USub [V] 100
NCD films used in the current
work Filament current IFil [A] 70 (10 A per filament)
Gas mixture CH4/H2 [%] 1/99
Total gas flow [sccm] 505
Deposition time T [min] 10–180
Pressure p [kPa] 2.5
from a 1% CH4/H2 gas mixture. A self-built setup with seven parallel tungsten
filaments (0.3 mm in diameter) was employed allowing homogeneous deposition on
a 3 in. wafer. The process parameters are summarized in Table 19.1.
19.3 Color Centers in Diamond
Diamond hosts hundreds of optically active point defects in its crystal lattice, the
so-called color centers. Although more than 500 luminescent centers in diamond are
known, only few of them have been perceived attention but some are even not fully
identified by their chemical and electronic structure [17]. These defects can be a
missing atom (vacancy), an impurity atom (substitutional or interstitial) or even
complexes of impurities [3].
The general classification of diamond materials is based only on the presence or
absence of boron and nitrogen impurities and how they are arranged in the diamond
lattice, as these impurities are decisive for the appearance of natural diamond but
does not make any statement on other impurities or their arrangement [18]. For
example it does not consider the GR1 color center emitting at 741 nm which is only
an uncharged vacancy in the diamond lattice or the 3H color center emitting at
503 nm which is thought to be an interstitial carbon atom in the diamond lattice.
Especially for nitrogen impurities certain arrangements in the diamond lattice are
well known such as the N3 center (415 nm) which consists of three nitrogen atoms
surrounding a vacancy or the H3 center (531 nm) consisting of two nitrogen atoms
separated by a vacancy [19]. The emission spectra of color centers in diamond range
from the blue to the near-infrared range [20, 21]. From the large variety of lumines-
cent centers in diamond only a few were identified (in addition to the NV and SiV
centers described below) as single photon emitters: nickel-related complexes,
germanium-vacancy (GeV) centers and some others which are up to now
unidentified [17]. Further information about the color centers in diamond and their
properties is reported in references [3, 22–24].
19.3.1 Nitrogen-Vacancy (NV) Centers
The most prominent nitrogen-related color center is the nitrogen-vacancy center

(NV center). It consists of a nitrogen atom adjacent to a vacancy (Fig. 19.1, left) and
occurs in an uncharged (NV0, with zero phonon line (ZPL) at 575 nm in the
photoluminescence spectrum) and a negatively charged state (NV, ZPL at
637 nm), see Fig. 19.1, right. The broad phonon side band in the PL spectrum
ranges from 600 to 800 nm. The chemical and electronic structure of the NV center is
well studied and can be described as a three level system (Fig. 19.2) [25].
Fig. 19.1 (left) Schematic of a NV center. A nitrogen atom (N) sits adjacent to a vacancy (V) along
the (111) axis; (right) room temperature photoluminescence spectrum showing the zero phonon
lines of NV0 and NV centers together with a broad phonon side band
Fig. 19.2 Electronic structure of (a) NV and (b) NV0 center (Reprinted with permission from
[26]. © 2013, Elsevier)
The lifetime has been found to be dependent on the host material; it is around
10 ns for a single NV in bulk material and 24 ns in nanodiamonds [27, 28].
19.3.2 Silicon-Vacancy (SiV) Center
Another color center that has attracted interest in recent years is the negatively
charged silicon-vacancy center (SiV center). It is a common impurity in CVD
grown diamond samples due to the presence of silicon containing quartz windows
and reactor walls or to the use of silicon substrates for growth [29, 30]. The center
consists of a silicon atom separating two vacancies [31] as shown in Fig. 19.3.
The ZPL is centered at 737 nm and has a complicated structure due to the split
ground and excited states as well as to the different silicon isotopes (Fig. 19.4)
[32]. The small FWHM of 5 nm even at room temperature is a result of the weak
electron-phonon coupling [33]. The linearly polarized emission spectrum shows a
Fig. 19.3 Schematic of a

SiV center, a silicon atom
(Si) separating two
vacancies
a b
1.0 C
upper branch
Excited Δc ≈ 250 GHz

Intensity [normalised]
state
<111> lower branch
0.5
D ZPL 737 nm
A B CD
B
A upper branch
0.0
Ground Δg ≈ 50 GHz
Δg Δc Δg
state lower branch
736.5 737.0 737.5
Wavelength [nm]
Fig. 19.4 Photoluminescence spectrum of SiV at 4 K (a) and its energy level diagram (b)
(Reprinted with permission from [32]. © 2014, Nature Publishing Group)
sharp peak without a large phonon side band. Although the quantum efficiency
(QE) is relatively low (0.05), the shorter lifetime of around 1 ns makes the SiV center
an interesting candidate for single photon applications. The QE as well as the line
width and ZPL center vary also with temperature and between samples grown under
different conditions [34].
19.4 Creation of Color Centers
19.4.1 Implantation and Electron Irradiation
The most efficient way to create NV centers is electron irradiation of diamond type
Ib (i.e. with isolated single N impurities) for the generation of vacancies and
subsequent annealing at temperatures above 900 C in vacuum. The high nitrogen
content in the sample is sufficient, the high annealing temperature ensures diffusion
of the vacancies towards the N atoms for the creation of ensembles of NV centers.
However, this method does not allow the fabrication of single color centers; further-
more, due to other imperfections type Ib diamonds provide an imperfect environ-
ment which may deteriorate the properties of the optical centers [35]. To achieve
single NV centers, different strategies employing ion implantation with subsequent
annealing steps are developed such as applying a low fluence of N ion irradiation,
implantation through a mask or even through a cantilever tip with a hole which
serves as a small aperture [36–41]. The possibility of SRIM (Stopping and Range of
Ions in Matter) simulations allows the prediction of the implantation results and vice
versa the calculation of the parameters for a desired implantation profile regarding
the depth, the concentration of vacancies, etc. In Fig. 19.5 the implantation condi-
tions (ion species, energy) for the creation of shallow and deep NV centers are given
as an example; the respective SRIM simulations are shown in Fig. 19.6. SiV centers
can be also created with ion implantation.
19.4.2 In Situ Doping of CVD Diamond During the Growth
Due to the facts that CVD takes place at low pressures and nitrogen is an abundant
component of the atmosphere it is always present in the chamber (except for ultra
high vacuum conditions) and facilitates the incorporation of NV centers during
growth [42, 43]. To increase the amount of nitrogen in the reactor it is possible to
add nitrogen to the gas mixture [44]. Besides the unintentional self-doping from
silicon substrates or glass windows, SiV centers can be created by introducing a
volatile compound such as silane into the process chamber. This method gives not
only the possibility for the formation of SiV centers on non-silicon containing
substrates but also allows for a better control of the amount of silicon in the gas
phase [45, 46].
Fig. 19.5 Conditions for the creation of shallow (ca. 15 nm) and deep (100 nm) NV centers in NCD
film
Fig. 19.6 SRIM simulations of the implantation profiles of 14N (as CN, 20 keV) (left) and 15
N
(as N2+, 600 keV) (right) for the creation of shallow and deep NV centers
19.5 Diamond Photonic Structures
The optical properties of color centers are influenced by their environment which
impacts for example the emission yield. The optical transitions of the NV and SiV
centers are located in the visible range making diamond with its high refractive index
of n ¼ 2.43 a suitable material for the realization of photonic structures. Further-
more, the collection efficiency of photons emitted by a NV center can be improved
utilizing diamond nanowires instead of bulk materials as determined by finite-
difference time-domain (FDTD) simulations by Hausmann et al. (Fig. 19.7). In
bulk diamond the light emitted from the NV center leaks into the bulk due to total
internal reflection at the air-diamond interface [47, 48].
The same authors also simulated the coupling efficiency between the NV center
and the nanowire mode as a function of the diameter. With an s-polarized dipole and
Fig. 19.7 Field profile of the radial E-field component in the case of a 2 μm long, 200 nm diameter
diamond nanowire (left) and a bulk diamond (right). The dipole is polarized parallel to the interface,
emitting at λ ¼ 637 nm. The fundamental nanowire waveguide mode (HE11) (inset) is the dominant
decay channel for the nanowire case (Reprinted with permission from [47]. © 2010, Elsevier)
Fig. 19.8 Coupling

efficiency as a function of
the nanowire diameter at
λ ¼ 637 nm. The dipole is
assumed to be placed at the
center of the nanowire with
a polarization perpendicular
to the nanowire axis
(s-polarized) (Reprinted
with permission from
[47]. © 2010, Elsevier)
a diameter between 180 and 230 nm more than 80% of the emitted photons can
couple to the nanowire (Fig. 19.8) allowing a huge increase in the photon collection
efficiency [47].
Besides nanopillars or nanowires there are more structures that enhance the
emission yield and increase the collection efficiency of the photons emitted from
the color centers in diamond. These include 1D and 2D photonic crystals [49–51]
micro rings [52], and waveguides [53], solid immersion lenses (SIL) [54] or gratings
[55] fabricated in poly- or nanocrystalline as well as in monocrystalline diamond.
Each of these materials has its advantages and disadvantages for the preparation of
photonic structures but also in view of the optical properties. For deposition of poly-
and nanocrystalline diamond a broad range of substrates is available, the structuring
processes are well established but the optical properties are alleviated due to grain
boundaries and the typical roughness of the films. Monocrystalline diamond exhibits
excellent optical properties, but the fabrication of some of the photonic structures
and the limit of substrate choices can be challenging.
19.6 Fabrication of Diamond Photonic Structures
For the fabrication of diamond nanostructures different top-down as well as bottom-

up techniques are known. The top-down approaches usually start with a lithographic
step which can be either photolithographic or electron beam lithographic (EBL)
transfer of the desired pattern into a resist. Depending on the etching recipe and the
etch time the resist can be sufficient as a mask, but often a hard mask is required
which can be patterned by a lift off process or by structuring the mask material itself
via dry etching. Common mask materials include gold, aluminum, chromium, but
also silicon or silicon dioxide. For the structuring of diamond itself almost exclu-
sively ion assisted plasma techniques, like reactive ion etching (RIE), are applied.
They can be divided into two groups with respect to the active gas used: oxygen or
oxygen-containing gas mixtures [47, 56–58] and hydrogen-containing gas mixtures
[59, 60]. The latter have the disadvantage of high process temperatures in the range
of the deposition temperature of diamond. Using oxygen and oxygen-containing gas
mixtures, such as O2/Ar or O2/CH4, the structuring can be performed at room
temperature achieving high etch rates.
19.6.1 Fabrication of Diamond Nanopillar Arrays
In our group nanocrystalline diamond pillars with diameters of 1 μm, 500 nm,
200 nm, 100 nm and 50 nm, and center-to-center distance of 5 μm were fabricated
using either a 200 nm gold mask with 5 nm titanium as an adhesion layer [61] or
100 nm aluminum masks. The dry etching was performed in an ICP-RIE set up with
only oxygen as reactive gas under the conditions described in detail in [62]. The etch
time was monitored with a laser interferometer to assure the etching of the entire
NCD film to the substrate and the reduction or even complete removal of the residual
diamond grass. The final structures were arrays of diamond nanopillars as shown in
Fig. 19.9.
19.6.2 Fabrication of Dense Nanopillar Arrays
Once the distances between the diamond nanopillars are reduced to obtain highly
dense arrays, further challenges could arise regarding the fabrication process. As
Fig. 19.9 Array of NCD

nanopillars with a diameter
of 500 nm
Fig. 19.10 SEM images of NCD nanopillar arrays with a diameter of 200 nm and a center-to-center
distance of 400 nm: (left) with the impact of the proximity effect, (right) after suitable proximity
corrections
soon as the dimensions of the structures are reduced and high package densities in
electron beam lithography (EBL) are desired, the well-known “proximity effect”
starts to affect severely the exposure resolution. As electrons penetrate through the
resist into the substrate, electron scattering phenomena occur leading to an undesired
exposure of resist areas adjacent to the scanned electron beam spot. The pattern
fidelity is therefore strongly limited by the proximity effect inherent in electron–solid
interactions and thus in EBL.
Especially in the case of fabrication of arrays with high densities of diamond
nanopillars, the proximity effect has a crucial impact on the developed structures as it
is evident in Fig. 19.10, left. The pillars are broadened and merged together leading
to a pattern that strongly deviates from the desired one. This effect is more pro-
nounced in the center of the array, due to the higher electron distribution in the center
compared to the edges thus exhibiting a higher impact of the proximity effect.
The proximity effect depends on many factors like the size, shape and package
density of the nanostructures as well as on the exposure conditions, but with
appropriate corrective action it is possible to fabricate well developed highly dense
Fig. 19.11 Implantation map of a IIa diamond sample
pillar arrays (Fig. 19.10, right) [63]. Concerning the pattern design for EBL,
proximity correction software was used to calculate a suitable dose distribution.
Additionally, an exposure dose variation was used to find the optimal value, which
leads to well developed nanopillar arrays.
19.6.3 Incorporation of NV Centers into Diamond Pillars
The approach employing N implantation and annealing followed by structuring can

also be transferred to monocrystalline diamond samples. N+ was implanted into IIa
diamond with an implantation spot size of 300 μm in diameter. The implantation was
performed with 5 keV and two different doses of 51012N+/cm2 and 51013N+/cm2
(Fig. 19.11). Prior to structuring the created NV centers were pre-characterized to
ensure a successful implantation process (not shown here).
The knowledge about the implantation spots made it possible to create pillar
arrays directly on implanted areas of the diamond. For this purpose a 100 nm Al
mask was chosen (Fig. 19.12, left). The structuring of pillars with diameters ranging
from 1 μm to 50 nm was performed with the standard etching recipe for 8.5 min
assuming an etch rate of 100 nm/min (derived from a laser interferometer). The etch
depth was around 850 nm (Fig. 19.12, right).
The fluorescence mapping of the structured sample exhibited the presence of NV
centers only in the pillars but not in the bulk material (Fig. 19.13). Furthermore, for
the 200 nm diameter pillars the strongest fluorescence signal (>100 kc/s) was
detected.
Room temperature PL measurements revealed the presence of the ZPL peak of
NV at 637 nm as well as the typical broad phonon side band (Fig. 19.14).
Fig. 19.12 Aluminum mask for structuring of pillars with 500 nm diameter on top of a monocrys-
talline diamond sample (left) and a final 500 nm diameter pillar (right)
Fig. 19.13 Fluorescence mapping of the implanted IIa sample after structuring of pillars with
different diameters
19.6.4 Incorporation of SiV Centers into Diamond Pillars
Incorporation of SiV centers into nanostructures was achieved by overgrowth of

existing NCD pillars on a silicon substrate. The structured sample was overgrown
Fig. 19.14 PL spectra of 500 nm (left) and 100 nm (right) monocrystalline diamond pillars
Fig. 19.15 A pillar with a

diameter of 500 nm after
overgrowth (Reprinted with
permission from
[65]. © 2016, Elsevier)
in the HFCVD chamber for 30 min using the same process parameters as for the
deposition. No additional pretreatment was applied. The overgrowth took place
only on the diamond pillars and not on the silicon substrate (Fig. 19.15). The bare
silicon substrate was etched by the atomic hydrogen generated in the gas phase
and served as silicon source for the creation of SiV centers during the growth
[24, 64, 65].
The PL measurements before the overgrowth step showed no signal of SiV
centers but only a broad phonon side band (Fig. 19.16a). After overgrowth the
side band was strongly reduced, and a peak at 737 nm attributed to the SiV ZPL
was clearly visible (Fig. 19.16b).
Comparing the SiV ZPL signal of different pillar diameters a dependency can be
observed (Fig. 19.17). The strongest signal was obtained for a 200 nm pillar
diameter.
The transfer of this technique for the incorporation of SiV centers into mono-
crystalline diamond pillars is under development.
Fig. 19.16 PL spectra (a)

before and (b) after the
overgrowth for a 100 nm
pillar (Reprinted with
permission from
[65]. © 2016, Elsevier)
19.7 Planarization of Nanocrystalline Diamond
Planarization of nanocrystalline diamond films is necessary for optical applications

in order to reduce the scattering of light at the edges of the surface crystallites. The
well-known chemical-mechanical polishing (CMP) method offers sufficient results
for thick PCD and NCD films, but it is not applicable in our case due to the large
amount of removed material (several μm) by the process (our NCD films have
thicknesses up to 1 μm). The simple dry etching using the NCD recipe [62] resulted
in less sharp crystallites which looked quite smooth, but the surface roughness was
not significantly reduced. Nevertheless, efforts were made to create photonic crystals
from these samples (not shown here).
To avoid the necessity of a thick diamond layer for smoothing and to overcome
problems like time consumption and the risk of decoration at the grain boundaries of
polycrystalline diamond samples Rabarot et al. developed a diamond layer
Fig. 19.17 PL signal intensity in dependence of the pillar diameter
Fig. 19.18 Smoothing process of polycrystalline diamond applying deposition of SiO2, CMP and
RIE (Reprinted with permission from [66]. © 2010, Elsevier)
smoothening process called DPE (deposition, planarization, etching) including an

intermediate layer of SiO2. A thick SiO2 layer is deposited on the diamond and
smoothed by conventional CMP techniques. After that a selectively controlled
reactive ion etching step (RIE) is carried out to transfer the flat surface into the
diamond (Fig. 19.18) [66].
The RIE process had to be adjusted to generate an etching selectivity (S) of 1 to
ensure the same etch rate of both materials, silicon dioxide and diamond. The chosen
gases were oxygen (O2) and sulphur hexafluoride (SF6) as the first increases the etch
rate of diamond, the second the etch rate of silicon dioxide (Fig. 19.19). With an etch
rate of 50 nm/min Rabarot et al. achieved a surface roughness of 1.5 nm for a 200 nm
thick polycrystalline diamond film [66].
To reduce the efforts for SiO2 layer deposition and CMP another method came to
the focus of interest. Checoury et al. spun hydrogen silsesquioxane (HSQ) on a NCD
surface which after baking on a hot plate turned into a smooth silica-like layer on top
of the diamond. The following dry etching and thus planarization process involved
oxygen and argon which was adjusted to etch both, HSQ and diamond, with the
Fig. 19.19 Etch rate of RIE process using an intermediate SiO2 layer on top of polycrystalline
diamond film (Reprinted with permission from [66]. © 2010, Elsevier)
Fig. 19.20 Planarized NCD surface: (a) SEM micrograph, (b) AFM image (Reprinted with
permission from [51]. © 2012, AIP Publishing LLC)
same speed. After the etching process residual silica was removed with hydrofluoric
acid. The root mean square (rms) roughness dropped from around 10 nm for the
as-grown layer to 1.6 nm (Fig. 19.20) [51].
Due to the relatively high price of HSQ another method was recently developed
in our group. NN120-20 from durXtreme is a spin-on-dielectric or spin-on-glass
(SOG) (20 wt% perhydropolysilazane (PHPS) in n-dibutylether) which should
possess similar properties as HSQ. PHPS can be thermally hardened turning the
liquid film into a SiOx layer. The spin-coating parameters were chosen to obtain a
smooth film covering all diamond crystallites (Fig. 19.21). After hardening of the
SOG the sample was etched in a SF6/O2 plasma using a recipe with a gas flux
comparable to the one given in literature [66] after adjusting the RF and ICP
Fig. 19.21 NCD film

completely covered with
SOG using 6000 rpm. The
charging of the film can be
seen
Fig. 19.22 SEM images of planarized NCD surfaces: (left) 45 view, (right) cross-section
powers. The residual SOG was removed with buffered HF; the resulting planarized
NCD surfaces were flat and smooth (Fig. 19.22).
The minimum roughness which can be achieved is limited by the initial rough-
ness of the SOG layer on top of the NCD film. Therefore, AFM images were taken
before (i.e. from as-grown NCD film) and after the coating with SOG and the baking
procedure. In Fig. 19.23 (right) it can be seen that there are no sharp edges or facets
that bulk out the SOG layer, although one could imagine the crystallites underneath.
With a peak to peak height of 16 nm and a rms roughness of around 2 nm of the SOG
coating the transfer of this topography onto the NCD surface would be a huge
improvement.
Different etch times were tested to prevent under- or over-etching of SOG or
NCD. An etch time of 8 min decreased the rms roughness from 23 to 14 nm
(Fig. 19.24 (left)). This improvement is not sufficient; therefore a second
planarization step was carried out on the same sample. Starting again with spin
coating and baking the SOG, the next ICP etch step needed again some adjustment
regarding the etch time. Another 8 min led to the destruction of the film, because the
Fig. 19.23 AFM images of as-grown NCD (left) and of a NCD surface covered with a baked SOG
layer (right)
Fig. 19.24 AFM images after the first etch step of 8 min (left) and after the complete planarization
process (right)
smoothening process is accompanied by a film thickness reduction due to material

removal. An etch time of 6 min for the second process seems to be adequate and
resulted in a rms roughness of around 6 nm (Fig. 19.24 (right)).
The evaluation of the film thickness revealed a reduction from 600 nm to around
250 nm which is in the range of thicknesses of the diamond membrane required for
photonic crystals. First attempts were made to create photonic crystal slabs with this
planarization procedure employing geometric parameters (hole diameters, period,
slab thickness) determined by simulations. The testing of different mask materials
such as Al and SiO2 (Fig. 19.25) as well as the optimization of the process
parameters are still ongoing.
Fig. 19.25 Planarized NCD

film with 150 nm SiO2 on
top (as a mask) for the
fabrication of diamond
photonic crystals
19.8 Summary
We presented the attractive properties of color centers in diamond, namely NV and

SiV color centers and their possible applications in quantum information technology
and sensing. The creation of the color centers was demonstrated using in situ doping
and implantation into different diamond types, namely NCD and monocrystalline
diamond. The successful fabrication of various photonic structures with a focus on
nanopillar arrays was performed by EBL and dry etching. The developed
planarization process will improve the optical characteristics of these structures
and will be applied also to the fabrication of photonic crystals.
Acknowledgements The authors would like to acknowledge the financial support of the German
Federal Ministry of Education and Research (BMBF) under the Program “Quantum Communica-
tion” (Project Q.com-H). They are grateful to Johannes Lang for the ion implantation.
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Chapter 20
Experimental Study of Spectral Parameters
of Silicon-Vacancy Centers in MWCVD
Nanodiamond Films Important for Sensing
Applications
L. Himics, M. Veres, S. Tóth, I. Rigó, and M. Koós
Abstract Microwave enhanced chemical vapor deposition (MWCVD) was used to

prepare nanodiamond (ND) films with different process parameters containing
silicon-vacancy (SiV) centers. The effect of the local environment on the spectral
parameters of SiV center’s zero phonon line emission, like peak position and full
width at half maximum (FWHM), being important for many applications, have been
studied in films having different morphological and structural properties. Relation-
ships between the residual internal stress of the nanodiamond films and the emission
parameters of the SiV centers were found and explained by shifting of the electronic
levels of ground and excited states of individual SiV centers within the probed SiV
ensembles due to the internal stress.
Keywords Silicon-vacancy center · Nanodiamond · Spectral parameters of ZPL ·

Photoluminescence
20.1 Introduction
Optically active defects or so-called color centers in nanosized diamond constitute

an intensively investigated field of research nowadays. Among them the SiV center
is a promising candidate for utilization in different fields like nanosensors, quantum
computing and cryptography, nanoscopy, medicine or cell biology [1–3]. Most of
the mentioned applications are based on the excellent light emission properties of the
SiV defect. This center has a narrow zero-phonon line (ZPL) in the near infrared
region around 1.68 eV (738 nm); it is a single-photon emitter and has a low electron-
phonon coupling, even at room temperatures [4–6]. Many applications require well
detectable (separated from the background) and indistinguishable photons, which
L. Himics (*) · M. Veres · S. Tóth · I. Rigó · M. Koós

Wigner Research Centre for Physics, Hungarian Academy of Sciences, Budapest, Hungary

216 L. Himics et al.
means that each individual center should emit at the same frequency; for special
applications a fine tuning of the emission properties is necessary. Thus a study of the
effect of deposition parameters and thereby the local environment of the SiV centers
on the emission properties is essential and it can offer an effective tool for tailoring
the light emission characteristics of the color centers.
In this work we investigated the behavior of the 1.68 eV SiV photoluminescence
(PL) emission line in different nanodiamond films prepared by changing the
MWCVD deposition parameters (H2/CH4 ratio and substrate temperature). The
properties of the ND films were characterized by micro-local residual stress obtained
from Raman spectra, while spectral parameters of the SiV ZPL were determined
from photoluminescence measurements. Correlations between the ZPL parameters
and the local stress were found.
20.2 Experimental Details
Nanocrystalline diamond films were grown from a CH4/H2 gas mixture by the
MWCVD technique at 1200 W microwave power and a frequency of 2.45 GHz.
Silicon wafers served as substrate material; bias enhanced nucleation on the substrate
surface was performed at 4% methane and 200 V bias voltage for 30 min to form
diamond nuclei. The chamber pressure was kept at 40 mbar for nucleation and
growth likewise. The total gas flow rate in each case was 100 sccm. The deposition
of SiV containing nanocrystalline diamond film was performed at methane concen-
trations of 0.2%, 0.5%, 1.0%, 1.5%, 2% and 3% of the feed gas, while the substrate
temperature was kept at 650, 700, 750, 800 and 850 C. The growth process was
performed for 2 h for each sample. The layer thickness was determined by in situ
laser reflection interferometry; it ranges around 200 nm.
In our experiments the source of silicon impurity atom is the silicon wafer used as
substrate for the ND films. The introduction of Si atoms into the methane-hydrogen
plasma is accomplished by sputtering the silicon substrate with the microwave
plasma. Therefore, the deposition parameters are expected to have influence on
both the formation and the local environment of the SiV centers.
A Renishaw 1000B micro-Raman spectrometer attached to a Leica DM/LM
microscope was used to study the light emission properties of SiV centers and the
Raman scattering properties of the ND films. The ZPL parameters of the SiV centers
were determined from luminescence spectra; Raman spectra were used to monitor
the ND film quality and to determine micro-local residual stresses. Spectral distri-
bution of the emitted light was analyzed in the 700–800 nm (1.77–1.41 eV) wave-
length region, while Raman spectra were measured in the 1000–2000 cm1
wavenumber range, with 1 cm1 spectral resolution. The photoluminescence and
Raman spectra were recorded from the same excited volume; for both measurements
the 488 nm line of a Spectra-Physics Ar-ion laser was used as excitation source.
20 Silicon-Vacancy Centers in MWCVD Nanodiamond Films Important. . . 217
Fig. 20.1 Spectral distribution of SiV centers emission lines measured at room temperature in ND
films grown at (S1) T ¼ 700 C and 2% CH4, (S2) T ¼ 750 C and 0.2% CH4, (S3) T ¼ 750 C and
3% CH4, (S4) T ¼ 800 C and 1% CH4, (S5) T ¼ 850 C and 0.2% CH4
The deposition parameters of the ND films have a significant effect on the properties
of the formed structures. This is especially true for the methane content of the feed
gas and the substrate temperature [7, 8]. Obviously, if the deposition parameters
influence the created structure, they should also affect the optically active defects
located within the structure. Therefore, PL emission spectra of SiV centers have been
studied in a large number of nanocrystalline diamond films deposited at different
growth conditions. Some typical spectra with characteristic ZPL around 1.68 eV are
shown in Fig. 20.1. These spectra were selected to demonstrate the variation of
spectral shape, peak position and ZPL broadening of SiV centers in samples having
distinct structural properties. The structural properties were altered by changing the
deposition conditions (CH4 content and substrate temperature). The PL spectra in
Fig. 20.1 show that these parameters have a significant effect on the SiV center
emission characteristics. In contrast to the line broadening, which is obviously
different from sample to sample, the variation of the peak positions is not so
impressive at first sight, but still detectable. A significant shift can be observed if
one compares values of the peak positions determined for individual SiV containing
ND films. PL scanning measurements performed on 40 40 μm2 areas of the films
-2,5
-2,0
Compressive
Residual Stress [GPa] -1,5
-1,0
-0,5
0,0
0,2
1,0
1,5
2,0
3,0
0,2
0,5
0,2
0,5
0,2
0,5
1,5
2,0
2,0
3,0
3,0
0,2
0,5
1,0
2,0
1,0
1,0
CH4(%): 2,0
Tensile
0,5
1,0
650 700 750 800 850
TSubstrate [oC]
Fig. 20.2 Variation of the residual stress determined form Raman spectra in ND films containing
SiV centers, grown at different substrate temperatures and CH4 contents. The negative sign
indicates a compressive, while the positive a tensile stress
showed that the peak position spread is about ~0.8 meV within one sample, which is
nevertheless several times smaller than the values determined for our sample series,
as will be shown later. Based on this it looks that the shift of the peak position is
sample (deposition parameter) specific.
The shift and line broadening of the SiV center ZPL observed in the literature is
mostly explained by stress acting in the vicinity of centers and by inhomogeneous
distribution of individual SiV centers within the probed ensemble. Uniaxial stress
dependence experiments performed on SiV ensembles showed that an increase of the
stress magnitude causes mainly a blue shift of the ZPL [9, 10]. In contrast, recent
work performed on single SiV centers states that the ZPL of individual centers is
dominantly red shifted [11]. It seems to be plausible to examine the stress depen-
dence of the SiV ZPL parameters for a large number of samples, because the results
can give more insight into the behavior of the SiV ZPL parameters or even resolve
contradictions reported in the literature. For this purpose we used Raman spectros-
copy to determine the type and magnitude of the residual stress present within the
probed sample volume from which the PL spectra of the SiV ensembles were
recorded (for the details see [12]). Figure 20.2 shows the stress values measured in
our samples grown at different conditions. All SiV center containing ND films
exhibit compressive residual stress, except one sample, deposited at 1.5% CH4
content and 800 C substrate temperature, which has tensile type. The sample with
highest compressive residual stress (2.25 GPa) was deposited at 750 C substrate
temperature and 2.0% methane content of the feed gas.
20 Silicon-Vacancy Centers in MWCVD Nanodiamond Films Important. . . 219
24
SiVZPL Peak Position [eV]
1,682
(a) 21
(b)
SiVZPL FWHM [meV]

18
1,680 15
12
1,678 9
6
1,676 Tensile Compressive 3 Compressive
Tensile
0
0,5 0,0 -0,5 -1,0 -1,5 -2,0 0,5 0,0 -0,5 -1,0 -1,5 -2,0
Residual Stress [GPa] Residual Stress [GPa]
Fig. 20.3 (a) Peak position and (b) FWHM of SiV center’s ZPL plotted against the estimated
residual stress. Trend lines (dashed lines) are added for each plot to guide the eyes. The green
rectangle shows the variation of ZPL parameters determined for one sample
Unfortunately, the Raman spectroscopy based method used to determine the type
and magnitude of the stress is not able to separate and identify the different stress
sources, like lattice mismatch of diamond and silicon substrate, grain boundaries and
sp2 carbon, or defect related stress sources, including optically active defects, which
can be present individually or even simultaneously. However, the relatively high
stress found in our samples implies that this influences the SiV centers defect
structure as well, and can cause differences in the SiV ZPL characteristics.
Figure 20.3 shows the peak position and FWHM of SiV center ZPLs as a function
of the estimated residual stress for all samples. Despite the variation of the values a
definite tendency can be observed: increasing the residual stress from tensile to
compressive type causes a blue shift of the SiV ZPL peak position. Additionally, a
spectacular narrowing of the ZPL can be observed when the residual stress gradually
turns from 0.75 GPa tensile to 2.25 GPa compressive type (Fig. 20.3b). The nearly
threefold difference indicates a more pronounced influence of the local environment
on the ZPL broadening compared to that on the peak position.
The observed phenomena can be explained by the electronic structure of the SiV
center induced by stress acting on the vicinity of individual centers. It has been
demonstrated that the electronic structure of the center consists of a ground (2Eg) and
an excited (2Eu) state both having E symmetry and double orbital degeneracy
[13]. The fourfold degeneracy is partially lifted by spin-orbit interactions in both
the ground and the excited states [14]. The spin-orbit interaction results in four
optical dipole transitions which can be well-resolved only at cryogenic temperatures.
As the degree of splitting and the proportion of the four optical lines are stress and
temperature sensitive, they can cause line broadening and peak position shift of the
measured ZPL. High strain fields result in an increased splitting of the ground and
excited electronic levels and give rise to reduced phonon occupation and suppressed
relaxation [10]. This is in good accordance with our observations related to the blue
shift of the peak position and the decrease of the line broadening.
20.4 Conclusions
Spectral parameters of the SiV centers were studied in a large number of ND films
prepared at different deposition conditions. It was found that the deposition param-
eters have a significant effect on the structure of ND films containing SiV centers
mainly in form of residual stress of different magnitude. Experimental results show
that an increase of residual compressive stress causes a decrease of line broadening
and a blue shift of the SiV ZPL. So the control of the residual stress by appropriate
growth conditions allows to tailor the ZPL parameters of the SiV centers.
Acknowledgments This work was supported by the National Research, Development and Inno-
vation Fund of Hungary with the NVKP_16-1-2016-0043 grant and the VEKOP-2.3.2-16-2016-
00011 grant and by the Hungarian Science Foundation under contract number OTKA K-115805
“Complex plasmas in Action”.
References
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5:397–405
4. Clark CD et al (1995) Silicon defects in diamond. Phys Rev B 51(23):16681–16688
5. Rogers LJ et al (2014) Electronic structure of the negatively charged silicon-vacancy center in
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6. Zaitsev AM (2001) Optical properties of diamond. Springer, Berlin/New York
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9. Sternschulte H et al (1995) Uniaxial stress and Zeeman splitting of the 1.681 eV optical center in
a homoepitaxial CVD diamond film. Diam Relat Mater 4(10):1189–1192
10. Jahnke KD et al (2015) Electron–phonon processes of the silicon-vacancy centre in diamond.
New J Phys 17(4):043011
11. Neu E et al (2011) Single photon emission from silicon-vacancy colour centres in chemical
vapour deposition nano-diamonds on iridium. New J Phys 13(2):025012
12. Himics L et al (2016) Spectral properties of the zero-phonon line from ensemble of silicon–
vacancy center in nanodiamond. Opt Quant Electron 48(8):394
13. Goss JP et al (1996) The twelve-line 1.682 eV luminescence center in diamond and the
vacancy-silicon complex. Phys Rev Lett 77(14):3041
14. Hepp C et al (2014) Electronic structure of the silicon vacancy color center in diamond. Phys
Rev Lett 112(3):036405
Chapter 21
Electrochemical Synthesis of PANI/
Graphene Nanocomposites Aimed
for Sensors
Aleksandar Petrovski, Perica Paunović, Anita Grozdanov,

Aleksandar T. Dimitrov, Gennaro Gentile, and Maurizio Avella
Abstract This study is concerned with the electrochemical synthesis of polyaniline

(PANI) based composites reinforced by carbon nanostructures (CNSs) such as
graphene. To determine the optimal conditions for electropolymerization of the
aniline to PANI, an electrochemical characterization was performed by means of
cyclic voltammetry, steady state polarization and galvanostatic measurements.
Within the CV spectra all steps of the transformation from aniline to polyaniline
were observed with corresponding potential regions. It was found that the optimal
potential for electropolymerization of the PANI based nanocomposites is 0.75 V
vs. saturated calomel electrode (SCE). The electropolymerization rate was observed
for two ways of involving of carbon nanostructures in the polymer matrix: dispersion
in the electrolyte and previous deposition at the working electrode. The produced
nanocomposites were characterized by means of Scanning Electron Microscopy
(SEM) and Raman Spectroscopy. Strong interaction between the quinoidal structure
of PANI and carbon nanostructures were detected. Electrical properties of the
nanocomposite tablets were tested using the four probe method. These measure-
ments show the great potential of the studied materials for sensors.
Keywords Nanocomposites · PANI · Graphene · Sensors · pH
21.1 Introduction
As result of different human activities such as industry, transportation etc., the

surface waters (rivers, lakes, seas, and oceans) are susceptible to pollution, which
disrupts the chemical and ecological balance of the ecosystem established in them.
A. Petrovski (*) · P. Paunović · A. Grozdanov · A. T. Dimitrov

Faculty of Technology and Metallurgy, SS Cyril and Methodius University, Rudjer Boskovic
16, Skopje 1000, Republic Macedonia
G. Gentile · M. Avella
Institute for Polymers, Composites and Biomaterials, National Research Council, Pozzuoli, Italy

222 A. Petrovski et al.
Monitoring of pH changes of the surface waters is an appropriate and fast way to

detect their acidification or alkalization that signalize the presence of undesirable
chemicals and corresponding chemical reactions, which can move the
bio-equilibrium. Application of nanocomposites based on conductive polymers
and carbon nanostructures as a pH nanosensor is a very promising new approach
for monitoring of pH changes, instead of the traditional methods for pH measure-
ments (optical, electrical etc.) [1].
As result of its excellent properties (electrical, electrochemical, redox behavior,
electroluminescence, environmental stability etc.), simple preparation and low cost
of the precursor (aniline), PANI has been considered as one of the most promising
materials among the family of the conductive polymers [2–4]. Green et al. [5], were
the first who mentioned the structure of polyaniline. They proposed the octameric
structure as the basic structural unit of the polymeric chain and called it
leucoemeraldine (completely reduced form). The emeraldine base is the only one
conductive form of polyaniline, when is converted in emeraldine salt by treating with
doping acids. Due to its appropriate properties, PANI has been recognized as a
suitable material for use in electronics, optical devices, energy storage devices,
sensors etc. [6–8]. But there are some limitations for PANI applications, due to its
poor mechanical properties and low processability.
After discovering the carbon nanostructures (CNSs) such as carbon nanotubes
(CNTs) [9] and graphene [10] with extraordinary properties, one of their effective
application is the reinforcing of polymers. Reinforcing of PANI with CNSs is a very
appropriate approach to overcome the previous mentioned limitation for PANI
applications. Because of the synergetic effect between the polymer matrix (PANI)
and reinforcement (graphene), the newly formed structure posses improved proper-
ties as compared to pure PANI, but in some cases they even are better than the
nanostructures [11, 12]. PANI/CNSs nanocomposites can be prepared by chemical
or electrochemical polymerization [3, 13, 14]. PANI and CNSs powders can be
mixed by mechanical blending, stirring or sonification.
The aim of this paper is to prepare conductive CNS/PANI nanocomposites by
electrochemical polymerization, with the possibility of further sensor applications.
21.2 Experimental
Electrochemical polymerization of aniline in presence of graphene (G) was

performed to obtain PANI/G nanocomposites. The electropolymerization process
was performed in a standard three electrode electrochemical cell with a capacity of
250 cm3. As working and counter electrodes, platinum tiles with a surface of 10 cm2
were used, while a saturated calomel electrode (SCE) was used as a reference
21 Electrochemical Synthesis of PANI/Graphene Nanocomposites 223
electrode. The electrolyte contains 0.1 M aniline and 0.5 M H2SO4 for each
experiment. The graphene (produced by molten salt electrolysis in the labs of the
Faculty of Technology and Metallurgy in Skopje) were firstly modified in concen-
trated solution of H2SO4 and HNO3 with a ratio 3:1, respectively, then purified with
boiled deionized water and dried at 70 C in air atmosphere.
Electropolymerization was conducted by dispersion of graphene in the electro-
lyte. Before the process starts, graphene was firstly dispersed in the electrolyte by
sonification (30 min) in an ultrasonic bath. Electropolymerization was carried out at
a constant potential of the working electrode of +0.75 V vs. SCE until the current
reaches 110 mA. These data were determined from electrochemical measurements:
cyclic voltammetry and steady-state polarization. The content of graphene was
varied (1, 2 and 3 wt % wt. of the aniline).
The morphology of the nanocomposites was analyzed by means of a scanning
electron microscope FEI Quanta 200 using a secondary electron detector and an
acceleration voltage of 30 kV.
Using a conventional resistivity meter, pH measurements were performed in
laboratory as well as field testing in marine water. Sensors were prepared by
electropolymerization of PANI/G nanocomposite over commercial gold electrodes.
The curves shown in Fig. 21.1 are cyclic voltammograms of the

electropolymerization of aniline in the presence of graphene. The measurements
were performed at different scan rates (10, 20 50 and 100 mVs1).
Four oxidation peaks and the corresponding reduction peaks can be observed in
the region of potential change of 0.2 to 1 V. The peak I denotes oxidation of
leucoemeraldine (0) to emeraldine (1), while the peak I0 denotes the opposite
transformation [15]. The redox pairs II/II0 correspond to the formation of secondary
products (benzoquinone/hydroquinone) or overoxidation/degradation of PANI
[15, 16], redox pair III/III0 to the transformation of p-aminophenol/
benzoquinonemine [17]. The peak IV can be ascribed to oxidation of emeraldine
to pernigranilline, IV0 to the opposite transformation. The working potential for
electropolymerization of PANI is in this potential region between 0.65 and 0.8 V.
At the intersection of voltammograms curves with the line L (in the region of
charge and discharge of electrochemical double layer), corresponding values of
anodic and cathodic currents can be used to determine double layer capacity (Cdl)
of the produced nanocomposite, using the following equation:
dicap
C dl ¼
dð∂E=∂t Þ
0.05
G/PANI
I
–2 0.04 0.1 M Aniline + 0.5 M H2SO4
0.03 Charge of the double layer

Current density, A·cm
IV
II III
0.02
–1
100 mV ·s
0.01 –1
50 mV ·s–1
L 20 mV ·s –1
0.00 10 mV ·s
-0.01
IV'
-0.02 I'
II' III'
Discharge of the double layer
-0.03
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Potential, V vs. SCE
Fig. 21.1 Cyclic voltammogram of the electropolymerization of a PANI/G composite (electrolyte:

0.1 M aniline +0.5 M H2SO4)
The calculated value of the double layer capacity was 121 mFcm2, which is
comparable with corresponding values of some carbon nanostructures such as
Vulcan XC-72 (180 mFcm2) and MWCNTs (330 mFcm2) [18].
For a more accurate determination of the working potential, steady-state polari-
zation measurements were performed (Fig. 21.2). The most suitable nanocomposite
with a green color which corresponds to the most conductive emeraldine salt (insert
in Fig. 21.1) was obtained at 0.75 V vs. SCE [19].
The morphology of the PANI/G nanocomposite is shown in Fig. 21.3. The
graphene sheets are well and uniformly wrapped with a PANI polymer matrix,
which is appropriate for their strong interaction. During the deposition time of
40 min, fibrous and porous structure of PANI was formed, with fibers diameter of
75–150 nm. This is in agreement with literature data [20], which have shown that for
an electropolymerization longer than 20 min, fibrous PANI was formed, instead of a
granular one.
The obtained PANI/G nanocomposites were first lab tested towards their sensing
activity in a simulated aqueous media in a closed pH range from pH ¼ 7,4 to
pH ¼ 10. The resulting curves are shown in Fig. 21.4. Besides the lab testing, the
obtained screen printed electrodes (SPE) were tested also in real sea water. Resis-
tivity changes of the PANI/G nanocomposite electrodes occurred due to the different
degree of protonation of the imine nitrogen atoms at the polymer chain in the
presence of graphene.
10
–2
Current density, mA·cm
8
0 0.1 M Aniline + 0.5 M H2SO4
0.6 0.7 0.8 0.9 1.0 1.1

Potential, V vs. SCE
Fig. 21.2 Polarization curve of electropolymerization of PANI (electrolyte: 0.1 M aniline +0.5 M
H2SO4)
Fig. 21.3 SEM images of the PANI/G nanocomposite

Fig. 21.4 Resistivity changes of PANI/G SPE nanosensor: (a) lab testing in closed pH range; (b)
field testing curve
21.4 Conlusion
In summary, using the method of direct electropolymerization of PANI/G

nanocomposites on the gold wires of SPE, pH nanosensors were produced. Charac-
terization was done by cyclic voltammetry and SEM. pH sensitivity was tested in the
lab as well as in real sea waters.
Acknowledgments This research was done within the FP7 Project “Cost-effective sensors, inter-
operable with international existing ocean observing systems, to meet EU policies requirements”
(Project reference 614155).
References
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sensors based on polymer composites with carbon nanotubes and graphene: the role of the
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2. ZhA B, Sergeyev VG (2014) Polyaniline: synthesis, properties, and application. Polym Sci Ser
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80:2377
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batteries. Synth Met 18:393
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Met 57:3623
8. Talaie A, Lee JY, Lee YK, Jang J, Romagnoli JA, Taguchi T, Maeder E (2000) Dynamic
sensing using intelligent composite: an investigation to development of new pH sensors and
electrochromic devices. Thin Solid Films 363:163
9. Iijima S (1991) Helical microtubules of graphitic carbon. Nature 354:56
10. Geim A, Novoselov K (2007) The rise of graphene. Nat Mater 6:183
11. Baibarac M, Romero PG (2006) Nanocomposites based on conducting polymers and carbon
nanotubes: from fancy materials to functional applications. J Nanosci Nanotechnol 6:289
12. Dai L (2007) Electrochemical Sensors Based on Architectural Diversity of the π-Conjugated
Structure: Recent Advancements from Conducting Polymers and Carbon Nanotubes. Aust J
Chem 60:472
13. Gvozdenović MM, Jugović BZ, Stevanović JS, Trišović TLJ, Grgur BN (2011) Electrochem-
ical polymerization of aniline (Chapter 4). In: Schab-Balcerzak E (ed) Electropolymerization.
InTech, Rijeka. ISBN:978-953-307-693-5
14. Sahoo S, Karthikeyan G, Nayak GC, Das CK (2012) Modified graphene/polyaniline
nanocomposites for supercapacitor application. Macromol Res 20:415
15. Mickova I, Prusi A, Grčev T, Arsov L (2006) Electrochemical polymerization of aniline in
presence of TiO2 nanoparticles. Bull Chem Technol Maced 25:45
16. Taranu BO, Fagadar-Cosma E, Popa I, Plesu N, Taranu I (2014) Adsorbed functionalized
porphyrins on polyaniline modified platinum electrodes. Comparative electrochemical proper-
ties. Dig J Nanomater Biostruct 9:667
17. Gu J, Kan S, Shen Q, Kan J (2014) Effects of sulfanilic acid and anthranilic acid on electro-
chemical stability of Polyaniline. Int J Electrochem Sci 9:6858
18. Paunović P, Dimitrov AT, Popovski O, Slavkov D, Hadži Jordanov S (2007) Effect of carbon
nanotubes support in improving the performance of mixed electrocatalysts for hydrogen
evolution. Bull Chem Technol Maced 26:87
19. Petrovski A, Paunovic P, Avolio R, Errico ME, Cocca MC, Gentile G, Grozdanov A, Avella M,
Barton J, Dimitrov A (2017) Synthesis and characterization of nanocomposites based on PANI
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polyaniline film. Chem Res Chin Univ 28:133
Chapter 22
Preparation of Metallic and Semiconducting
SWCNT Inks by a Simple Chromatographic
Method: A Two-Parameter Study
Ana Santidrian, Nekane Lozano, Ana M. Benito, Wolfgang K. Maser,

and Alejandro Ansón-Casaos
Abstract Single-walled carbon nanotubes (SWCNTs) show either metallic or

semiconducting character, and are potential candidates for the development of
small electronic devices. However, commercial SWCNT materials consist of a
mixture of many different SWCNT conformations and certain impurities. In this
work, SWCNTs are dispersed in an aqueous medium, purified by centrifugation, and
finally separated into metallic and semiconducting inks by a gel chromatography
method. The separation is directly performed at ambient conditions, and the influ-
ence of the ink concentration and the chromatography column length are thoroughly
evaluated. The most efficient separation, distinguishing between families of semi-
conducting SWCNT with different diameters, is achieved at the lowest concentration
and with the longest column. These results provide a promising base for availability
of SWCNTs with well-defined characteristics needed for the development of elec-
tronic devices.
Keywords Carbon nanotube · Purification · Separation · Electronic properties ·

Concentration · Gel chromatography
22.1 Introduction
A single-walled carbon nanotube (SWCNT) can be described as a graphene sheet

that is rolled into a seamless cylinder. Since the graphene sheet can be rolled up with
different angles, the possible SWCNT conformations, defined by the chiral vector
(n, m), are numerous. The chiral vector (n, m) determines their unique electronic and
optical properties. Based on the electronic properties, SWCNTs can be classified into
metallic and semiconducting [1]. Moreover, SWCNTs show a rich solid-state
A. Santidrian (*) · N. Lozano · A. M. Benito · W. K. Maser · A. Ansón-Casaos

Instituto de Carboquímica ICB-CSIC, Zaragoza, Spain

230 A. Santidrian et al.
chemistry that is often influenced by their electronic properties [2, 3]. The charac-
teristics of SWCNTs make them potential elements for nanoscale electronics [4–6].
The properties of SWCNTs are only observable for well-purified and individual-
ized samples. However, SWCNT synthesis methods produce SWCNTs mixed with
different amorphous and crystalline impurities such as catalyst particles, graphitic
nanoparticles, and amorphous carbon. In most cases, SWCNT purification schemes
involve air oxidation, acid treatments, centrifugation, filtration, etc. [7] The ultra-
centrifugation method has proved to be appropriate and fast for the purification of
SWCNT inks. We have previously demonstrated the elimination of graphite parti-
cles, amorphous carbon and big bundles of SWCNTs by centrifugation in a
surfactant [8].
Semiconducting SWCNTs find application as channels in field-effect transistors
(FETs) and switches, while metallic SWCNTs could be used as conducting wires in
nanoelectronic circuits. SWCNT sensor applications include resistive gas sensors
[9, 10], field-effect transistor sensors for biomedical applications [11, 12] and
electrochemical sensors [13, 14]. Therefore, the separation between metallic and
semiconducting species is needed to improve the performance of those devices.
Different approaches have been reported to achieve the separation of SWCNTs
according to their electronic properties including density gradient ultracentrifuga-
tion, gel chromatography and selective polymer phase separation [15–17]. The
chromatographic sorting of SWCNTs has been successfully tested as a separation
method, often being a relatively complex slow process.
In this work, we study the influence of different variables in the chromatography
sorting method, specifically the concentration of the starting SWCNT dispersion and
the column length. In this way, aqueous SWCNT dispersions were ultracentrifugated
and passed through a Sephacryl gel chromatography column. The resulting sorted
SWCNT fractions were characterized by optical absorption and Raman spectroscopy
in the aqueous phase. The relevance of this work is the understanding of the
parameters involved in the gel chromatography separation in order to optimize the
method and find the conditions for a large-scale process. In addition, we aim to keep
the process in a relatively simple procedure.
22.2 Experimental
22.2.1 Materials
SWCNTs were purchased from Nanointegris Inc. Boisbriand, Quebec, Canada. The
material is produced by the HiPco method and contains a residual mass of <35%
from thermogravimetric analysis. The SWCNTs have diameters of 0.8–1.2 nm and
lengths of 100–1000 nm, according to the provider. Sodium dodecyl sulfate (SDS)
98.5% was purchased from Sigma-Aldrich. Sephacryl gel (s-200, GE Healthcare)
was used for SWCNT chromatographic sorting.
22 Preparation of Metallic and Semiconducting SWCNT Inks 231
22.2.2 Purification and Sorting
The experimental procedure for purification and sorting consisted of three steps:
dispersion, centrifugation and chromatographic separation. In a typical experiment,
SWCNTs were tip-sonicated for 1 h in 10 mL of a 0.5% SDS aqueous solution.
Different concentrations of the SWCNT initial dispersion were investigated: 2, 1, 0.5,
0.25 mg/mL. To avoid heating, the vial was kept in an ice bath during ultrasonication.
Then, the dispersion was purified by ultracentrifugation at 200.000 g for 1 h,
removing residual catalyst particles, amorphous carbon, and big tube bundles
[18]. Once the SWCNTs are individualized and purified, Sephacryl gel was used to
sort metallic and semiconducting SWCNTs. Briefly, 3 mL of the SWCNT purified
dispersion was allowed to pass through a plastic syringe containing the gel column at
room temperature and pressure. Two different column lengths, 5 and 10 cm, were
investigated, using a column diameter of 1.35 cm. Elution was done using sequentially
3 mL of 0.5%, 1%, 2% and 4% SDS, and the different fractions were collected [19].
The collected fractions were characterized by optical absorption and Raman
spectroscopy. UV-Vis-NIR spectra of the dispersions were measured in 2 mL quartz
cuvettes of 1 cm optical path. Raman spectra measurements were acquired using a
LabRAM HR Raman spectrometer (Horiba Jobin-Yvon), and laser excitation ener-
gies of 2.33 eV and 1.58 eV.
Figure 22.1a shows a schematic diagram of a single chromatographic process

consisting of only two elution stages. Specifically, 3 mL of 0.5% and 2% SDS
were subsequently passed through a 5 cm column to obtain two fractions: Fr. I and
Fr. II, respectively. The colors of the two fractions were different, reddish and
blueish (Fig. 22.1b).
To determine the compositions of the SWCNT fractions, we measured the optical
absorption spectra of the dispersions using both UV-Vis-NIR and Raman spectro-
photometers. The optical absorption spectra (Fig. 22.1c) confirm the separation
efficiency. While the starting SWCNTs present peaks of both semiconducting and
metallic electronic transitions, the fractions Fr. I and Fr. II present predominant
peaks in the region of metallic (EMii) and semiconducting (ESii) electronic transi-
tions, respectively. Therefore, the Fr. I was enriched in metallic SWCNTs, and the
Fr. II enriched in semiconducting SWCNTs. In the analysis of the Raman spectra we
focus on one of the main SWCNT features, the so-called radial breathing modes
(RBMs). The RBMs are observed between 100 and 300 cm1, where all atoms of the
tube vibrate radially in phase with diameter-dependent energies [1]. Spectra in the
RBM region were deconvoluted into Lorentzian line-shapes (Fig. 22.2).
The positions of the most intense RBM bands were first studied in the starting
HiPco SWCNT dispersion for two laser energies (Fig. 22.2). The diameters of the
Fig. 22.1 (a) Schematic diagram of the SWCNT chromatographic separation with two elution
stages. (b) Photograph of the starting SWCNT dispersion and the two collected fractions. (c)
Optical absorption spectra of the starting SWCNT dispersion (black line) and the collected
SWCNT fractions: Fr. I (red dotted line) and Fr. II (blue dashed line)
Fig. 22.2 Raman spectra in the RBM region measured on the starting SWCNT dispersion (black
line) and excited by (a) 1.58 eV and (b) 2.33 eV laser energies. The RBMs are fitted with Lorentzian
line-shapes. The dotted grey curves correspond to the fitted components and to the sum of them
SWCNTs in resonance were calculated from the RBM frequency values. The
transition energies (denoted as Eii), as well as the (n, m) index, were assigned
using the Kataura plot (Table 22.1) [20, 21].
The fractions collected from the chromatography columns were also characterized
by Raman spectroscopy (Fig. 22.3). The Raman spectroscopy results show that the
former fraction (Fr. I) is enriched in SWCNTs in resonance via E11M transitions and
the latter fraction (Fr. II) mainly contains SWCNTs in resonance via E22S transitions.
So far, it is evident that the SWCNT adsorption to the gel is critically influenced by
the surfactant concentration; the results show that the technique effectively separates
the SWCNTs between metallic and semiconducting. Now, we will study 2 process
variables in the separation of SWCNTs by gel chromatography: the effect of the
starting HiPco SWCNT dispersion concentration and the chromatography column
length effect. Figure 22.4a shows the schematic diagram of the loading process and the
Table 22.1 Diameter Elaser (eV) ωRBM (cm1) dt (nm) Index (n, m) Eii
distribution of the starting
1.58 204 1.2 (12, 5) E22S
SWCNT dispersion calculated
from the Raman RBM 215 1.15 (9, 7)
frequencies (ωRBM) 225 1.05 (10, 5)
232 1.01 (11, 3)
235 0.99 (12, 1)
267 0.92 (12, 0)
2.33 230 1.07 (12, 1) E11M
240 1.03 (9, 6)
245 0.9 (10, 4)
274 0.85 (9, 3)
278 0.82 (10, 0) E22S
290 0.79 (9, 2)
Fittings were performed with Lorentzian line-shapes. The Kataura
plot was used for the assignment of the electronic transitions
Fig. 22.3 Raman spectra in the RBM region measured on the starting SWCNT dispersion (black
line), Fr. I (red dotted line) and Fr. II (blue dashed line) excited by (a) 1.58 eV and (b) 2.33 eV
fractions obtained after the separation. A volume of 3 mL of 0.5%, 1%, 2% and 4%

SDS was subsequently added to obtain Fr. 1, Fr. 2, Fr. 3 and Fr. 4, respectively.
The efficiency of the gel-chromatography columns was semi-quantitatively eval-
uated from absorbance spectroscopy data. Each spectral band was evaluated follow-
ing a practical procedure similar to that proposed by Itkis et al. [22]The procedure is
based on the calculation of a normalized peak area, as it is explained in Fig. 22.5.
The value ratio Ap/At % was calculated by integrating the areas under the curves
for the spectra as in Fig. 22.5 and applying the expression
0 1
B =At, i C
Ap, i
B C
A p, i
=At, i % ¼ B 4 C 100 ð22:1Þ
@P Ap, i A
=A t , i
i¼1
Fig. 22.4 (a) Schematic diagram of the SWCNT chromatographic separation with four elution
stages. (b) Photograph of the starting SWCNT dispersion and the four collected fractions
Fig. 22.5 Schematic

illustration of one optical
absorption band in a typical
SWCNT sample. It aims to
illustrate the calculation of
the normalized area
where Ap,i and At,i are the areas under each band of the spectra as given in Fig. 22.5
(i denotes the band at 555 (dt ¼ 0.96 nm), 646 (dt ¼ 0.90 nm), 733 (dt ¼ 0.98 nm)
and 795 nm (dt ¼ 1.10 nm)).
The top part of Fig. 22.6 shows the absorbance spectra of the collected fractions
Fr. 1, Fr. 2, Fr. 3 and Fr. 4, using different starting HiPco SWCNT concentrations. The
normalized coefficients Ap/At of the peaks at 555 (dt ¼ 0.96 nm), 646 (dt ¼ 0.90 nm),
733 (dt ¼ 0.98 nm) and 795 nm (dt ¼ 1.10 nm) are shown for all collected fractions.
In the absorbance spectra presented in Fig. 22.6, the region marked in grey is
assigned to metallic SWCNTs being in resonance with the first optical transition energy
E11M and represent the band at 555 nm that corresponds to a diameter distribution of
0.96 nm. The orange, purple and yellow regions represent the tubes excited via the E22S
Fig. 22.6 Absorbance spectra of the starting SWCNTs and collected fractions Fr. 1, Fr. 2, Fr. 3 and
Fr. 4 for different concentrations of the starting SWCNT dispersion: a. 2 mg/mL; b. 1 mg/mL;
c. 0.5 mg/mL; d. 0.25 mg/mL. In Figures a.1., b.1., c.1., and d.1.,the grey, orange, purple and yellow
regions correspond to SWCNTs in resonance via the E11Mwith dt ¼ 0.96 nm and via the electronic
E22S transitions with dt ¼ 0.90, 0.98 and 1.10 nm, respectively
Fig. 22.7 Absorbance spectra of the starting SWCNTs (1 mg/mL) and the collected fractions:
Fr. 1, Fr. 2, Fr. 3 and Fr. 4 for two different column lengths: a. 5 cm, and b. 10 cm. In Figures a.1,
and b.1 the grey, orange, purple and yellow regions correspond to SWCNTs in resonance via the
E11M electronic transitions with dt ¼ 0.96 nm and via E22S with dt ¼ 0.90, 0.98 and 1.10 nm,
respectively
electronic transition, and comprise the strong bands at 646 nm (dt ¼ 0.90 nm), 733 nm
(dt ¼ 0.96 nm) and at 795 nm (dt ¼ 1.10 nm), assigned to semiconducting nanotubes. In
the bottom panels of Fig. 22.6, the Ap/At of the most intense bands in each region
(555 nm, 646 nm, 733 nm, and at 795 nm) is represented for the fractions collected:
Fraction 1 (Fr. 1), Fraction 2 (Fr. 2), Fraction 3 (Fr. 3) and Fraction 4 (Fr. 4).
In Fig. 22.6a.2, which corresponds to 2 mg/mL of the starting SWCNT concentra-
tion, the ratio Ap/At does not present significant changes among the different SWCNT
fractions. However, in the case of 1 mg/mL (Fig. 22.6b.2) the bands corresponding to
SWCNTs in resonance via E11M are the most intense in the first fraction (Fr. 1). On the
contrary, the following fractions (Fr. 2, Fr. 3 and Fr. 4) present the most intense bands in
resonance via E22S. Besides, in the case of 0.5 mg/mL (Fig. 22.6c.2), not only were the
SWCNTs sorted by metallic and semiconducting but also those in resonance via E22S are
sorted by diameter. The last SWCNTs to be eluted are the thinnest ones (Fr. 4). Even
more, if the concentration is lower (0.25 mg/mL Fig. 22.7d.2) the separation is more
specific, and the largest diameter SWCNTs are eluted in the first place (Fr. 2). The last
fractions (Fr. 3 and Fr. 4) are enriched in the thinnest SWCNTs. Decreasing the
concentration of the starting SWCNT dispersions improves the SWCNT separation.
Similarly, the length of the column was evaluated using 5 and 10 cm columns
(Fig. 22.7). The results shown in Fig. 22.7a.2 correspond to a column length of 5 cm.
The bands corresponding to SWCNTs in resonance via E11M are the most intense in
the first fraction (Fr. 1). On the contrary, the following fractions (Fr. 2, Fr. 3 and
Fr. 4) present the most intense bands in resonance via E22S. In general, the separation
between semiconducting and metallic was successful. In the case of the 10 cm
column (Fig. 22.7b.2), not only the SWCNTs were sorted between metallic and
semiconducting but also those in resonance via E22S are being sorted by diameter.
The last SWCNTs to be eluted are those with the thinnest diameter (Fr. 4), and those
with largest diameter are eluted in the first place (Fr. 2).
22.4 Conclusions
The results show that this simple chromatography technique effectively separates the
SWCNTs into semiconducting and metallic. In addition, the concentration of the raw
SWCNTs dispersion and the length of the column play important roles towards the
separation of SWCNTs with specific diameters. The optimum conditions are reached
with low SWCNT concentrations and long columns. This study provides new
relevant data towards the up-scaling of chromatographic separation of SWCNTs.
Obtaining SWCNTs with a well-controlled electronic character and specific diam-
eters is a critical stage for the development of electronic devices and nanocircuits
based on SWCNTs.
Acknowledgments This work has received funding from the European Union’s Horizon 2020
research and innovation programme under the Marie Skłodowska-Curie grant agreement No
642742.
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Part VI
Materials: Nanowires and Fibers
Chapter 23
Loaded Nanofibers: Force Protection,
Filtration, Decontamination
Ashok Vaseashta and Nimet Karagülle-Bölgen
Abstract In asymmetric and complex warfare environments, it is critical to deploy

the latest technological innovations for tactical advantage over adversaries. Among
others, improvements in outerwear of soldier uniform provide a significant tactical
advantage. We have studied the use of loaded nanofibers, which demonstrate
capabilities such as light weight, mechanical resilience, and breathability, i.e. the
possibility for the evaporation of perspiration. In addition, the fibers are capable of
sensing chemical/biological environment and delivering therapeutics thus providing
temporary relief from injury. Furthermore, nanofibers include communication capa-
bilities for enhanced situational awareness. This investigation outlines an ongoing
research on loading electrospun nanofibers with selected materials to produce
outerwear for soldiers providing tactical superiority. Fabrication and characteristics
of some of such fibers are presented here along with future pathways to integrate
additional capabilities.
Keywords Electrospinning · Nanofibers · Filtration · Mechanical strength · Sensors
23.1 Introduction: Justification and Methodology
In most conventional warfare, the adversaries deploy forces of a similar type and the
outcome can be predicted by estimating the quantity of the opposing forces and/or by
their quality. In the current asymmetric warfare scenario, this assumption does not
hold because the composition or strategy of the opposition forces makes it
A. Vaseashta (*)
USA
NJCU – State University of New Jersey, NJ, USA
e-mail: [email protected]; [email protected]
N. Karagülle-Bölgen
Chemical Engineering Department, Mersin University Engineering Faculty, Mersin, Turkey

242 A. Vaseashta and N. Karagülle-Bölgen
impossible for either side to close-in during battle. Naturally, the first line of defence
is self “protection”. With this as the basis, the study presented here outlines a
systematic methodology to develop micro/nanofibers using electrospinning loaded
with selected nanomaterials which are mixed into the solutions of high-performance
polymers. The methodology involves systematic identification and selection of
novel combinations of loading of nanomaterials with high-performance polymers
to provide a desired set of characteristics, which include increased mechanical
strength, improved sensitivity to contaminants, better filtering capabilities, improved
response to electromagnetic stimuli, on-demand or time-released drug delivery,
optical tunability or adaptation and conductivity, leading to system-on-fibers (SoF)
and e-textiles. Additionally, high surface area of nanofibers coupled with its poten-
tial biocompatibility and biodegradable nature, offers tremendous promise for
diverse applications in tissue engineering, targeted drug/vaccine delivery,
non-thrombogenic materials for blood contacting applications, and sensing of chem-
ical and biological environments.
Parallel to this work, our objective has been aimed at the use of advanced science
convergence methodologies to develop automated data mining tools such as auto-
mated data analysis, mining and surveillance (ADAMS™), technology foresight and
road-mapping (TechFARM™) and New and Emerging Science and Technology
Trends and Surveillance (NESTTS™) to provide additional knowledge and data-
bases. The objective of such data mining tools has been to learn technological
capabilities and gaps, to provide tactical advantage, as stated earlier. Preliminary
data of fibers using loaded high-performance polymers are presented here with the
objective to fabricate multi-functional nano/microfibers embedded with several
materials for military outerwear and gears that provide an integrated solution
pathway through a revolutionary approach of using novel nanomaterials and
ceramers embedded in high performance polymers, as outerwear materials for
suits, masks, and embedded sensors.
23.2 Electrospinning and Nanofiber Formation
Electrospinning is a process in which polymer fibers are produced through the action
of an electric field imposed on a polymer solution. The concept of electrospinning
was first introduced by Formalas in his series of patents in 1934. This technique has
gained scientific popularity in the last couple of decades, when several groups
developed several micro and nanofibers [1–10]. A simple electrospinning apparatus
consists of a high voltage power supply, a capillary to deliver the polymer and a
collector electrode, as shown in Fig. 23.1. A typical laboratory electrospinning
system consists of a microprocessor-controlled syringe pump with a high metering
precision at a low, pulse-free pre-set rate and volume control. The internal diameter
of the syringe is used by the control program to calibrate the pump and deliver a
pre-determined volume and flow rate. The electric field is applied with a high voltage
(typically ~30 kV) power supply by connecting the metal discharge needle and a
23 Loaded Nanofibers 243
Fig. 23.1 A typical

electrospinning apparatus
(E field, g gravity, γ drag, ξ
viscosity)
grounded stationary or rotating collector electrode. The strong electric field on a

polymer fluid generates an electrostatic force on the surface against the viscous
stresses of the polymeric mass, thus producing elongation jets towards the other
electrode (Fig. 23.1). A Taylor cone is generated in the jet when a hydraulic effect
produced by the syringe plunger to the polymer solution is modified by the strong
electrostatic field. The shape of the cone, employing parameters such as viscosity;
conservation of mass, charge, and momentum; electric field; surface tension; air
drag; and Coulombic and gravitational forces has been modelled by several inves-
tigators [7]. Upon application of the high voltage, a polymer jet is formed and
undergoes an elongation process before reaching the collector screen, the solvent
evaporates, and the polymer is collected as a solidified interconnected web of
nanofibers.
Several synthetic and natural polymers, polymer composites, polymers impreg-
nated with nanoparticles, carbon nanotubes, and compounds for mechanical, elec-
trical, and biological applications were attempted using single, double or triple jet
electrospinning apparatus [11]. Table 23.1 provides a list of polymers (synthetic,
natural, and biodegradable), ceramers, electro-ceramers, and bio-ceramers that were
studied and reported earlier [8]. The table lists their composition, molecular weight,
approximate range of loading, and intended applications. The study was later
extended for several new categories of materials, including negative refractive
index (NIR) materials, bioactive compounds with powerful medicinal properties,
and certain oxides to study phytotoxic and genotoxic effects. Table 23.2 provides a
list of materials that are currently being tested with the intended applications.
Figure 23.2 shows a conceptual schematic of the possible spectrum of applications
that are potentially feasible [8].
We describe below applications of loaded nanofibers in the context of force
protection, filtration, and decontamination. Force protection refers to mechanical
Table 23.1 A sample list of polymers (synthetic, natural, and biodegradable) and loading materials
– ceramers, electro-ceramers, and bio-ceramers [8]
Polymers and Molecular Applications/
composites Composition weight Loading comments
Synthetic Polystyrene/dichloroethane 299,000 CNT Field emission
Nylon (6,12)/1,1,1,3,3,3 – CNT Flexible
Hexafluoro-2-propanol substrates
Poly(etheremide)/1,1,2- 30,000 CNT Mechanical
Tricholoroethane strength – SoF
Polyacrylonitrile (PAN)/ 114,000 M CNT ZnO Strength sen-
dimethylformamide (DMF) vol. sors (SoF)
(also dimethyl acetamide
(DMAc))
Polymethylmethacrylate 540,000 None Porous fibers
(PMMA) in acetone, chloro-
form, Toluene
Polyvinylpyrrolidone/Ethanol/ 58K-1.3M Bi2S3 CT imaging
DMF
Polyprrole in Acetonitrile – TEA BF4 Conducting
(ACN), and dichloromethane polymers -SoF
(DCM)
Polyeurathane/DMF polycar- 42,000 CNT Protective
bonate/DMF clothing
Natural Lecithin/dimethylformamide – None Biomembranes
Lecithin/dimethylformamide – Bi2S3 CT imaging
Biodegradable Poly (ε-caprolactone) (PCL) – PLA/PGA Wound
dressing
Poly (L-lactide/co 150,000 PLA/PGA Stents tissue/
ε-caprolactone) (PLLA/CL) collagen scaffold
Poly (ethylene oxide)/water 400,000 PCL Hollow fibers
Polyglcolide PCL
Poly (ethylene oxide)/water 400,000 MoO3, ZnO, Sensors
TiO2
Poly (L-lactide/co 150,000 Bi2S3 CT imaging
ε-caprolactone) (PLLA/CL) collagen
Poly (L-lactide/co 150,000 Metal Targeted drug
ε-caprolactone) (PLLA/CL) nanoparticles delivery
Ceramers Polyacrylonitrile (PAN)/ 150,000 M TiO2 Conductive
dimethylformamide (DMF) vol. and PV
polymer
Polydiphenooxyphosphazene SiO2 (Y, Er) Glass/ceramic
PDPP
Electro-optic Poly(acrylic acid) -polypyrene 50,000 Optical
polymers methanol (PAA-PM)/ sensors
dimethylformamide
Poly (vinyl acetate)/Acetone GeO2 1D Opto-
electronics
Bio-ceramers Poly(l-lactic) acid, poly 70K/ Collagen Bone repair
(glycolic) acid, Poly(l-lactide/ >150K/10- mefoxin antibiotics
glycolide) 20K
Table 23.2 List of polymers and loading materials under investigation

Polymer composition Loading Applications/comments
Nylon (6,12)/1,1,1,3,3,3 Hexafluoro-2- NRI NPs Camouflage
propanol
Poly(etheremide)/1,1,2-Tricholoroethane NRI NPs Camouflage/mechanical Strength
Polyacrylonitrile (PAN)/ NRI Camouflage/strength
dimethylformamide (DMF) (also NPs/ZnO
dimethyl acetamide (DMAc))
Lecithin/dimethylformamide Ag Biomembranes
Lecithin/dimethylformamide Bi2S3 CT imaging
Poly (ε-caprolactone) (PCL) Turmeric Wound dressing
Poly (L-lactide/co ε-caprolactone) Turmeric/ Tissue/scaffold
(PLLA/CL) collagen
Polymers including polyamide, Ag, TiO2, Flame retardancy, UV protection,
polyviniyl alcohol, polyurethane, poly- Cu, ZnO, self cleaning, antistatic and antimi-
propylene, nylon-6, poly(viniyl chloride), MgO, ZrO2 crobial activities
polysulfone, poly(methyl methacrylate),
cellulose acetate
Polyacrylonitrile (PAN)/ MgO, TiO2 Chem./Bio Decon
dimethylformamide (DMF)
Fig. 23.2 Potential applications

properties that renders products mechanically strong, resilient, flexible, light weight,
breathable, and with additional capabilities such as resistance to chemical and
biological environment and the ability to camouflage. Additional built-in features
include therapeutic capabilities, either built-in or through add-on layers. Filtration
and decontamination capabilities include protection against ambient chemical/bio-
logical/radiological contaminants.
23.3 Characteristics and Application of Loaded Nanofibers
23.3.1 Smart Textiles: Force and Chem.-Bio Protection,

and Situational Awareness
The process of electrospinning offers a unique opportunity to yield nanofibers of

varying porosity with a large surface area with respect to its geometrical dimensions.
Loading of various materials, such as carbon nanotubes, metal oxides, ceramers, etc.
allow the formation and improvement of barrier materials for force protection.
Electrospun nanofibrous materials, are light weight, breathable, comfortable and
have applications in functional protective clothing for the military personnel. Several
of these loaded nanofibers include: catalytic active nanofibers; chemical/biological
sensors; nanofibers for reinforcement; insulating nanofibers; selective gas permeat-
ing materials; and high mechanical strength composites due to carbon nanotubes
embedded in a polymeric matrix. Yet other applications that we investigated are
biomimicking and optical cloaking – all of which offer promising and direct
applications of loaded micro/nano fibers in outerwear for safety and security. The
use of negative refractive index materials offers the outstanding possibility of optical
cloaking, providing a distinct advantage in combat situations. We also investigated
the use of metal-organic frameworks for visual identification in emergency situa-
tions. A selection of nano-taggants offers the possibility to trace, track, and authen-
ticate biological threats.
Another critical feature that is relevant are embedded informational and commu-
nication technology capabilities for signal receiving and communication and sensors
that respond to environmental contaminants. The ability to disperse ceramics, metal
oxides, nanoparticles, and carbon nanotubes in polymer solutions and develop
nanofibers ha produced new pathways for functional fibers that have electronics
and interconnections woven into them. The advent of mobile and pervasive com-
puting; wireless-networks; network appliances; flexible substrates; and e-textiles are
enabling the development of systems on textile or system on fibers (SoF). Such
systems demonstrate a tremendous potential towards the development of portable
functional devices, such as functional fibers embedded with data communications
systems, medical and health monitoring information systems, personal fitness,
defence systems, mobile computing, radio frequency identification devices, global
positioning systems, and interactive geographical information systems. The
technology offers feasibilities for the development of systems with physical flexi-
bility and sizes unachievable with current and conventional manufacturing technol-
ogies. The vision of SoF represents a scenario that enables context-aware
functionalities, a data communication interface, parallel detection of chemical/bio-
logical sensors, and provides for invaluable real-time information for soldiers in
combat theatres to execute critical decisions in a timely manner.
The high surface area combined with biocompatibility and the biodegradable
nature of certain fibers offer tremendous promise for diverse biomedical applications
from tissue engineering, targeted vaccine delivery, and non-thrombogenic materials
for blood contacting applications. Biodegradable polymers are highly desirable for
long-term drug delivery applications since they degrade in the body to biologically
inert and compatible molecules. By incorporating a drug into biodegradable poly-
mers, dosage forms of various shapes and sizes yield built-in time-released or
physiological condition based-released therapeutics. Secondary surgical procedures,
common after the completion of dosing regimens are rendered moot due to such
polymers.
Many biodegradable polymer chemistries have been proposed for such applica-
tions; however, the most common and successful are biodegradable polyester
sutures. These polymers include poly(glycolide), poly(D,L-lactide), and their related
copolymers poly(D,L-lactide-co-glycolide). Current commercial products based on
these materials include Decapeptyl®, Lupron Depot®, and Sandostatin LAR®. Under
suitable conditions, most synthetic and natural polymers are suited for
electrospinning; thus, allowing nanofiber preparation from nanoparticles or
vaccine-impregnated polymers. It was further demonstrated that antibiotic loaded
biodegradable and biocompatible polymeric electrospun nanofibrous membranes
can prevent post-surgery induced intra-abdominal adhesions by providing a physical
barrier during the wound healing process and at the same time serve a functional
barrier against strains of microorganisms, thereby reducing the local inflammatory
response. The results of our previous studies including synthesis of biocompatible
and biodegradable polymers, production and characterization of electrospun
nanofibers from those polymers, their loading with drugs and the release of the
drugs from therapeutic loaded polymeric matrices would provide a linkage for the
development of new functional barriers for protection applications.
The use of biodegradable polymeric systems is an alternative and efficient route
for vaccine administration, peripheral nerve regeneration, and tissue engineering,
which finds interesting applications in the context of safety and security. Some
relevant polymers include bio-degradable polymers which are specifically investi-
gated for time-controlled release characteristics; copolymers with desirable hydro-
philic/hydrophobic interactions; dendrimers for the immobilization of enzymes,
drugs, peptides, or other biological agents; and certain blends of hydrocolloids and
carbohydrate-based polymers. These biomaterials with desirable functional groups
are being created for innovative drug delivery systems and as potential linings for
artificial organs, as substrates for cell growth and as agents in drug targeting and
immunology testing, as biomedical adhesives and bioseparation membranes, and as
substances able to mimic biological systems. Some of the most promising medical
applications include treatment of primary pulmonary hypertension and pulmonary

arterial hypertension by time-controlled release templates impregnated with antico-
agulants and calcium channel blockers; bioscaffold that mimic the extracellular
matrix topology [10], polyesters combined with phosphatidyl choline for biomimetic
applications [12], intravascular stents from a blend of polyactide and trimethylene
carbonate [13], dystrophin gene immobilized templates for curing aging skeletal
muscles [14], cellulose based scaffolds for cartilage tissue engineering [15] and
esophageal tissue engineering [16], as few examples (Fig. 23.3).
23.3.2 Filtration and Decontamination
Presently, applied protective clothing includes the use of activated charcoal impreg-
nated with metal ions, which physically adsorb agents against chemical and biolog-
ical agents. Metal oxide nanoparticles such as TiO2 and MgO are proposed as
potential catalysts for the decontamination of chemical and biological agents. The
significant properties of such adsorbents are due to their high surface areas and high
surface concentrations of reactive defect sites. However, there are disadvantages of
modification of e-textile surfaces with nanoparticles, especially the ones which are
not stabilized on the surface of the textiles. In addition to altering the physical and
mechanical properties of the textile materials, associated toxic effects of
nanoparticles on human systems are still under discussion. Furthermore, inhalation
of those nanoparticles in high doses can result in pulmonary inflammation and
allergic reactions, therefore the use of nanoparticles in powder form is difficult in
protective clothing. To overcome this limitation, research effort was directed to
incorporate nanoparticles with nanofibers by including of nanoparticles with poly-
mer solution before electrospinning [17]. Nanofiber based materials suggest novel
protecting clothing materials with comfortable, adsorptive and lightweight proper-
ties with active detoxyfying/decontaminating nanomaterials, primarily facilitated by
their nature at nanoscale [18]. Several intended applications are listed in Table 23.3,
also consistent with the priorities of defence agencies.
Electrospun chromatography is a cost-effective methodology for obtaining dif-
ferent surface selectivity by changing the polymer materials to electrospun filtration
systems. Fabrication of polymer derived electrospun nanofibers by electrospinning
as chromatographic sorbent bed for ultra-thin layer chromatography offers on-plate
identification and separation of analytes from their mixture solutions. It has been
reported that electrospun fiber based stationary phases in ultra-thin layer chroma-
tography (UTLC) have an enhanced separation efficiency to provide separation of
analyte mixtures in a shorter development time than those of the traditional particle-
based stationary TLC phases. In addition to UTLC, incorporation of a given target
molecule into a membrane to express permselectivity is also investigated for molec-
ular recognition sites into synthetic membranes.
Fig. 23.3 (a) Use of nanofibers in information and communications technology; (b) Intended
applications in soldier uniforms
23.4 Discussion and Path Forward
Due to the increasing interest in materials at the nanoscale and the associated
interesting properties, research on electrospinning processes has increased signifi-
cantly in the recent years. Using several innovative spinning techniques and
Table 23.3 Nanoscale filtration applications

Wearable kidney
Water desalination
Water purification (collagen based)
Breathable protection clothing
Wearable anti-dehydration systems
Advanced rebreathers for indefinite-length underwater presence – artificial gills
Superior gas masks
MoS2 nanoparticles – especially for volatile organic compounds (VOC)
modified collectors [11], structures with different compositions, complex architec-

tures [8], fiber morphologies [19], improved properties [20–22], varying degradation
rates, and functional moieties have been produced. Electrospun nanostructured
polymer structures of natural or synthetic origin have a multitude of possible
applications in addition to defence as demonstrated here, including medicine, phar-
macy, optoelectronics, sensor technology, catalysis, and filtration. Development of
new and smart protective textiles for future applications include, integration of
nanoparticles with multiple threat sensing capability and energy storing/harvesting
devices built in the protective clothing. Smart protective textiles are still at the
development phase but some of the materials are already quite close to commercial
production. However, there are limitations, viz. nanofiber based protective textiles
still require extensive research before large scale production. Life cycle analysis, as it
relates to health and safety in all stages of the products, requires an extensive
investigation and evaluation for its short and long-term health risks [23]. The
selection of a polymer for use as a degradable biomaterial must match the mechan-
ical properties and the degradation rate to specific parameters. The greatest advan-
tage of biodegradable polymers is that they are fragmented into biologically
acceptable, metabolized and removable molecules. However, biodegradable mate-
rials do produce degradation by-products that must take place with little to no
adverse reactions within the biological environment. These degradation products
must be tested thoroughly. Some of the factors affecting biodegradation of polymers
are the presence of ionic groups, low-molecular-weight compounds, and unexpected
units or chain defects. Several other contribution factors are configuration structure,
molecular weight and its distribution, morphology, functionalization process,
implantation site, adsorbed and absorbed compounds (water, lipids, ions, etc.),
physicochemical factors (ion exchange, ionic strength, pH), and associated physical
factors. Much of the development of novel materials in controlled drug delivery
focuses on preparation and use of these responsive polymers with specifically
designed macroscopic and microscopic structural and chemical features. These
new biomaterials with desirable functional groups are being created by researchers
who envision their use not only for innovative drug delivery systems but also as
potential linings for artificial organs, as substrates for cell growth or chemical
reactors, as agents in drug targeting and immunology testing, as biomedical adhe-

sives and bio-separation membranes and as substances that are able to mimic
biological systems.
References
1. Huang ZM, Zhang YZ, Kotaki M, Ramakrishna S (2003) A review on polymer nanofibers by
electrospinning and their applications in nanocomposites. Compos Sci Technol 63:2223–2253
2. Chua KN, Lim WS, Zhang P, Lu H, Wen J, Ramakrishna S, Leong KW, Mao HQ (2005) Stable
immobilization of rat hepatocyte spheroids on galactosylated nanofiber scaffold. Biomaterials
26:2537
3. Xang W, Drew C, Lee SH, Senecal KJ, Kumar J, Samuelson LA (2002) Electrospun
nanofibrous membranes for highly sensitive optical sensors. Nano Lett 2(1):1273
4. Kim JS, Renekar DH (1999) Mechanical properties of composites using ultrafine electrospun
fibers. Polym Compos 20(1):124
5. Locher I, Kirstein T, Troster G (2004) Temperature profile estimation with smart textiles. In:
Kiang K, Gorton J, Alert M (eds) Proceedings of 37th international symposium on microelec-
tronics, IMAPS, p 204
6. E-Textile. Virginia Tech, Blacksburg. www.ccm.ece.vt.edu/etextiles
7. Rutledge S, Hohman MM, Shin MY, Brenner MP (2001) Electrospinning and electrically
forced jets: I. Stability theory Phys. Fluids, 13 2201, and Electro-spinning and electrically
forced jets: II. Apps., Phys. Fluids (2001) 13 2221
8. Vaseashta A, Stamatin I (2007) Electrospun polymers for controlled release of drugs, vaccine
delivery, and system-on-fibers. J Optoelectron Adv Mater 9(6):1606–1613
9. Lu Y, Chen S (2004) Micro and nanofab. of biodegradable polymers for drug deli-very. Adv
Drug Deliv Rev 56:1621
10. Kim TG, Park TG (2006) Biomimicking ECM: cell adhesive RGD peptide modified
electrospun Poly(D,L-lactic-co-glycolic acid) nanofiber mesh. Tissue Eng 12(2):221
11. Vaseashta A (2007) Controlled formation of multiple Taylor cones in electrospinning process.
Appl Phys Lett 90:093115
12. Hillborn J (2005) Non-thrombogenic biodegrad-able polymers for the new generation of
phospholipid analogues Priv. Com
13. Medical Device Link. http://www.devicelink.com
14. Vaseashta A, Boskovic O, Webb A, Ozdemir N, Ozturk E (2006) Effect of dystrophin gene
immobilized nano-structured therapeutic templates on aging skeletal muscles. In: Kassing R,
Petkov P, Kulisch W, Popov C (eds). Springer, Funct. Prop of Nanostructured Mater, p 511
15. Muller FA, Muller L, Hofman I, Greil P, Wenzel MM, Staudenmaier R (2006) Cellulose-based
scaffold materials for cartilage tissue engineering. Biomaterials 27(21):3955
16. Zhu Y, Chian KS, Chan-Park MB, Mhaisalkar PS, Ratner BD (2006) Protein bonding on
biodegradable poly(L-lactide-co-caprolactone) membrane for esophageal tissue engineering.
Biomaterials 27:68
17. Vaseashta A, Dimova-Malinovska D, Marshall JM (eds) (2005) Nanostructured & advanced
materials. Springer, Dordrecht
18. Vaseashta A (2005) Nanostructured materials based next generation devices and sensors,
nanostructured and advanced materials. In: Vaseashta A, Dimova-Malinovska D, Marshall
JM (eds) . Springer, Dordrecht, pp 1–30
19. Sundarrajan S, Chandrasekaran AR, Ramakrishna S (2010) An update on nanomaterials-based
textiles for protection and decontamination. J Am Ceram Soc 93:3955–3975
20. Thilagavthi G, Raja ASM, Kannanian T (2008) Nanotechnology and protective clothing for
defence personnel. Def Sci J 58:451–459
21. Dhineshbabu NR, Karunakaran G, Suriyaprabha R, Manivasakan P, Rajendran V (2014)

Electrospun MgO/Nylon 6 hybrid nanofibers for protective clothing. Nano-Micro Lett 6:46–54
22. Balasubramanian Kandasubramanian R (2013) Advancement in textile technology for defence.
Def Sci J 63:331–339
23. Vaseashta A (ed) (2015) Life cycle analysis of nanoparticles – risk, assessment, and sustain-
ability. Destech Publishers, New York 978-1-60595-023-5, (404 pages)
Chapter 24
Nanocomposites of Electrospun Polymeric
Materials As Protective Textiles Against
Chemical and Biological Hazards
Nimet Bölgen and Ashok Vaseashta
Abstract Chemical and biological agents effects tissues and organs which cause
poisoning, disease, and deterioration. Chemical or biological weapons show signif-
icant threats to humankind. Therefore, many studies have presented approaches for
protection from biological and chemical agents. There are various types of defence
equipments to protect a body from those agents such as developed detectors,
protective clothing materials, functional decontaminants, and others. A number of
studies have reported about protective clothing against chemical and biological
agents, because many of them are dermally active. New protective clothing materials
(comfortable, adsorptive, light-weight) combined with active detoxifying/
decontaminating nanomaterials have been produced recently. Electrospinning is
one of the simplest and most versatile methods to fabricate nanofibers with high
surface areas. Electrospun polymeric nanofibers were used as a protective barrier on
the textile fabrics. Attempts have been made to incorporate nanoparticles, nanotubes
and antimicrobials into electrospun fibers to enhance their functionality. In this
contribution, a selection of studies about the use of electrospun nanofibers for
protective clothing against chemical and biological agents is summarized.
Keywords Nanofibers · Electrospinning · Nanocomposites · Protective clothing ·

Chemical agents · Biological agents
N. Bölgen (*)
Mersin University, Engineering Faculty, Chemical Engineering Department, Mersin, Turkey
A. Vaseashta
Institute for Advanced Sciences Convergence, and Int’l Clean Water Institute, Herndon,
VA, USA
NJCU - State University of New Jersey, NJ, USA

254 N. Bölgen and A. Vaseashta
24.1 Introduction
Chemical and biological agents effects tissues and organs which cause poisoning.
There are various types of defence equipments to protect a body from those agents
including protective clothing. Electrospinning is one of the simplest and most
versatile methods to fabricate nanofibrous textiles with a high surface area.
Electrospun polymeric nanofibers were used as a protective barrier. In this contri-
bution, studies about the use of electrospun nanofibers for protective clothing against
chemical and biological agents is summarized.
24.2 Electrospinning
Electrospinning is a process in which polymer fibers are produced with diameters

down to the nanometer range through the action of an electric field imposed on a
polymer solution/melt. This technique became very popular in the last 10 years in the
scientific area, although the fundamental idea was first described by A. Formalas in
his series of patents in 1934 [1]. In a simple electrospinning system a high voltage
power supply, a capillary and a collector are used (Fig. 24.1). One electrode is placed
into the polymer solution present in the capillary and the other one is attached to the
collector. As the high voltage is applied, the polymer jet undergoes an elongation
process before reaching the collector screen, the solvent evaporates and the polymer
is collected as a solidified interconnected web of nanofibers [2].
Distinct properties that make electrospun nanofibrous materials unique are their
high surface area, porosity, tensile strength (stronger than steel on weight basis) and
Fig. 24.1 Components of an electrospinning system

24 Nanocomposites of Electrospun Polymeric Materials 255
high extensibility (comparable to rubber elasticity). Indeed, the size of the fibers
down to the nanometer scale make the final structures unique. Electrospinning
enables to produce non-woven nanofibers which are homogeneous in size and
geometry. But also it is possible to prepare oriented nanofibers. The orientation of
the fibers can be accomplished using a rotating mandrel or a rotating disk collector.
The applications of electrospun nanofibers include the use of pesticide containing
ones or using them as a physical barrier to insects. They can also be used in the
filtration of unwanted ingredients in the gases released from a factory. Space or
construction technologies can apply them. Biomedicine is another area of applica-
tion of the nanofibers, they can be used as tissue engineering scaffolds since they
mimic very well the structure of the extracellular matrix [3]. And they can be used in
protective clothing.
24.3 Protective Clothing for Chemical/Biological Hazards
Chemical and biological warfare agents target tissues and organs which cause
poisoning, disease and deterioration. Chemical or biological weapons cause signif-
icant threats to humankind. For example, nerve gases can enter the body by
inhalation or by skin absorption, resulting in death from acute poisoning occuring
in a minute by asphyxia. Blood agents interfere with the body’s ability to absorb
oxygen; as a result the victim dies as the body tissues are starved of oxygen. Choking
agents attack the lungs and cause them to fill with fluid.
There are different types of defence equipments to protect the body from the
chemical and biological agents such as detectors, protective clothing,
decontaminants and medical counter measures. A variety of studies have reported
about protective clothing against chemical and biological agents, because many of
the agents enter the body through the skin.
Presently applied protective clothing against chemical and biological agents
include the use of activated charcoal impregnated with metal ions, which physically
adsorb agents thereby creating disposal waste after its usage. Metal oxide
nanoparticles such as TiO2 and MgO are currently suggested as potential catalysts
for the decontamination of chemical and biological agents. The significant properties
of these “destructive adsorbents” are due to their high surface areas and high surface
concentrations of reactive defect sites. However, there are disadvantages of modifi-
cation of textile surfaces with those nanoparticles: nanoparticles are not stable on the
surface of the textiles; they need to be stabilized by using some processes, and those
processes may change the mechanical and physical properties of the textile materials
such as tensile strength, softness, flexibility and appearance. In addition, the toxic
effects of nanoparticles on human systems is still under discussion; inhalation of
these nanoparticles in high doses can result in pulmonary inflammation and allergic
reactions, therefore the use of nanoparticles in powder form is problematic in
protective clothing. To overcome this limitation, research effort was directed to

incorporate nanoparticles into nanofibers by including nanoparticles into the poly-
mer solution before electrospinning [4].
24.4 Electrospun Membrane Based Protective Clothing
Nanofiber based materials suggest novel protecting clothing materials with comfort-
able, adsorptive and lightweight properties conntaining active detoxyfying/
decontaminating nanomaterials, due to their extraordinary physical and chemical
properties at the nano level. Electrospinning is one of the simplest and cheap
methods to produce nanofibrous materials [5]. There is a variety of developments
related to the application of electrospun nanofibrous materials in fabricating light-
weight, comfortable and functional protective clothing for military personnel. The
new developed materials include catalytic active nanofibers (for chemical and
biological breakdown); sensors (sensitive to absorbtion and subsequent change);
nanofibers for reinforcement (antiballistic application); insulating nanofibers; selec-
tive gas permeating properties; high strength composites (carbon nanotube-poly-
meric nanofibers) [5].
24.5 Antibacterial Nanofibers
Studies have been made to incorporate nanoparticles into electrospun nanofibers to

enhance their properties [6]. Polymers including polyamide, polyviniyl alcohol,
polyurethane, polypropylene, nylon-6, poly(viniyl chloride), polysulfone, poly
(methyl methacrylate), and cellulose acetate, were combined with nanoparticles
such as Ag, TiO2, Cu, ZnO, MgO, and ZrO2. The composite materials gained
functional properties like flame retardancy, UV protection, self cleaning, antistatic
and antimicrobial activities.
Current developments related to the potential use of electrospun nanofibers in
protective clothing include the production of antimicrobial nanofibers. Most textile
materials recently used in military are open to diseases caused by microorganisms.
To avoid infections and attack of microorganisms, antimicrobial properties can be
gained in textile material by incorporating functional agents (metal oxides such as
Ag, TiO2, Cu, ZnO, MgO) onto fibers and fabrics. In addiditon, drug loading into
textile material can be obtained by incorporating a drug during the preparation of the
textile material or after the formation of it by incubating the drug with it [7].
The toxicity of elements to microorganisms is considered to be in the following
sequence: Ag > Hg > Cu > Cd > Cr > Pb > Co > Au > Zn > Fe > Mn. The principle of
the mechanism of the antibacterial effect of those toxic elements to microorganism
includes the electrostatic interaction between negatively charged bacterial cells and
24 Nanocomposites of Electrospun Polymeric Materials 257
positively charged nanoparticles. As an example, the mechanism of action for Ag is

to strongly bind to electron donor groups containing S, O, or N and to bring about
structural and functional changes in the cell. When Ag binds to proteins in the cell
wall, the wall is destroyed, and the internal cell content leaks out, resulting in the
death of the bacterial cell. Consequently, this prevents the microorganism from
performing its functions, like carrying out processes necessary for respiration or
processing nutrients leading to the subsequent death of the bacterial cell [8].
Related to the potential use of antibacterial nanofibers, a variety of studies is
present in the literature. As example from previous studies, Magnesia (MgO)
nanoparticles were produced from magnesite (MgCO3) using ball milling; Nylon
6 pellets were dissolved in a mixture of formic acid and acetic acid. MgO
nanoparticles were added into the prepared homogenous Nylon 6 polymer solution.
MgO/Nylon 6 hybrid nanofibers were coated on a cotton fabric. The values of
flammability and antibacterial activity were evaluated. The burning time for
MgO-Nylon fabrics were found to be higher than that of Nylon and uncoated cotton
fabrics. In addition, the MgO-Nylon 6 fabric showed a higher bacterial reduction
percentage when compared to the pure Nylon fabric. The MgO-Nylon6 fabric has
enhanced protective surface properties through antibacterial activity [6].
The conventional electrospinning technique was not satisfactory due to the
coverage of the nanoparticles by the polymeric nanofibers. To overcome this
constraint, the electrospraying technique was combined with the electrospinning
method. Electrospraying has been demonstrated to be one of the most promising
approaches to prepare nanofibers with nanoparticles on their surfaces. The produc-
tion of functionalized nanofibrous materials was carried out by electrospinning of
nanofibers and electrospraying of nanoparticles. Two types of membranes were
fabricated. Electrospinning of a polysulfone polymer and electrospraying of TiO2
nanoparticles dispersed in the presence of surface modifier can be given as an
example to the application of this combined technique [4].
In another work, silver loaded titania was prepared by introducing silver
nanoparticles onto a titania surface. Polyurethane was dissolved in a solvent mixture
of N,N-dimethylformamide and tetrahydrofuran. Polyurethane solutions were
electrospun to nanofibrous structures by using an electrospinning setup with a two
robot system. The equipment was basically composed of a rotating drum collector, a
high voltage power supply and a syringe pump.A silver-titania spreaded polyure-
thane nanofibrous composite was prepared by a simultaneous electrospinning/
electrospraying process. The photocatalytic degradation of a chemical agent stimu-
lant for the nerve agent Sarin (Dimethyl methylphosphonate (DMMP)) was evalu-
ated; the nanofibrous composite material showed photocatalytic degradation of
DMMP under visible light and UV-A irradiation. The antimicrobial activity of the
material was quantified against Staphylococcus aureus. The composite material
showed a good functional antimicrobial activity against Staphylococcus aureus.
The composite demonstrated to be able to act as a functional protection layer with
the photocatalytic and antimicrobial activities against chemical and biological
agents [9].
24.6 Conclusions
The development of new and smart protective textiles for future applications include
the integration of nanoparticles with sensing properties, sensors and electronic
devices attached into the textile structures to produce smart protective textile mate-
rials, and energy storing protective clothing. Smart protective textiles are still in the
development phase and some of the materials are already quite close to commercial
production. However, there are limitations: nanofiber based protective cloths are still
at the development stage; extensive research is needed for the adequate production
of these materials on a large scale. Furthermore, the health and safety problems
related to the products which include nanoparticles require a completed investigation
and evaluation in view of short and long term health risks.
References
1. Huang ZM, Zhang YZ, Kotaki M, Ramakrishna S (2003) A review on polymer nanofibers by
electrospinning and their applications in nanocomposites. Compos Sci Technol 63:2223–2253
2. Pişkin E, Bölgen N, Eğri S, İşoğlu İA (2007) Electrospun matrices made of poly(α-hydroxy
acids) for medical use. Nanomedicine 2:441–457
3. Pişkin E, İşoğlu İA, Bölgen N, Vargel İ, Griffiths S, Çavuşoğlu T, Korkusuz P, Güzel E, Cartmell
S (2009) In vivo performance of simvastatin-loaded electrospun spiral-wound polycaprolactone
scaffolds in reconstruction of cranial bone defects in the rat model. J Biomed Mater Res Part A
90:1137–1151
4. Sundarrajan S, Chandrasekaran AR, Ramakrishna S (2010) An update on nanomaterials-based
textiles for protection and decontamination. J Am Ceram Soc 93:3955–3975
5. Thilagavthi G, Raja ASM, Kannanian T (2008) Nanotechnology and protective clothing for
defence personnel. Def Sci J 58:451–459
6. Dhineshbabu NR, Karunakaran G, Suriyaprabha R, Manivasakan P, Rajendran V (2014)
Electrospun MgO/Nylon 6 hybrid nanofibers for protective clothing. Nano-Micro Lett 6:46–54
7. Ramdayal K (2013) Balasubramanian, advancement in textile technology for defence. Def Sci J
63:331–339
8. Lala NL, Ramaseshan R, Bojun L, Sundarrajan S, Barhate RS, Ying-Jun L, Ramakrishna S
(2007) Fabrication of nanofibers with antimicrobial functionality used as filters: protection
against bacterial contaminants. Biotechnol Bioeng 97:1357–1365
9. Ryu SY, Park MK, Kwak SY (2013) Silver-titania/polyurethane composite nanofibre mat for
chemical and biological warfare protection. Int J Nanotechnol 10:771–788
Part VII
Materials: Nanocomposites
Chapter 25
Temperature Effect on the Dielectric
Response of Carbon Nanotubes Particles
Filled Polyester Polymer Composites
Z. Samir, S. Boukheir, Y. El Merabet, M. P. F. Graça, M. E. Achour,

and L. C. Costa
Abstract Polyester/carbon nanotubes composites were prepared, and the frequency

and temperature dependence of the electrical properties were studied at concentra-
tions below and above the percolation threshold. The analysis of the complex
permittivity using the derivative formalism allows us to overcome difficulties caused
by the high electrical conductivity, which can mask the dielectric relaxation pro-
cesses. The dielectric permittivity was analyzed using the Havriliak-Negami model
taking into account the effect of electrode polarization. This analysis enabled us to
describe quantitatively the experimental data, to calculate the ohmic conductivity
and the parameter characterizing the contribution of the ohmic conduction to the
complex dielectric permittivity. Above the percolation threshold, using the complex
permittivity the dielectric data were analyzed at several temperatures. Both below
and above the percolation threshold, the activation energy decreases with an increase
in the concentration of carbon nanotube in the composite, which may be due to an
increase of charge carrier density leading to a decrease of the domain boundary
potential of carbon nanotube aggregates in the polyester matrix.
Keywords Carbon nanotubes · Composites · Electrical conductivity · Havriliak-

Negami model
Z. Samir · Y. El Merabet · M. E. Achour (*)

LASTID Laboratory Department of Physics, Faculty of Sciences, University Ibn Tofail,
Kenitra, Morocco
S. Boukheir
LASTID Laboratory Department of Physics, Faculty of Sciences, University Ibn Tofail,
Kenitra, Morocco
Laboratoire LN2E, Faculté des Sciences, Université Cadi Ayyad, Marrakech, Morocco
M. P. F. Graça · L. C. Costa

262 Z. Samir et al.
25.1 Introduction
Carbon nanotubes (CNT) are tiny cylindrical structures, characterized by a high

aspect ratio, that is, a significant length relative to their nanometric diameter, and
possess exceptional transport and mechanical properties [1, 2]. CNTs can have either
conducting or semiconducting properties [3, 4], which make them functional for
many applications, such as polymer based nanocomposites for electromagnetic
interference shielding, electrostatic discharge and electrically conductive parts of
devices [5–7]. The electrical conductivity of polymer/CNT composites depends
strongly on the filler network formation, providing the path of external electrical
currents through the material [8–12].
Relaxation phenomena in solid dielectrics are one of the most studied topics in
materials science and usually the spectra of the real and imaginary parts of the
complex permittivity are extensively used to present this kind of dielectric behaviour
[13]. However, this analysis may be rendered difficult because of a DC conductivity
contribution that hides the dielectric relaxation processes. In order to overcome this
shortcoming caused by the high electrical conductivity, a suitable alternative is
introduced in this study.
In this paper, the effect of frequency and temperature on the dielectric response of
CNT filled polyester matrix was studied at concentrations below and above the perco-
lation threshold. Below the percolation threshold, we have studied the nature of the
relaxation mechanisms by analyzing the frequency and temperature dependence of the
real and imaginary parts of the dielectric permittivity, revealing the ohmic conductivity
and the parameters characterizing that contribution, and calculating the activation
energies using the Vogel-Tammann-Fulcher (VTF) equation. We have found that the
calculated activation energy values decrease as the filler concentration of CNTs inside
the polymer matrix increases. Above the percolation threshold, the dielectric data were
also analyzed using the complex permittivity at different temperatures. The temperature
dependence of the DC conductivity follows the VTF equation which allows us to
estimate the activation energies of the processes in the composite materials. By adding
low concentrations of CNTs the values of the activation energy decrease as a result of the
impact of space charge. The addition of low concentrations creates local energy levels in
the energy gap which could act as traps for charge carriers, which move by hopping
between these levels. By increasing the CNT concentration, the activation energy
decreases as a result of the increase of local centers.
25.2 Experimental
25.2.1 Materials
Multiwalled carbon nanotubes were purchased from Cheap-Tubes, USA,

possessing average diameters about 50 nm, lengths between 10 and 20 μm and
25 Carbon Nanotube Particle Filled Polyester Polymer Composites 263
a purity above 95 wt%. The matrix used in this work was the unsaturated
polyester resin 154TB, including 31 wt% of the styrene monomer, requiring
30 min for gelation at room temperature. It was acquired from Cray Valley/
Total, USA. The polyester/CNT nanocomposites were prepared by mixing 5.87 g
of liquid polyester resin and 0.2% weight of cobalt octanone as reaction activator.
CNTs were introduced before adding 1.0% of hardener to make each mixture
cohesive. Each polyester/CNT composite was mixed at room temperature for
5 min, promoting the gelation and then it was poured into a mould. After a few
hours, the samples were unmoulded, taking 24 h for having a complete
polymerization.
25.2.2 DC Electrical Conductivity
For the electrical measurements, we used samples with a shape of discs, possessing a
thickness of about 3 mm and diameter of 12 mm. Prior to these measurements, the
sample surfaces were polished and covered with a thin layer of silver paint. DC
conductivity measurements σ DC were carried out using a 617 Keithley electrometer.
The electrical contacts were made with silver paint. The experiment consists in
measuring the electrical resistance of each sample in order to determine the DC
conductivity of the different series of the composites at a constant temperature of
300 K.
25.2.3 AC Electrical Conductivity

0 00
The complex permittivity function ε∗(ω) ¼ ε (ω) + ε (ω), was measured using an
0
Agilent 4294A precision impedance analyser. The relative permittivity ε , and the
00
∗
loss factor ε , of the sample were calculated from the admittance Y (ω) ¼ G(ω) + iB
0 00
(ω) ¼ iC0ωε∗(ω) of the equivalent circuit leading to ε (ω) ¼ 2h B/ε0 d2π 2F and ε
(ω) ¼ 2h G/ε0 d π F, where B is the susceptance, G the conductance, F the
2 2
frequency, ε0 the vacuum dielectric constant, and h and d are the thickness and the
diameter of the sample, respectively. The measurements were performed in the
frequency range 100 Hz to 1 MHz under isothermal conditions, for temperatures
00
ranging between 300 and 380 K. The imaginary part of ε can be written as the sum
00
of two terms: ε ðωÞ ¼ εcond ðωÞ þ εrelax ðωÞ, where εcond and ε00relax represent the
00 00 00
contributions of an eventual conduction mechanism and relaxation phenomena in the

sample, respectively.
264 Z. Samir et al.
Fig. 25.1 DC conductivity

as a function of ϕ/ϕc of the
polyester/CNT composites
25.3.1 DC Conductivity
Figure 25.1 shows the DC conductivity of the composites as a function of CNT

concentration, normalized by the percolation threshold ϕc. At low CNT loading, the
composite is still an insulating material. A sharp increase in conductivity is observed
at the critical concentration, indicating the formation of a percolation network. The
DC conductivity above the percolation threshold can be correlated to the conductive
filler volume concentration given by σ / (ϕ ϕc )t [14], where t is the percolation
exponent related to the dimensionality of the system. In our previous work [15, 16],
using least squares fits, we found the percolation threshold ϕc 0.60% and the
experimental exponent t ¼ 1.58.
25.3.2 Dielectric Response Below the Percolation Threshold

0 00
Figure 25.2 illustrates the variation of the real ε , and the imaginary ε , parts of the
complex permittivity versus frequency, for different CNT concentrations below the
0
percolation threshold at a constant temperature T ¼ 300 K. It is noticed that both ε
00
and ε decrease with increasing frequency and increase with increasing CNT
concentrations.
0 00
The frequency dependence of ε and ε at constant temperatures for a fixed
concentration of CNTs close to the percolation threshold (ϕ ¼ 0.5%), is shown in
0
Fig. 25.3a, b. The analysis of these curves reveals that ε decreases with frequency
which can be a signature of a relaxation process in the composite. In addition, we can
0 00
Fig. 25.2 ε and ε for different concentrations of CNT below ϕc, at a constant temperature
T ¼ 300 K
0 00
Fig. 25.3 The frequency dependence of ε and ε at constant temperatures of polyester/CNT
composites with 0.5% CNT inclusions
00
see that there is no sign of dielectric relaxation peaks in ε (Fig. 25.3b). These peaks
are however hidden by ohmic conduction losses. In order to eliminate the ohmic
conduction from the measured loss spectra and to highlight the dielectric relaxation
peaks in fine, the trend towards using Kramers-Kronig relations (KK) [17, 18] seems
to be the best way
Z 1
00 σ DC 2 ω0
ε ð ω0 Þ ¼ ε00cond ðω0 Þ þ ε00relax ðω0 Þ ¼ þ ε0 ð ω Þ 2 dω ð25:1Þ
ω0 ε 0 π 0 ω ω20
where σ DC is the ohmic conduction, ε0 the vacuum permittivity and ω0 the relaxation
0 00
frequency. It should be noted that both ε and ε contain the information about the
266 Z. Samir et al.
Fig. 25.4 Variation of ε00deriv

with frequency at different
temperatures of polyester/
CNT composites with 0.5%
CNT inclusions
0
relaxation process. However, ε has made no conspicuous contribution to the fre-
quency independent ohmic conduction. For this reason, the determination of the
dielectric loss from the real part of the permittivity removes the conduction contri-
bution. One useful technique is based on the derivation, which transforms the real
0
part of the complex permittivity ε into ε00deriv , as given by Eq. (25.2) [19–23]
π ∂ε0 ðωÞ
ε00 ðωÞ ε00deriv ðωÞ ¼ ð25:2Þ
2 ∂ ln ðωÞ
00
As seen in Fig. 25.4, ε deriv possesses a sharp peak indicating the existence of a
dielectric relaxation process which was previously totally masked by the DC con-
ductivity. Indeed, when using the derivative technique, dielectric relaxation peaks
are henceforth undeniably visible.
The frequency dependence of the real and imaginary parts of the dielectric
permittivity reveals that the relaxation processes in these composites are rather
complex. In order to determine the parameters of this processes, we analysed the
results using the Havriliak–Negami model (MHN), taking into consideration the
ohmic conduction losses. In this model, the expression of the complex dielectric
permittivity is given by Eq. (25.3) [24]:

εs ε1 1 σ DC N
ε ∗ ð ωÞ ¼ ε 1 þ β
þ : ð25:3Þ
ð1 þ ðiωt Þα Þ i ωε0
where εs and ε1 are the dielectric constants at zero and infinite frequency respec-
tively, τ is the relaxation time, and α and β are empirical exponents. σ DC is the ohmic
conductivity and N a parameter characterizing the contribution of the ohmic con-
duction in the complex dielectric permittivity. It is worthy to notice that we are
interested only in the parameters σ DC and N.
00
Fig. 25.5 Variation of ε ,
with frequency for different
temperatures below
percolation threshold.
Symbols are the
experimental points and the
solid lines are the fits for
MHN model
0 00
The real ε and imaginary ε parts of the complex permittivity in this model are
defined as follows (Eqs. (25.4) and (25.5)) [24]:
ðεs ε1 Þð cos ðβ tan 1 ðρÞÞÞ

ε 0 ð ωÞ ¼ ε 1 þ : ð25:4Þ
ξβ=2

00 ðεs ε1 Þð sin ðβ tan 1 ðρÞÞÞ σ0 N
ε ð ωÞ ¼ ε 1 þ þ : ð25:5Þ
ξβ=2 ε0 ω
α
where ϱ ¼ 1þððωτ Þ sin ðαπ=2Þ
ðωτÞα cos ðαπ=2ÞÞ
and ξ ¼ 1 + (ωτ)2α + 2(ωτ)α cos (απ/2)
In order to calculate the values of σ DC and N, we analyzed the experimental
00
results of ε using the Havriliak-Negami model. Figure 25.5 shows that this model
00
presents a very good adjustment for the experimental values of ε in the explored
00
range of frequencies. Figure 25.6 illustrates the parameter N obtained by fitting ε as
a function of temperature. One can clearly see that this parameter varies between 0.3
and 1.
In order to calculate the activation energy, we used the parameter σ DC calculated
00
by adjustment of ε . Figure 25.7 shows that the conductivity increases exponentially
with temperature, indicating that it is a thermally activated process, governed by the
VTF law [25, 26]:

E
σ DC / exp : ð25:6Þ
K B ðT T 0 Þ
Here E is the activation energy of σ DC and KB, T and T0 are Boltzman’s constant,
absolute temperature and ordering temperature, respectively. It should be noted that
E was calculated from the slopes of the straight lines of ln (σ DC) versus 1/(TT0)
(Fig. 25.7) for the volume CNT concentrations of 0.0%, 0.2% and 0.5%. The values
of the activation energy for the three concentrations were calculated and are resumed
in Table 25.1. As can be seen there is a decrease in the activation energy as the filler
268 Z. Samir et al.
Fig. 25.6 Parameter 0 0

N obtained by fitting ε as a
function of temperature, for
different volume
concentrations of CNT
(0.0%, 0.2% and 0.5%)
Fig. 25.7 ln(σ DC)

vs. 1/(TT0) for different
volume concentrations of
CNT (0.0%, 0.2% and
0.5%)
Table 25.1 Summary of VTF fitting parameters E and T0 for different volume concentrations of
CNT (0.0%, 0.2% and 0.5%)
ϕ (%) E (meV) T0 (K)
0.0 128.50 7.22 201 4
0.2 87.45 5.30 190 4
0.5 30.07 3.62 154 6
concentration of CNT increases. Similar to a study of the effect of carbon black

particle on epoxy [27, 28], this behavior may be due to an increase of charge carrier
density leading to a decrease of the domain boundary potential of CNT aggregates in
the polyester matrix.
0 00
Fig. 25.8 ε and ε for
different concentrations of
CNTs above ϕc, at constant
temperature T ¼ 300 K
25.3.3 Dielectric Response Above the Percolation Threshold
For ϕ > ϕc, the composite material is characterized by the formation of an infinite
cluster of carbon nanotube particles, which allows the displacement of electrons over
large distances of the sample. The interfacial polarization phenomenon on surfaces
of the finite clusters can always exist but it is masked by the conduction process ε00relax
0 00
ε00cond [29]. In Fig. 25.8, we depict ε (a) and ε (b) at a temperature of 300 K for
different volume concentrations above ϕc of the CNT. The figure clearly demon-
00
strates that the spectra of ε strongly depend on frequency and decrease with increas-
ing frequency. These spectra are also marked by a linear behavior in the logarithmic
representation in both the low and the high frequency regions. The slopes of these
curves for various concentrations are practically identical (very close to 1) which is a
signature of ohmic conduction losses.
The study of the AC electrical conductivity σ AC, is normally carried out to better
understand the frequency dependence of the electrical transport properties of the
composites. Figure 25.9 shows the AC conductivity for ϕ ¼ 1.0% > ϕc in the
frequency range from 100 Hz to 1 MHz and temperatures between 300 and 380 K.
We note that the value of σ AC, increases with rise in frequency and becomes
independent in the low frequency region; this is identified as the DC conductivity
σ DC. This type of behaviour is very similar to that of previous reports for carbon
black composites [15, 30]. Figure 25.10 shows temperature dependence of the DC
conductivity, which increases exponentially with temperature. It is noticeable that
this temperature dependence also follows the VTF model (Eq. (25.6)) [25, 26].
The measured values of the activation energy E and T0 as a function of the CNT
volume fraction are given in Table 25.2, showing that there is a decrease in the
activation energy as the filler concentration increases.
270 Z. Samir et al.
Fig. 25.9 Electrical

conductivity versus
frequency for a sample with
a CNT concentration
ϕ ¼ 1.0%> ϕc of CNT
Fig. 25.10 ln (σ DC)

vs. 1/(TT0) for different
concentrations of CNT
above ϕc (0.8%, 2.0% and
3.0%)
Table 25.2 Summary of VTF fitting parameters E and T0 for different volume CNT concentrations
ϕ (%) E (meV) T0 (K)
0.8 5.17 0.36 231 2
2.0 4.26 0.28 240 3
3.0 1.93 0.32 261 4
25.4 Conclusion
In summary, the dielectric properties of polyester filled with different concentrations

of CNTs have been investigated. From the obtained results, the following conclu-
sions can be drawn. The Kramers-Kronig based derivative technique that we have
applied to the real and imaginary parts of the complex dielectric seems to be more
suited when considering the objectives of our study. Indeed, when using this
technique, the relaxation peaks are undeniably visible. The dielectric permittivity
is found to be well fitted by the Havriliak-Negami model taking into account the
effect of electrode polarization. From this model, this analysis enabled us to describe
quantitatively the experimental data from which we extracted the ohmic conductivity
and the parameter characterizing the contribution of the ohmic conduction in the
complex dielectric permittivity. Furthermore, the temperature dependence of DC
conductivity follows the VTF equation which allows us to estimate the activation
energies of the processes in the composite materials. We have found that the
calculated activation energy values decrease as the filler concentration of CNT
contents inside the polymer matrix increases.
Acknowledgments The authors acknowledge support from CNRST-Maroc (Centre National de la

Recherche Scientifique et Technique) for their financial support, and FEDER by funds through the
COMPETE 2020 Program and National Funds through FCT – Portuguese Foundation for Science
and Technology under the project UID/CTM/50025/2013.
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2. De Volder MFL, Tawfick SH, Baughman RH, Hart AJ (2013) Carbon nanotubes: present and
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microtubules. Phys Rev Lett 68:1579–1581
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properties of multiwall carbon nanotube/polycarbonate composites for electrostatic discharge
and electromagnetic interference shielding applications. RSC Adv 4:13839–13849
7. Park IS, Kim KJ, Nam JD, Lee JS, Yim WS (2007) Mechanical, dielectric, and magnetic
properties of the silicone elastomer with multi-walled carbon nanotubes as a nanofiller. Polym
Eng Sci 47(9):1396–1405
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Oueriagli A (2017) Fractal structure and temperature-dependent electrical study of carbon
nanotubes/epoxy polymer composites. Spect Lett 50(4):183–188
12. Boukheir S, Len A, Füzi J, Kenderesi V, Achour ME, Eber N, Costa LC, Outzourhit A,
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Chapter 26
Nanosized Ferrite Materials for Absorption
of and Protection from MW Radiation
Svetoslav Kolev and Tatyana Koutzarova
Abstract Ferrite materials suitable for mm-wave circulators should exhibit ferro-
magnetic resonance (FMR) in the mm range with high a saturation magnetization. In
addition, the magnetic and dielectric losses and the temperature dependence of the
magnetocrystalline anisotropy and of the saturation magnetization should be as low
as possible. Therefore, compositionally and microstructurally homogeneous mate-
rials are required. The object of the work presented was to investigate the microwave
(MW) absorbing properties of nanocomposite bulk samples. As a filler we used
magnetite (Fe3O4) with different particle sizes in a silicone rubber matrix and
investigated the influence of the filler concentration and particle size in the polymer
matrix on the MW nonlinearity in a large frequency range (1–20 GHz). We found
that the intensity and the frequency at the reflection loss minimum depend on the
particle size and particle concentration of magnetite in the samples.
Keywords Nanosized ferrites · Magnetite · Shielding · Absorption · MW radiation
26.1 Introduction
Protection from electromagnetic radiation (EMR) in the MW range has lately

become a problem of pressing interest due to the world-wide spread of technologies
such as cellular phones, to name but one. MW radiation shielding in medical
research and in MW domestic appliances has also focused the attention of
researchers. Over the last 30 years, the transmission density has doubled every
4 years, meaning that the electromagnetic pollution has gone up by around
100 times. The wavelengths used are getting shorter; we have now entered the
MW era where we are dealing with minuscule dimensions. However, the shorter
the waves, the more energy they produce.
S. Kolev (*) · T. Koutzarova

Institute of Electronics, Bulgarian Academy of Sciences, Sofia, Bulgaria

274 S. Kolev and T. Koutzarova
The health consequences of EMR exposure vary in intensity from mild symptoms
to serious diseases. Some symptoms are termed as “radio-wave sickness”. EMR
from transmission towers and mobile phones are suspected of initiating cancer
because of interfering with the electric field inside human cells. People working or
living in continuous exposure to EMR are under the greatest risk.
A solution to the above problem may be provided by the new scientific branch of
nanoscience and nanotechnology, which has undergo an extraordinarily fast devel-
opment in the last three decades. Tools were created that allow us to obtain materials
with very small dimensions and unique physical and chemical properties. The aim of
this work was to prepare and investigate materials, in particular nanosized ferrites, to
be used as shields and absorbers (as films with different thickness) of electromag-
netic radiation in the MW range.
The aim of our study was to clarify the contribution of a Fe3O4 ferrite filler
(commercial and laboratory-made) to the formation of the MW and magnetic
properties of composite absorbing structures.
There exists a wide variety of absorbing materials that can be used for
suppressing electromagnetic radiation, depending on the requirements for a narrow
or wide absorbing frequency band, or for low- or high-frequency application of the
absorber. Concerning the MW range, the absorbing materials most often used are
rubbers, plastics, thermoplastics etc. These are non-magnetic substances which are
resistant to atmospheric influences and often contain magnetic fillers, such as
ferrites, iron, or cobalt-nickel alloys. The additives alter the values of the dielectric
constant and the magnetic permeability so as to achieve maximal absorption of
electromagnetic radiation.
The MW absorbing structures are commonly divided into several types according
to their technical parameters and the principle of functioning.
26.2.1 Functioning Principles of Absorbers
26.2.1.1 Absorbing Structures of the First Type
When an electromagnetic wave reaches a free-space/material boundary surface, a

part of the incident wave is reflected back from the front surface without penetrating
into the respective material (Fig. 26.1), while another part of the wave is transmitted
through the material. The amplitude and phase of both the reflected and the trans-
mitted waves change depending on the material’s characteristics. In particular, the
amplitude of the transmitted wave diminishes or is attenuated. This attenuation
26 Nanosized Ferrite Materials for Absorption of and Protection from MW Radiation 275
Fig. 26.1 Absorbing

structures of the first type
Fig. 26.2 Absorbing

structures of the second type
results from dielectric or magnetic losses or both. It is a measure of the energy

absorbed due to transmission only and can be calculated based on the material’s
properties.
The insertion losses are a measure of the total loss of energy that is due not only to
attenuation but also to the reflection of part of the energy from the sample surface.
The insertion losses are a function of both the material’s characteristics and the
thickness.
26.2.1.2 Absorbing Structures of the Second Type
When an electromagnetic wave is incident on a medium with electric characteristics

different from those of free space, this medium will act as a reflector; the larger the
medium’s dielectric constant (i.e., the larger the difference between the impedance of
free space and that of the front surface), the larger the reflection. In other words, any
medium with high losses is a reflector; thus, in order to bring reflection to a
minimum, the front surface impedance of the absorber should be chosen so as to
be as close as possible to that of free space (Fig. 26.2).
Making use of a gradual impedance variation, namely, changing the impedance
from a value close to that of free space at the front surface to a value of a high-loss
medium, one can achieve a wide band absorption (Fig. 26.3).
Fig. 26.3 Functioning

principle of an absorber with
a gradual impedance
variation
Fig. 26.4 Functioning

principle of a quarter-wave
absorber
26.2.1.3 Absorbing Structures of Third Type (¼ Wavelength Thickness)
The electromagnetic wave reflected from the absorber’s front surface (the primary
reflected wave) changes its amplitude and phase. The transmitted wave is attenuated
partly in the medium and is reflected from the absorber’s back surface (in the case
illustrated in Fig. 26.4, from a total reflector) and leaves the front surface, thus
forming a secondary reflected wave. When the phase difference of the primary and
the secondary reflected waves is 180 (a quarter-wave absorber), destructive inter-
ference takes place, and the overall reflected wave amplitude is minimized.
The present interest in MW absorbing materials concerns mainly studies on
ferrimagnetic composites in order to avoid radar detection in the GHz range [1–
12]. These materials dissipate efficiently the electric and magnetic energy of an
incident magnetic field. A widely-applied way of preparing such absorbing media is
dispersing an electrically conductive powder in an insulating matrix. In the study
reported here, we dealt with magnetite, which, unlike most ferrites, is a
semiconductor exhibiting a high electrical conductivity; as a consequence bulk

magnetite behaves as reflector when irradiated by an electromagnetic wave. One
can avoid this problem by homogeneously dispersing magnetite powder in an
insulating matrix. The experiments on studying these material properties consist in
irradiating them with a plane electromagnetic wave of a given frequency and
detecting the transmitted and reflected signals. The latter are processed appropriately
to obtain the material’s dielectric constant and magnetic permeability, and to attempt
to clarify the mechanisms giving rise to the magnetic losses.
Typically, the particle size of the fillers used in such experiments is 3–20 μm. In
the study reported here, we compared the performance of a composite with a 30-nm
Fe3O4 filler with that of a composite with a commercial magnetite filler with particle
sizes of 300 nm and 3000 nm. With the advances in nanotechnologies allowing the
preparation of nanostructured Fe3O4, its use as a filler has attracted growing interest
due to its larger effective surface and, thus, higher potential efficiency.
To follow the characteristics of the composite structures prepared by us, we used
an absorber described above as the third type. A TEM electromagnetic wave was
directed normally to a one-layer absorber, with a perfect conductor placed behind it
(short circuit) [13, 14]. This is a fast and accurate technique, allowing one to
measure directly the reflection losses RL (the ratio of the incident and the reflected
power in dB).
The experimental setup employed to find the relationship between the sample’s
absorption properties, its thickness and the MW frequency range consisted of a
scalar network analyzer (Hewlett Packard 8756 A, frequency band 1–20 GHz) and a
sample mounted perpendicularly to the incident MW signal and short-circuited by a
perfect conductor.
We evaluated the MW performance of magnetite powder dispersed in a polymer
matrix (silicon rubber). The samples characterized contained magnetite powders
with an average particle size of 30 nm (prepared by a soft-chemistry technique in
the “Microwave Magnetics” laboratory IE BAS), as well as commercial products
with particle sizes of 300 nm and 3000 nm (Nanostructured & Amorphous Materials
Inc., USA). The ferrite powders were dispersed homogeneously in the polymer
matrix. Two sets of samples were prepared for each of the three powder sizes. The
first set consisted of toroidal specimens with an outer diameter of 7 mm, an inner
diameter of 3 mm, different thicknesses of 1, 2, 3 and 4 mm (samples 1, 2, 3, 4) and
the same filler-polymer weight ratio (Table 26.1).
The second set of samples had a thickness of 4 mm and different (increasing by
the same step) degrees of filling, namely, samples A, B, C, and D – Table 26.2.
Table 26.1 Samples with different thicknesses of 1-4 mm and the same filler-polymer weight ratio
Sample Filler-polymer weight ratio, g/cm3 Sample thickness, mm
1 1,5:1 1
2 1,5:1 2
3 1,5:1 3
4 1,5:1 4
Table 26.2 Samples with thickness of 4 mm and different degrees of filling

Sample Filler-polymer weight ratio, g/cm3 Sample thickness, mm
A 1,2:1 4
B 1,5:1 4
C 1,8:1 4
D 2,1:1 4
The plots shown and commented on below were obtained under the conditions
described earlier in the report, namely, a plane electromagnetic wave incident
normally to a composite sample with a perfect conductor placed behind. The minima
of the reflection losses curves RL, i.e., the minimal reflected MW power, occur at
certain frequencies, called matching frequencies. Generally, the plots demonstrate
that the number of matching frequencies rises with the samples’ thickness.
The frequency dependences of the reflection losses for nanocomposite absorbers
with the same filler-polymer weight ratio and different thicknesses (1, 2, 3, 4 mm)
and particles sizes of 30, 300 and 3000 nm are shown in Fig. 26.5.
Figure 26.6 illustrates the frequency dependence of the reflection losses (RL) of
nanocomposite absorbers with different filler-polymer weight ratios and equal thick-
ness (4 mm) as well as of a polymer without filler for the three magnetite powder
particle sizes (30, 300 and 3000 nm). The chosen thickness of 4 mm allowed the best
conditions of measurement.
As one can see for the case of the composite absorber with a particle size of
30 nm, the sample with a thickness d ¼ 1 mm exhibits one matching frequency only,
with practically no reflection losses. For d ¼ 2 mm, however, the losses appear at
higher frequencies. For d ¼ 3 mm and d ¼ 4 mm, the matching frequencies shift to
the lower frequencies range. The values of the matching frequencies are related to
the thickness d of the samples, namely, as a sequence of odd multiples of ¼ of the
wavelength, or,
d ¼ nλ=4 ðn ¼ 1; 3; 5; 7; 9; . . . . . . :Þ,
where n ¼ 1 corresponds to the first matching frequency at low frequency.

For the absorber with a filler particle-size of 300 nm, the second matching
frequency appears first for the sample with a thickness of d ¼ 2 mm, compared
with the samples with the same thickness but with others fillers; in general, the
reflection losses rise with the growth of the magnetite particle size.
For a proper thickness, as mentioned above, namely, when the primary and the
secondary reflected waves are de-phased by 180 , the destructive interference
practically extinguishes the overall reflected wave at the free-space/sample
boundary.
Figure 26.7 illustrates how the value of the first matching frequency varies with
the samples’ thickness and the fillers’ particle size.
Figure 26.8 yields information on the variation of the first matching frequency
value as a function of the filling density for the different magnetite particle-sizes for
samples’ thickness of 4 mm. For a filler particle-size of 30 nm, the matching
Fig. 26.5 Frequency dependence of the reflection losses RL of nanocomposite samples of different
thickness as a function of the Fe3O4 particle size
Fig. 26.6 Frequency dependence of the reflection losses RL of nanocomposite samples with
different filler-polymer weight ratios and a polymer without filler (P) as function of the Fe3O4
particle size
Fig. 26.7 Fe3O4 particle

size influence on the
matching frequency
dependence on the sample
thickness
Fig. 26.8 Fe3O4 particle

size influence on the first
matching frequency
dependence on the particle
size
frequency value practically does not change as the filler-polymer weight ratio is
raised; it varies within the 6.5–6.9 GHz interval. For the cases of 300 nm and
3000 nm particle sizse, the matching frequency value varies within much wider
limits, namely, 6.3–3,7 GHz and 5,3–3,2 GHz, respectively.
Figure 26.9 provides information on the reflection losses RL at the first matching
frequency as dependent on the filling density for the different magnetite particle sizes
for a sample thickness of 4 mm. The reflection losses rise as the particle size is
increased. For particle sizes of 300 nm and 3000 nm, an optimal filling exists, for
which the reflection losses are the highest; when the filling density is increased
further, the reflected power begins to increase.
Fig. 26.9 Reflection losses

RL dependence on the
filler’s particle size at the
first matching frequency
The results presented demonstrate that the technique used by us to determine the
MW parameters of composite materials (in our case, a ferrite filler in a polymer
matrix) offers a fast and efficient way of measuring the reflection losses and
evaluating the material’s applicability as an antireflection coating.
26.3 Conclusions
Our results prove that one can vary the matching frequencies and the reflection losses
of a nanocomposite sample in a controlled way by varying the particle size of the
ferrite filler while keeping the sample thickness and filler-polymer weight ratio
constant; or alternatively, by varying the sample thickness and maintaining all
other parameters constant. The nanocomposite structures prepared could find appli-
cations as detectors of MW electromagnetic waves or as antireflection coatings.
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Chapter 27
Dielectric Relaxation in Biocomposites
Based on Olive Pomace Grains
L. Kreit, Z. Samir, I. Bouknaitir, A. Triki, M. E. Achour, L. C. Costa,

A. Kallel, A. Oueriagli, and M. Mabrouki
Abstract A polyester polymer matrix filled with olive-pomace grains was

investigated using impedance spectroscopy in the frequency range 100 Hz to
1 MHz and temperatures from 300 to 360 K. Two relaxations processes were
identified. One could be attributed to the α relaxation associated with the glass
transition and observed in the neat matrix, while the second was attributed to the
accumulation of charges at the pomace grains/polyester interfaces. The relaxation
parameters were evaluated from isothermal dielectric spectra by applying the
empirical Havriliak-Negami function.
Keywords Biocomposites · Dielectric relaxation · Havriliak-Negami function
27.1 Introduction
The use of natural fibers as a reinforcing agent is a development that has been gained
global attention over the last few years [1–6]. Thanks to their many advantages such
as renewability, recyclability, biodegradability, low specific gravity, and high
L. Kreit · Z. Samir · I. Bouknaitir · M. E. Achour (*)

LASTID Laboratory, Sciences Faculty, Ibn Tofail University, Kenitra, Morocco
A. Triki · A. Kallel
LaMaCoP, Faculty of Sciences of Sfax, University of Sfax, Sfax, Tunisia
L. C. Costa
A. Oueriagli
LPSCM Laboratory, Faculty of Sciences Semlalia, Cadi Ayyad University, Marrakech,
Morocco
M. Mabrouki
Laboratory LGI, Faculty of Sciences and Technics, Sultan Moulay Slimane University, Beni
Mellal, Morocco

286 L. Kreit et al.
specific strength [7, 8] natural fibers have received increasing attention from both of
the academic world and the industry [9, 10]. The most interesting aspect of natural
fibers is the positive environmental impact [11] and their help to eliminate the
increasing cost of the use of petroleum-based materials.
Relaxation phenomena are one of the most studied topics in materials sciences;
the spectra of the real and imaginary complex permittivity are used extensively to
evaluate this kind of dielectric behavior. The electric modulus is also proposed in
this paper for the description of systems with ionic conductivity and related relax-
ation processes, which presents advantages in comparison to the classical approach
using the real and imaginary parts of the dielectric permittivity. Furthermore, an
alternative method, consisting of applying the Havriliak-Negami [12] model has
been used to analyze the relaxation phenomena of the composite, exploring the
interfacial region of polyester/olive pomace grains. The mechanisms inducing relax-
ation processes are not yet clearly understood. So, it is appropriate to investigate how
the dielectric properties of such bio reinforced composites are affected by additional
polarization effects caused by the presence of nanoparticles.
27.2.1 Materials
We used natural olive-pomace grains of about 63 μm size, loaded in a polyester

polymer matrix, forming pellets with 13 mm diameter and a thickness of about
3 mm. The matrix used in this work was unsaturated polyester resin 154TB,
including 31 wt% of the styrene monomer, requiring 30 min for gelation, at room
temperature, which was acquired from Cray Valley/Total, USA. The pomace/poly-
ester nanocomposite has been prepared by mixing 5.87 g of liquid polyester resin
and 0.2% weight of cobalt octanone as reaction activator. Pomace particles were
introduced in different fractions before adding 1% of hardener to make each mixture
cohesive. Methyl ethyl ketone peroxide (MEKP) was used to harden the mixtures
and to facilitate the fabrication process. Each olive pomace grains/polyester com-
posite was mixed at room temperature for 5 min, promoting the gelation; thereafter it
was poured into a mold. After 2 h the samples were unmolded, taking 24 h for
achieving a complete polymerization. In this work, different samples were prepared
with concentrations in volume, Φ, between 0.0% and 15.0%.
27.2.2 Dielectric Measurements
The complex permittivity of the composite samples was measured in the frequency f
range from 100 Hz to 1 MHz and in the temperature range from 300 to 360 K, using
an impedance analyzer HP 4294A. Before the measurements, the samples surfaces
27 Dielectric Relaxation in Biocomposites Based on Olive Pomace Grains 287
were polished and covered with a thin layer of silver paint. The real ε0 (ω) and
imaginary ε00 (ω) parts of the complex permittivity were deduced from the capaci-
tance and resistance values of the sample, respectively.
27.3.1 Polyester Matrix
Figure 27.1 shows the real and imaginary parts of the dielectric permittivity versus
temperature at several frequencies. The relaxation, observed above 350 K was
identified as α relaxation, which is associated with the glass–rubbery transition of
the polymer [13]. The increase in permittivity was attributed to the increase of the
segmental mobility of the polymer molecules with temperature near the glass
transition temperature [14].
27.3.2 Composites
The dependence of the real ε0 (ω) and imaginary ε00 (ω) parts of the complex permit-
tivity of the composites with 15.0% olive pomace grains loading versus frequency at
different temperatures is shown in Fig. 27.2. The increase of the permittivity at low
frequencies is due to the presence of impurities and water in the composite. The
comparison with the net matrix shows that the reinforcement induces a new relax-
ation phenomenon, which can be assigned to water dipole polarization [14, 15].
The polarization of water molecules related to cellulosic olive pomace grains
formed a monomolecular layer enveloping the outer surface of the fibers. Polar
relaxation of water was also highlighted by Chand and Jain in sisal composites based
Fig. 27.1 (a) Real ε0 (ω) and (b) imaginary ε00 (ω) parts of the complex permittivity versus
temperature for the resin matrix
288 L. Kreit et al.
Fig. 27.2 (a) Real part ɛ0 (ω) and (b) imaginary part ε00 (ω) of the complex permittivity of the
composite (ϕ ¼ 15.0%) versus frequency at different temperatures
on a polyethylene or epoxy matrix and did not completely disappear after different
chemical treatment of the cellulose fibers [16]. The α relaxation, which was previ-
ously seen in the polyester, was totally hidden by the water dipole polarization due to
the hydrophilicity of the lignocellulosic pomace grains present in the composite.
27.3.3 Complex Modulus Analysis
Complex modulus analysis is an alternative approach to explore the electrical

response of materials containing some degree of ionic conductivity [17–20]. The
complex electric modulus M*(ω) ¼ 1/ε*(ω) was calculated by using the complex
dielectric permittivity with the following relations [21]:
ε 0 ð ωÞ
M 0 ð ωÞ ¼ ð27:1Þ
ε0 2 ðωÞ þ ε00 2 ðωÞ
ε00 ðωÞ
M 00 ðωÞ ¼ 0 2 ð27:2Þ
ε ðωÞ þ ε00 2 ðωÞ
Where M0 (ω) and M00 (ω) are the real and imaginary parts of the electric modulus.
This formulation is mainly suitable to minimize the effect of the dc conductivity. It
allows to diminish the large values of dielectric permittivity ε0 (ω) and loss factor
ε00 (ω) at low frequencies, which are usually associated with the electrode material
and their contacts, space charge injection phenomena and absorbed impurity con-
duction effects [22]. Hence, bulk relaxation properties can be interpreted.
Figure 27.3 shows the frequency dependence of the imaginary part of the complex
modulus with volume fraction (ϕ ¼ 15.0%). at different temperatures. From this figure,
it can be observed that the peak moves to higher frequencies, indicating a decrease in the
relaxation times. The frequency dependence has been analyzed by using the modulus
Fig. 27.3 Imaginary part of

the electric modulus M00 as a
function of frequency for
different temperatures for
15.0% volume fraction of
filler
Havriliak–Negami formalism, which is an empirical modification of the Debye relaxa-

tion model given by the following equations [17, 23]:

0 M s Aβ þ ðM 1 M s Þ cos βφ Aβ
M ¼ M1 ð27:3Þ
M 2s A2β ðM 1 M s ÞM s cos βφ þ ðM 1 M s Þ2
½ðM 1 M s Þ cos βφAβ
M 00 ¼ M 1 M s ð27:4Þ
M 2s A2β ðM 1 M s ÞM s cos βφ þ ðM 1 M s Þ2
h ωτ i1=2
A ¼ 1 þ 2ðωτÞ1α sin þ ðωτÞ2ð1αÞ ð27:5Þ
h ατ 2 ατi
1α
φ ¼ arctg ðωτÞ cos = 1 þ ðωτÞ1α sin ð27:6Þ
2 2
where Ms ¼ 1/εs and M1 ¼ 1/ε1- α and β are relaxation exponents, and Ms and M1
the moduli at low and high frequencies, respectively.
In Fig. 27.4 the Nyquist plot of the composites for different temperatures, with
olive pomace grains (ϕ ¼ 15.0%) is shown. We should also point out that the solid
curves were produced by the best fitting of the experimental points, using the
Havriliak–Negami data shown below. It also noted that these plots are linked to
the water dipole polarization. The parameters evaluated for the experimental data by
the Havrialk-Negami-fitting method are presented in Table 27.1, for 5.0%, 10.0%,
12.0% and 15.0% volume fractions.
To further explore the dielectric relaxation in this composite, it is often useful to
estimate the activation energy with the Arrhenius equation [13]:

E
f max / f 0 exp ð27:7Þ
kB T
where E, KB and T are the activation energy, Boltzmann’s constant and absolute
temperature, respectively. Figure 27.5 is a plot of ln(fmax) as a function of the inverse
temperature for different olive pomace grains. It should be mentioned that the
activation energy was calculated using Eq. (27.7) with the slope of the straight
290 L. Kreit et al.
Fig. 27.4 Nyquist plot of the electric modulus M* of the composite with Φ ¼ 15% at 340, 350 and
360 K
Table 27.1 Parameters evaluated by fitting data according to the Havriliak–Negami equation, for
5.0%, 10.0%, 12.0% and 15.0% of filler volume
Concentration (%) T(K) A β Ms M1 Δε
5 340 0.54 0.58 0.24 0.16 4.92
350 0.48 0.42 0.24 0.14 6.94
360 0.55 0.51 0.23 0.15 8.33
10 340 0.51 0.59 0.22 0.11 7.26
350 0.47 0.74 0.22 0.11 8.50
360 0.38 0.97 0.22 0.10 10.28
12 340 0.34 0.76 0.26 0.08 3.78
350 0.38 0.82 0.25 0.09 4.54
360 0.35 0.90 0.25 0.08 5.65
15 340 0.415 0.95 0.24 0.10 1.90
350 0.45 0.68 0.24 0.09 2.50
360 0.42 0.87 0.24 0.09 2.79
Fig. 27.5 Water dipole

polarization relaxation with
Arrhenius plots of the
frequency of the dielectric
modulus versus inverse
temperature for the polyester
with olive pomace grains
(ϕ ¼ 15.0%)
Table 27.2 Activation energies for pomace grains/polyesters composites

Concentration ϕ(%) 0.0 5.0 10.0 12.0 15.0
Activation energy (kJ/mol) 150.00 58.48 50.46 51.54 38.97
lines of Fig. 27.5 and reported in Table 27.2. The obtained values are between 38.97
and 150.00 kJ/mol. These values are in agreement with those reported for polyester
reinforced with Alfa fibers [22] and palm tree fibers [14, 22, 24].
27.4 Conclusion
In the present work, composite materials based on polyester reinforced with olive
pomace grains were investigated. The dielectric behavior of the neat matrix and the
composite based on olive pomace grains has been studied over the temperature range
from 300 to 360 K and over the frequency range from 100 Hz to 1 MHz. In addition
to the α relaxation associated with the glass transition of the epoxy resin matrix, the
presence of pomace grains in the composite gives rise to other relaxation associated
with water polarization. The data results were analyzed using the modulus formal-
ism, which is a very useful approach to explore the electrical response of materials
containing some degree of ionic conductivity.
Acknowledgments The authors acknowledge support from CNRST-Maroc (Centre National de la

Recherche Scientifique et Technique) and the FCT-CNRST bilateral cooperation, and FEDER by
funds through the COMPETE 2020 Program and National Funds through FCT – Portuguese
Foundation for Science and Technology under the project UID/CTM/50025/2013.
References
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cellulose fibers. Compos Interfaces 12:41–75
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Chapter 28
Green Synthesis of Silver Nanoparticles
and Their Application in Thin Polymer
Films
Zhana Petkova, Irena Kostova, and Ginka Antova
Abstract The focus of the present study is on synthesis procedures, morphology

and application of silver nanoparticles (AgNPs). A green synthesis approach was
performed with aqueous extracts from lawn grass and parsley (Petroselinum crispum
Mill.), both of them microwave assisted. The formation of the silver nanoparticles
was observed using UV-Vis spectroscopy (Boeco S26 spectrophotometer); they
were characterized by transmission electron microscopy (TEM). The absorption
spectra show peaks in the range 380–400 nm for all products. The TEM images
depicted that the synthesis method yield nanoparticles with spherical shape and
different size. This gives rise for a wide range of application of AgNPs which may
be used as additives in papers and polymers due to their antimicrobial properties
which depend on particle size and shape.
Keywords Green synthesis · Silver nanoparticles · Lawn grass · Parsley
28.1 Introduction
Nanotechnology has spread globally and appeared to be one of the most explored
areas of research in materials sciences [1, 2]. Noble metal nanoparticles are applied
in many areas such as medical industry, electronics, chemistry and can be potentially
used in cosmetics and foods as well [1–3]. Many methods for the synthesis of silver
nanoparticles are reported but nowadays green synthesis is prefered and commonly
used, because it is considered as environmentally friendly and there is no use of toxic
chemicals [2]. Different researchers have reported to use plant extracts as agent for
the reduction of Ag+ to Ag0; the obtained silver nanoparticles are smaller in size with
a good dispersion [2, 4–8]. Silver nanoparticles possess an antibacterial activity and
show strong inhibitory and bactericidal effects [2, 8]. For these reasons, they can be
Z. Petkova (*) · I. Kostova · G. Antova

Department of Chemical Technology, University of Plovdiv ‘Paisii Hilendarski’, Plovdiv,
Bulgaria

294 Z. Petkova et al.
used to prevent and treat various diseases [8]. On the other hand, the antibacterial
effect of silver nanoparticles is related to their well-developed surface which can be
obtained by controlling the size and the shape of the particles [2].
One of the possible applications of silver nanoparticles is their addition into thin
polymer films in order to become conductive, flexible and stable [9]. The application
of the AgNPs could also depend on their shape. According to Kostova et al. [9] silver
nanowires possess electrical conductivity and could be used in electrical devices
such as touch screen displays and solar cells conductive layers. On the other hand,
silver nanospheres may be used as additives in papers and polymers because of their
antimicrobial properties.
The aim of the present study was to synthesize silver nanoparticles by using
aqueous plant extracts from lawn grass and parsley (Petroselinum crispum Mill.) as
well as their characterization. Furthermore, microwave-assisted synthesis was used
for reducing the reaction time. The second focus of the study was to prepare thin-
layer polymer films with addition of the obtained silver nanoparticles and their
morphology and topography was examined.
The plants used in the study were a mixture of lawn grass and parsley (Petroselinum
crispum Mill.). The grass material was collected from the park area of an urban
district of Plovdiv (Bulgaria) and the parsley (with Bulgarian origin) was purchased
on the local market. The aqueous plant extracts were prepared by taking 20 g of the
plants (washed and finely cut) in 500 mL Erlenmeyer flask with 200 mL of distilled
water and then boiling the mixture for 20 min. After that the extracts were filtered
through Whatman No.1 filter paper (pore size 25 μm). They were stored at 4 C and
used within a week.
0.01 M aqueous solution of silver nitrate (AgNO3) was prepared and used for the
synthesis of silver nanoparticles. Twenty-five milliliter of the extracts was added into
25 mL of aqueous solution of 0.01 M silver nitrate for the reduction of Ag+ ions and
was heated in microwave (CEM MDS 81D) for 5 min at 100% power. Then, the
silver nanoparticle solution was purified by repeated centrifugation at 5000 rpm for
10 min followed by redispersion in deionized water. The yield was estimated by
atomic spectrometry of the residual Ag+ in the filtrate.
The reduction of pure Ag+ ions was observed by measuring the UV-Vis spectrum
of the nanoparticle solution after diluting a small portion of the sample into distilled
water. UV-Vis spectral analysis was done by using UV-Vis spectrophotometer
Boeco S26. The average particle diameters have been estimated by a model equation
on the basis of their absorption peak wavelength (nm) in their UV-Vis spectra.
The morphology and phase composition of the samples were analyzed by trans-
mission electron microscopy (HRTEM, JEOL JEM-2100, 200 kV). Before mea-
surement the sample suspensions were dispersed by ultrasound sonication for 3 min
(42 kHz).
28 Green Synthesis of Silver Nanoparticles 295
A polymer emulsion (trademark Styacryl V700, vinyl acetate/acrylate ester/

VeoVa vinyl ester copolymer) with medium water resistance was used for the
polymer film. Thin layer films were prepared as follows: 0.01 g of silver
nanoparticles was thoroughly mixed up with polymer and 3 mL deionized water to
a total volume of 15 mL and casted onto a plastic substrate (printing transparency
sheet) using a roll hand proofer. The topography and internal characteristic of the
polymer-metal nanoparticle composite films were studied by atomic force micros-
copy (AFM, Nanosurf Flex).
Two plant extracts were tested as reducing agent for the green synthesis of AgNPs
(grass and parsley). The yield of silver nanoparticles, estimated by atomic spectrom-
etry of the residual Ag+ in the filtrate, was established to be over 90% for all samples.
Silver nanoparticles are known to exhibit a yellowish brown colour in aqueous
solution which is due to the excitation of surface plasmon (SPR) vibrations in the
silver nanoparticles [10]. The colour change of the plant extract solution is an
indicator of the reduction of the silver ion to silver nanoparticles [3]. Their size
and shape could be examined by UV-Vis spectral analysis (Fig. 28.1) after synthesis.
The absorbance peak of the silver nanoparticles was observed at 396 nm and
404 nm for grass and parsley extracts, respectively; the broad peaks suggest that
more polydisperse particles were formed [1].
The particle size could be estimated using the following formula:
D½nm ¼ 0:715 λmax 258 ð28:1Þ
where D is particle diameter (nm), and λmax the SPR peak position in the UV-Vis
absorbance spectrum.
The estimated particle diameter of the synthesized silver nanoparticles by using
grass extract was 25 nm, that from the parsley extract 31 nm. These average sizes
a b
1 1
0,8 0,8
Absorbance
Absorbance
peak maximum
0,6 peak maximum 0,6 404 nm (AgNPs)
396 nm (AgNPs)
0,4 0,4
0,2 0,2
0 0
300 800 300 800
Wavelength, nm Wavelength, nm
Fig. 28.1 UV-Vis absorption spectrum of silver nanoparticles. (a) Grass extract; (b) Parsley extract
Fig. 28.2 TEM images of silver nanoparticles. (A) Grass extract; (B) Parsley extract
as well as the shape of the nanoparticles are confirmed by transmission electron

microscopy (TEM) images (Fig. 28.2).
TEM analysis reveals spherical shape highly polydisperse nanoparticles with an
average size about 25 nm for the grass and the parsley extract synthesis method.
Selected area electron diffraction (SAED) pattern confirm the crystalline nature of
the silver particles with a face-centered cubic lattice (a ¼ 4.0772 Å). The measured
interplanar distance matches well with the reference (JCPDS file no. 87-0720). TEM
images of AgNPs from both used extracts depict that they are well separated. It also
can be seen that the silver nanoparticles do not have a secondary capping of organic
material which is present in the plants that were used. On the other hand, such of
capping was noticed by Song and Kim [3] and Raut et al. [11] who used different
plant extracts, such as pine, persimmon, ginkgo, magnolia, platanus and Gliricidia
sepium, for reducing the silver ions.
The results from the present study were confirmed by Roy et al. [12] who
synthesized silver nanoparticles by using parsley leaf extract and observed that
they possessed spherical shapes with an average diameter of 30–32 nm.
The obtained silver nanoparticles were implemented in thin layer polymer films;
their morphology and topography were examined by AFM. The thickness of the
films was measured by micrometer screw gauge and was established to be 5 μm.
AFM images of the thin films with added silver nanoparticles produced by grass and
parsley extracts are shown in Fig. 28.3.
The AFM images show difference between the surfaces of the films. The grain
size of the polymer composite filled with the larger sized AgNPs of the grass extract
is larger than that of the parsley extract AgNPs polymer. The segment profile of the
last has sharp points sticking up from the top, while the former display a flatter
micro-profile. The images also reveal that silver nanoparticles obtained by using
grass extract are evenly distributed within the thin film.
28 Green Synthesis of Silver Nanoparticles 297
Fig. 28.3 AFM images of the thin layer films with added silver nanoparticles produced by: (A)
grass extract; (B) parsley extract. The glittering spots are clusters of small silver nanoparticles
28.4 Conclusion
The plant extract synthesis of silver nanoparticles is a simple and efficient low-cost
green method for the large-scale production of nanoparticles for manufacturing
material with special characteristic such as antibacterial and specific optical proper-
ties. The obtained AgNPs are spherical in shape and have a face-centered cubic
lattice. Their average size is 25 nm for both grass and parsley extracts.
The prepared thin polymer films with added silver nanoparticles are transparent
and flexible which is a good indicator for their potential application. A variety of
polymer composite thin films are suitable for thin layer coating of surfaces through
their transparency or matte look, UV-protection properties, easy-laying, and
plasticity.
Acknowledgments The authors are grateful to Dr. Sotir Sotirov, University of Plovdiv ‘Paisii
Hilendarski’, Faculty of Physics for AFM analysis. The study was carried out with the support of
MU17HF024.
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Chapter 29
Synthesis of Iron Oxide Nanoparticles
Modified with Silanes and Their Heating
Ability in Alternating Magnetic Fields
L. Storozhuk and N. Iukhymenko
Abstract Magnetite nanoparticles with controlled particle sizes and a

hexadecyltrimethoxysilane surface coating have been synthesized as a model system
to investigate the effect of surface coatings on the specific loss power (SLP) under
exposure a to low-power alternating magnetic field. It is shown that with decreased
surface coating thickness the SLP was improved.
Keywords Magnetite · Surface modification · Nanocomposite · Silane · Specific

loss power · Low-power alternating magnetic field
29.1 Introduction
The development of magnetic nanocomposites (NPs) for medical applications is

caused by the needs of medicine of a directed transport of medical preparations,
which localizes activity in the desired part of a body and reduces undesirable side
effects [1]; further applications are magnetic agents for the hyperthermia of tumors
[2] and selective magnetic adsorbents [3].
Dispersion of superparamagnetic iron oxide nanoparticles SPIONs in water
medium were investigated as MRI contrast agents [4]. Some of these materials are
already used in clinical practice: Endorem (Guerbet, Belgium), Feridex (США),
Feraheme (AMAG Pharmaceuticals, USA), Primovist and Eovist (Bayer Schering
Pharma AG, Germany), some of them are in preclinical trial stage: Supravist-
SHU555C (Bayer Schering Pharma AG, Germany), VSOP-C184 (Ferropharm
L. Storozhuk (*)
Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine, Kyiv,
Ukraine
N. Iukhymenko
Faculty of Chemistry, Macromolecular Chemistry Department, Kiev Taras Shevchenko
National University, Kyiv, Ukraine

300 L. Storozhuk and N. Iukhymenko
GmbH, Germany), Ferumoxtran-AMI-227 and Ferumoxide-АМI-25 (AMAG

Pharmaceuticals, USA [5–7].
One of the promising areas is the design of SPIONs based dispersions in a
radiopaque Lipiodol preparation and other iod-based oil preparations. This allows
for the diagnostics, delivery and retention of magnetic material in tumors with a
following use of magnetic hyperthermia [8–10].
In order to ensure an effective control over the colloidal stability of magnetic
nanoparticles, the nanoparticles were coated with organic compounds by attaching
functional groups to the NP surface via either electrostatic interactions or covalent
bonding [11, 12]. However, the overlayer can decrease the magnetic properties of
NPs, which reflects in the magnetic properties and thus the heating efficiency of
nanoparticles in alternating magnetic fields AMFs [13, 14].
This paper proposes a method to the modication of magnetite nanoparticles by
biocompatible silanes, namely hexadecyltrimethoxysilane (HDTMS), which creates
a hydrophobicity of the surface of the nanoparticles to obtain their stable dispersion
in non-polar oil media such as Lipiodol for further use in magnetic hyperthermia.
29.2 Experimental
Magnetite was obtained using a co-precipitation reaction from a solution of salts of

two- and trivalent iron in an alkaline medium according to the protocol described
in [15].
The first step of magnetite surface modification by HDTMS consists in hydrolysis
reactions of HDTMS and the following condensation of the products of the hydro-
lysis [16, 17]. The physicochemical mechanism of the silane modificationof the
methoxy groups on the surface of iron oxide NPs is the formation of Si–O bonds and
the creation of terminal functional groups available for immobilization other sub-
stances. We obtained samples with different contents of silane on the surface, the
concentration of which was determined by thermal gravimetric analysis (TGA) and
total organic carbon measurements (TOC) (Table 29.1). The properties of the
as-prepeared magnetite and the nanocomposites based on them were investigated
by a combination of physical and chemical methods.
Table 29.1 Magnetic properties of iron oxides NPs and HDTMS-modified Fe3O4 NPs
Concentration of org. phase (wt %)
Sample TOC TGA Ms, (Am2/kg) Hc, (kA/m)
S1 44,45 43.6 35.52 1 0.69 0.09
S2 23,2 22.77 49.71 0.32 0.933 0.10
S3 14,25 12.0 55.94 1.4 0.826 0.15
S4 11,1 10.2 57.83 1.2 1.016 0.16
S5 9,8 8.25 60.8 1.88 1.025 0.2
Fe3O4 – 70.40 0.68 0.975 0.04
29 Synthesis of Iron Oxide Nanoparticles Modified with Silanes 301
The obtained samples were characterized by a PANalytical X-Ray powder

diffractometer using a cobalt target X-ray tube (λ ¼ 0.179021 nm). The average
crystallite size has been determined using Scherrer’s formula: dXRD ¼ 0,89λ/Bcosθ,
where dXRD is the mean crystallite diameter of the particles, λ is the wavelength of the
X-ray radiation, θ is the diffraction peak angle, and B is the line width at half-peak
intensity.
Infrared (IR) spectra of powdered samples were recorded using a FTIR Nicolet
iS5 spectrometer with a Ge-crystal, collecting 64 scans in the 400–4000 cm1 range
with a resolution of 2 cm1.
Magnetization curves were measured using a Vibrating Sample Magnetometer
(Lake Shore 7404) at room temperature in air in a magnetic field of up to 0,795 kA/m
The amplitude and the frequency of vibration were 1.5 mm and 82 Hz, respectively.
The samples to be measured were in the form of powders.
The thermal response of iron oxide nanoparticles in an AMF was studied using
calorimetric measurements according to the method described in [18]. The measur-
ing system consisted of a signal generator (Agilent 33521A), a RF broadband
amplifier (AR RF/Microwave Instrumentation 800A3A), an induction coil (90 mm
diameter), interchangeable capacitors, and measuring units for temperature and
magnetic field. The test tubes with Si-O-R coated iron oxide nanoparticles
immobilized in a silicone polymer (Sylgard) and oleic acid were subjected to
alternating magnetic field of 1048 kHz and 5.8 kA/m. The specific loss power
(SLP) was calculated according to the equation:
1 dT
SLP ¼ C,
m dt
where C is the heat capacity of the sample, m is the mass of the magnetic material, T
is the temperature and t the time. The SLP is measured in Watts per gram of magnetic
material (nanoparticles including Si-O shell) (Wg1). The heat capacity of a sample
in the form of a n-component dispersion was calculated as follows:
X
n Xn
C¼ xi C ¼ xm,
i¼1 i i
i¼1
where xi [Jg1K1] is the specific heat capacity and mi [g] the mass of the ith
component. The following values were used in the calculations: x (sili-
cone) ¼ 1.3 Jg1K1 and x (magnetite) ¼ 0.62 Jg1K1.
The covalent bonding between silane and magnetite was confirmed by FTIR
measurements. The FTIR spectrum of a powder of the as-prepared magnetite NPs
is presented in Fig. 29.1a. The representative peak at 594 cm1 characterizes
(a) (b)
2915
637
594
Absorbance (a.u.)
2848
Adsorbtion (a.u.)
1467
895
1010
1642
1121
1070
1440
1047
890
3500 3000 2000 1500 1000
3500 3000 2500 2000 1500 1000
Wavenumber (cm-1
) Wavenumber (cm-1)
Fig. 29.1 FTIR spectra of (a) the as-prepared magnetite NPs and (b) the HDTMS-modified Fe3O4
NPs
oscillations of the Fe–O bonds of the iron oxides which cover the surface of the
magnetite particles [10, 19]. The peaks at 895, 1047 cm1 and 1121 cm1 belong to
deformation oscillations of the Fe–OН groups [19]. The peak at 1642 cm1 is
assigned to by the deformation vibrations of water molecules adsorbed on the
magnetite surface.
The adsorption of the silane polymer onto the surface of the magnetite particles
was confirmed by bands at 1070 and 1010 cm1 assigned to the Si-O–H and Si–O–
Si groups (Fig. 29.1b). The absorption band at 890 cm1 reveals the presence of Si–
O–H stretching and OH vibrations on the surface of magnetite. The peaks at 1467,
2848 and 2915 cm1 are attributed to asymmetrical C-H bending vibrations of alkyl
groups [-(CH2)n-]. The peak appearing at about 637 cm1 is assigned to Fe–O–Si
stretching vibration [20].
The phase and crystallinity of the as-prepared magnetite and HDTMS-modified
Fe3O4 NPs were investigated using the XRD technique; the results are given in
Fig. 29.2.
The XRD patterns in Fig. 29.2 display several characteristic peaks at 2θ ¼ 21.2, 35.2,
41.43, 50.6, 63.3, 67.7 and 74.6 representing the corresponding lattice planes (111),
(220), (311), (400), (422), (511) and (440), respectively, of the crystalline magnetite
Fe3O4 phase with a cubic structure of the spinel type, which are consistent with the
standard data for magnetite (JCPDS, PDF № 9005839). Comparing the initial magnetite
nanoparticles with the coated one, the XRD patterns show similar diffraction peaks.
The nano-crystalite sizes of the HDTMS-modified Fe3O4 NPs were estimated
from XRD patterns using Scherrer’s equation [21]. The calculated crystal size of the
NPs is 12–15 nm for all samples.
To identify the influence of the silane overlayer on the static and dynamic magnetic
properties of the magnetite NPs, were investigated. It was observed that the saturation
magnetization decreases from 60.8 up to 35.5 Am2/kg in accordance with concentration
of silane (Fig. 29.3). It is well known that such decrease is determined by an increase of
the non-magnetic phase concentration in the material [13]. Herewith the coercivity
(311)
the as-prepared magnetite
(1) and HDTMS-modified
Fe3O4 NP (2–4) samples 9000
(440)
(220)
(400)
(511)
(111)
Intensity (a.u.)
6000
(422)
4
3000 3
0 1
10 20 30 40 50 60 70 80
2θ (degree)
Fig. 29.3 Magnetization S5

60 S4
curves of HDTMS-modified S3
Fe3O4 NPs with different S2
Magnetization, Am2/kg
overlayer thicknesses S1
30
-30
-60
-700 0 700
Field, kA/m
increases from 0.69 to 1.025 kA/m it indicates the occurrence of magnetic losses of
magnetostrictive nature in samples with a high content of silane.
The thermal response of NP based dispersions in silicone and oleic acid was
studied in magnetic AC fields allowed for medical application. The concentration of
theNPs in the dispersions was 5 wt. %, which is typical for in-vivo and clinical
studies in MH [15]. The test tubes with HDTMS-modified Fe3O4 NPs were
subjected to an alternating magnetic field of 1048 kHz and 5.8 kA/m. The results
obtained are listed in Table 29.2.
Table 29.2 The heating rate and the SLP of the dispersions
Silicone Oleic acid Lipiodol
Heating Heating
rate, C/ rate, C/ Heating rate,

Sample min SLP, W/g min SLP, W/g C/min SLP, W/g
S1 6.25 0.08 2.7 0,03 – – 12.47 1.04 11.53 0.98
S2 9.47 0.12 4,0 0,08 – – 17.8 1.8 16.88 1.7
S3 7.27 0.09 3,1 0,03 14.7 1,3 14,0 1.3 16.31 1.92 15.3 1.8
S5 3.68 0.1 1,6 0,07 11,1 1.2 14,6 1,2 18.8 2.0 17.96 1.9
Fe3O4 7.87 0.25 3,4 0.2 13.5 1.8 14.12 1.23 33.9 1.95 32.08 1.85
According to the obtained results, the SLP value is higher for magnetic disper-
sions in Lipiodol compared with oleic acid and silicone based dispersions, which can
be explained by contributions of both relaxation process, Neel and Brownian.
However, in the case of silicone based dispersions, the Brownian relaxation is
negligible because of the immobilization of the NPs in the viscous silicone matrix.
The effect of the coating on the SLP is clearly expressed for the case of dispersions in
silicone. Sample S2 shows significantly higher SLP values; this can be explained by
an additional contribution from hysteresis losses due to the appearance of magneto-
strictive stresses in the nanoparticles.
29.4 Conclusion
Magnetite nanoparticles obtained by the coprecipitation method were modified by

silanes thus formating nanoparticles with a “core-shell” structure. FTIR results
showed that during the modification formation of a silane coating occurs due to
the formation of Fe-O-Si- bonds.
The Si-O-R coating leads to a decrease in the absolute value of the effective
saturation magnetization due to the presence of the non-magnetic phase (shell) in the
sample. However, as the thickness of the coating increases, the coercivity increases
due to an increase in the effective value of the magnetic anisotropy of magnetostric-
tive nature.
The investigation of the heating ability of dispersions based on HDTMS-
modified Fe3O4 NPs showed that the coating does not lead to a significant
decrease in the SLP value.
Acknowledgments This work was carried out in the Centre of Polymer Systems, Tomas Bata
University in Zlin, Czech Republic; the authors would like to acknowledge Dr. Natalia Kazantseva
for her intense help in that time.
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Part VIII
Materials: Glasses and Polymers
Chapter 30
Ureasil-Based Polymer Matrices As
Sensitive Layers for the Construction
of Amperometric Biosensors
T. S. Kavetskyy, O. Smutok, M. Gonchar, O. Šauša, Y. Kukhazh,

H. Švajdlenková, T. Petkova, V. Boev, and V. Ilcheva
Abstract Ureasil and ureasil-chalcogenide glass composites of different history

(fresh and aged during 1 year) were used for the immobilization of laccase and
the construction of amperometric biosensors. A correlation between the micro-
scopical free-volume of the polymer matrices as revealed by low-temperature
positron annihilation lifetime spectroscopy and biosensor characteristics of the
laccase-containing ureasil based biosensors is established. The observed findings
could be applied for improvement of the operational parameters of the
constructed biosensors, which may have potential for monitoring the level of
pollution of wastewater.
Keywords Organic-inorganic hybrid · Ureasil · Enzyme · Amperometric biosensor
T. S. Kavetskyy (*)
O. Smutok · M. Gonchar
Institute of Cell Biology, National Academy of Sciences of Ukraine, Lviv, Ukraine
O. Šauša
Institute of Physics, Slovak Academy of Sciences, Bratislava, Slovak Republic
Y. Kukhazh
H. Švajdlenková
Polymer Institute, Slovak Academy of Sciences, Bratislava, Slovak Republic
T. Petkova · V. Boev · V. Ilcheva
Institute of Electrochemistry and Energy Systems, Bulgarian Academy of Sciences, Sofia,
Bulgaria

30.1 Introduction
Modern science, medicine, clinical diagnostics, biotechnologies, as well as environ-

mental technologies all need highly selective, sensitive, rapid, and reliable methods
of identifying the key ingredients or metabolites which determine the quality of
products or serve as markers for diseases, the physiological state of human organism
or environmental safety. Biosensors are the most novel achievement of analytical
biotechnology. Development of novel nanocomposites and polymers suitable for
construction of biosensor with improved operational parameters is an important field
in sensor technologies. Polymer matrices based on ureasil composites [1–5] have
been tested for immobilization of laccase from Trametes versicolor and the con-
struction of amperometric biosensors for the first time in [6]. The biosensor charac-
teristics such as sensitivity of the bioelectrode were determined and analyzed for
ureasil, ureasil-chalcogenide glass composites, and ureasil-chalcogenide glass com-
posites with incorporated silver nanoparticles (NPs) synthesized by high-dose
30 keV Ag+ implantation. A very high sensitivity of the amperometric biosensor
with ureasil-chalcogenide glass composite was established, and a well expressed
influence on the sensor characteristics by the polymer matrix and the Ag NPs was
detected [6]. It should be noted here that some other novel techniques for the
fabrication of organic-inorganic hybrid nanocomposites based on chalcogenide
glasses and manganese phtalocyanine has also been reported in literature [7],
showing a potential for photonics applications. In other words, incorporation of
inorganic chalcogenide glasses into an organic matrix is an attractive innovative
approach for the fabrication of novel materials suitable for practical use in
optonanoelectronics and biosensorics. In the present work, ureasil and ureasil-
chalcogenide glass composites of different history (fresh and aged during 1 year)
were used for the construction of laccase-containing amperometric biosensors. The
relationship between the microscopical free-volume of the polymer matrices as
revealed by low-temperature positron annihilation lifetime spectroscopy (PALS)
[8] and the biosensor characteristics of the laccase-containing ureasil based bio-
sensors is examined.
30.2 Experimental
The synthesis of the pure ureasil matrix (K0) and the ureasil-chalcogenide As2S3
composite matrix (K4) was reported elsewhere [4, 5, 9]. Polymer matrices of
different history – K0-fresh and K4-fresh (2 months after preparation) and
K0-aged and K4-aged (1 year after preparation) – were used for examination
[8]. The low-temperature PALS experiment was carried out as described in
[8]. The PAL spectra were taken using plastic scintillators coupled to
photomultiplier tubes as detectors with a 22Na positron source and analyzed with
the free of charge LT program. The time resolution (FWHM) of spectrometer was
30 Ureasil-Based Polymer Matrices 311
about 320 ps, measured with a defect free Al sample. A three component fitting
procedure was applied for PALS data treatment. The long lifetime component τ3 and
its intensity I3, ascribing to the ortho-positronium (o-Ps) pick-off annihilation in
free-volume holes [10] were finally taken into account for analysis. The
low-temperature measurements were performed in the range of 15–350 K using a
helium cryostat (Closed Cycle Refrigerator, Janis Research Company, Inc., USA)
with an accuracy of 1 K and a vacuum equipment (Pfeiffer Vacuum, HiCUBE,
Germany) with automatically controlled vacuum in the system. The samples were
measured in ‘cooling-heating’ cycles of with 20 K steps and an elapsed time of 3–5 h
per point. Biosensitive layers of the amperometric biosensor was formed on the
surface of solid state transducers as reported in [6]. The laccase enzyme was
immobilized on the surface of the planar gold electrodes using the fresh and aged
composites as a matrix agent. All stages for the immobilization of the laccase
enzyme, the preparation of the bioelectrode using 4 mm diameter planar gold
electrodes DRP-С220АТ from “DropSens” (Llanera, Asturias, Spain), the estima-
tion of the optimal working potential with cyclic voltamperometry and the conduc-
tion of an analysis with a chronoamperometric approach in respect to the
corresponding substrate (2,20 -azino-bis(3-ethylbenzothiazoline-6-sulphonic acid,
ABTS) were the same as previously done in [6].
Figure 30.1 shows the o-Ps lifetimes and their relative intensities for the investigated
samples as a function of temperature in the range of 15–350 K. The temperature
where the free-volume (o-Ps lifetime) changes its slope is assigned as glass transition
temperature Tg1.
The determined values of the free-volume (Vh(Tg1) ¼ 4πR3/3) with radius R at the
glass transition temperature Tg1 and the thermal expansion coefficient αfv1 ¼ (1/Vh(Tg1))
(ΔVh/ΔT) [10] of the microscopical free-volume are presented in Table 30.1. In
addition to the glass transition temperature Tg1, the lower temperature at which the
slope of the Vh(T ) also changes in some cases, is designated as glass transition
temperature Tg2, although the nature of the two Tg remains not understood yet.
Figure 30.2 shows calibration curves of the response on increasing concentrations
of ABTS, obtained by chronoamperogramms of the bioelectrodes based on laccase
immobilized by pure ureasil (K0-fresh and K0-aged) and ureasil-chalcogenide glass
composites (K4-fresh and K4-aged) on the surface of the planar gold electrode.
Figure 30.3 shows calibration curves of the response on increasing concentrations of
ABTS for the planar gold electrodes modified by 10 μL laccase and 4 μL pure ureasil
(K0) and ureasil-chalcogenide glass composites (K4) under the following condi-
tions: 50 mM acetate buffer (рН 4.5), working potential 100 mV versus Ag/AgCl
(reference electrode) under constant stirring with a magnetic mixer. Estimated from
the calibration curves were the biosensor response Imax, the Michaelis-Menten
constant KM to ABTS as the substrate, the slope of the curve B, and the sensitivity
Fig. 30.1 o-Ps lifetime τ3 (left) and intensity I3 (right) as a function of temperature for the four
samples of this study. The error bars are within the size of the symbol. The solid lines are drawn as a
guide for the eye (See the text for details. Adapted from [8])
Table 30.1 Free-volume Vh1 at the glass transition temperature Tg1, the lower temperature at which
Vh(T ) changes its slope, designed as glass transition temperature Tg2, and the thermal expansion
coefficient αfv1 of the microscopical free-volume near Tg1 for the investigated polymer samples [8]
αfv1 (T < Tg1) (104 αfv1 (T > Tg1) (104
Sample Vh1 (nm3) Tg1 (K) Tg2 (K) K1) K1)
K0-fresh 0.123 0.002 216 13 – 25 3 286 21
(c and h)
K0-aged 0.123 0.003 230 19 166 89 53 22 273 99
(c and h)
K4-fresh 0.104 0.001 227 18 126 38 48 10 344 63
(c and h)
K4-aged (c) 0.134 0.001 178 19 88 58 46 17 206 56
K4-aged (h) 0.123 0.004 228 38 130 38 56 22 237 84
c cooling, h heating
Fig. 30.2 Calibration curves of responses to increasing concentrations of ABTS for planar gold
electrodes modified by laccase immobilized by pure ureasil (K0-fresh and K0-aged) and ureasil-
chalcogenide glass composites (K4-fresh and K4-aged)
Fig. 30.3 Calibration curves of responses to increasing concentrations of ABTS for planar gold
electrodes modified by 10 μL laccase and 4 μL pure ureasil (K0-fresh and K0-aged) and ureasil-
chalcogenide glass composites (K4-fresh and K4-aged)
Table 30.2 Biosensor response Imax, Michaelis-Menten constant KM to ABTS as the substrate, the
slope of the curve B, and the sensitivity of bioelectrode constructed based on laccase immobilized
by the investigated polymer samples
Sample Imax (μA) KM (mM) B (μАmM1) Sensitivity (AM1m2)
K0-fresh 7.62 1.7 0.64 0.17 10.0 794
K0-aged 10.96 3.38 0.35 0.14 22.2 1762
K4-fresh 43.77 2.71 0.045 0.005 501.7 39,817
K4-aged 86.8 0.9 0.030 0.008 761.2 60,413
of the bioelectrode, calculated as the ratio of the slope B to the area of the electrode
(12.6 mm2); these data are gathered in Table 30.2.
As seen from Table 30.2, the KM value gradually decreases from K0-fresh to
K0-aged and then to K4-fresh and K4-aged. The well-known Michaelis-Menten
saturation curve for an enzyme reaction shows the relation between the substrate
concentration and the reaction rate, where the constant KM is the substrate concen-
tration at which the reaction rate is half of the maximum rate achieved in the system
at saturating substrate concentration. A lower value of KM for the bioelectrode
indicates a high efficiency of direct electron transfer from the reduced form of the
enzyme on the surface of the planar gold electrode. So, the K4-aged sample showed
the best results in this regards. The biosensor sensitivity increases by a factor of 2.2
for the aged K0 sample. Likewise, the biosensor sensitivity increases 1.5 times for
the aged K4. At the same time, the increase of the biosensor sensitivity is 34.3 times
between the aged K4 and K0-aged samples, but 50.1 times K4-fresh and K0-fresh.
Thus, K4-fresh shows the most remarkable changes in the sensitivity of the amper-
ometric biosensor. According to the PALS results (Table 30.1), this sample K4-fresh
also shows the smallest free volume. Therefore, a correlation between the micro-
scopical free-volume of the polymer matrices and the biosensor characteristics of the
laccase-containing ureasil based biosensors is established. It must be noted here, that
the K4-fresh samples also showed the lowest crosslinking density and the highest
swellability [8]. Thus, by controlling the network properties of polymer matrix one
may control the functionality of amperometric biosensors based on a polymer
matrix. The observed findings could be further applied for improvement of the
operational parameters of the constructed biosensors, which may have potential for
monitoring the level of pollution of wastewater.
30.4 Conclusion
Ureasil and ureasil-chalcogenide glass composites of different history (fresh and

aged during 1 year) have been used for the immobilization of laccase and the
construction of amperometric biosensors. A correlation between the microscopical
free-volume of the polymer matrices as revealed by low-temperature positron
annihilation lifetime spectroscopy and the biosensor characteristics of the laccase-
containing ureasil based biosensors has been established.
Acknowledgments This work was supported by the Ministry of Education and Science of Ukraine
(projects Nos. 0116U004737; to TK, OS, MG and YK, and 0117U007142 (for Young Scientists; to
YK), by the Slovak Grant Agency VEGA (project No. 2/0157/17; to OŠ) and Slovak Research and
Development Agency (project No. APVV-16-0369; to OŠ and HŠ) and by the National Science
Fund of the Bulgarian Ministry of Education (project No. FNI-DN09/12-2016; to TK, TP, VB and
VI).
References
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nanoparticles. Langmuir 20:10268
2. Boev VI, Silva CIR, Hungerford G, Gomes MJM (2004) Synthesis and characterization of a
sol–gel derived ureasilicate hybrid organic-inorganic matrix containing CdS colloidal particles.
J Sol-Gel Sci Technol 31:131
3. Boev VI, Soloviev A, Silva CJR, Gomes MJM, Barber DJ (2007) Highly transparent sol-gel
derived ureasilicate monoliths exhibiting long-term optical stability. J Sol-Gel Sci Technol
41:223
4. Kavetskyy T, Lyadov N, Valeev V, Tsmots V, Petkova T, Boev V, Petkov P, Stepanov AL
(2012) New organic-inorganic hybrid ureasil-based polymer and glass-polymer composites
with ion-implanted silver nanoparticles. Phys Status Solidi C 9:2444
5. Kavetskyy T, Sausa O, Kristiak J, Petkova T, Petkov P, Boev V, Lyadov N, Stepanov A (2013)
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Chapter 31
Impedance Characterization of Gas
Sensitive Chalcogenide Films
Dumitru Tsiulyanu, Marina Ciobanu, and Olga Mocreac
Abstract The gas sensing performance of chalcogenide thin films, investigated by

the method of impedance spectroscopy is reported and discussed in order to assess
their use in future gas sensors operating at room temperature. Along with the
traditional use of Te films for such applications, impedance spectra of quaternary
As2S3Ge8 – Te alloys have been investigated in both dry synthetic and humid air, as
well as in their mixtures with different harmful gases. To elucidate the effect of
tellurium, the quaternary compositions As2Te13Ge8S3 and As2Te130Ge8S3 with
increasing concentration of Te have been investigated along with pure tellurium
films. The films have been prepared by thermal vacuum evaporation onto Pyrex or
sintered alumina (Al2O3) substrates carrying pre-deposited platinum interdigital
electrodes. As shown by AFM, SEM and X–ray analysis the phase/state of the
films depends on the composition, nature of the substrate and growth rate. The
morphology of the films grown on sintered alumina substrates appears to consist of
interconnected islands and dots, which facilitate a solid-gas interaction. It is shown
that impedance spectra, being strongly influenced by the gaseous environment are
also strongly influenced by material composition and phase/structural state of the
film. Analyses of these spectra in the Cole – Cole interpretation allowed to evaluate
the characteristic frequency, time constant, resistance and capacity of the films in
both dry air and its mixture with target harmful gases. Modification of the chemical
composition via addition of As, S and Ge atoms leads to structural/phase trans-
formations, along with the appearance of new mechanisms of charge transport that
influence the gas sensing performance of the chalcogenide based films.
Keywords Impedance measurements · Chalcogenide films · Gas sensors
D. Tsiulyanu (*) · M. Ciobanu · O. Mocreac

Department of Physics, Technical University, Chisinau, Moldova

318 D. Tsiulyanu et al.
31.1 Introduction
Glassy chalcogenide based films may be used for the detection of harmful gases at
room temperature. This possibility has already been pointed out in the early 2000s,
when Ge-As-Te based gas sensors for atmospheric pollution control have been
proposed [1, 2]. Later gas sensitive films based on (As2S3)(100x)(AgI)x [3], silver
doped SnSe2 and Ge2Sb2Te5 [4], different compositions in the binary, ternary and
quaternary systems of As-S–T(Se)-Ge [5] have been reported, as well as amorphous
films based on pure Te [6–8]. In order to estimate possible applications of these
materials in gas sensors, the authors have measured the variation of different
physical quantities (resistivity, current, resonance, work function etc.) during gas
sorption. Also, different pollutant and toxic gases (NO, NO2, CO, NH3, NH4, etc.),
as well as volatile organic compounds or water vapor have been used as a target gas.
Although the cross sensitivity to the gases mentioned is essentially different, the
distinguishing between them becomes important. One possibility to obtain a selec-
tive detection of gases has been mentioned at the early stages of the investigation of
semiconducting gas sensors [9] and consists in fast sweeping of the sensitivity of a
single sensor at different frequencies. The sensitivity of a sensor to different gases at
different frequencies can be quite different. That is, by monitoring the
a.c. conductance at specific frequencies, the sensitivity to different gas components
can be enhanced [10]. Moreover, a.c. measurements allow obtaining impedance or
admittance spectra of a sensor, calculating an equivalent circuit and distinguishing
between contributions from the surface, bulk or contacts to the film
conductivity [11].
In the present work, we report the results of gas sensing measurements performed
by means of impedance spectra in a large frequency range (5 Hz–13 MHz) at room
temperature. In order to get evidence on effect of tellurium, we have investugated
As2Te13Ge8S3 and As2Te130Ge8S3 as well as pure Te for comparison.
The glassy alloys were prepared by the melt-quenching method from pure (99.99%)
As, S, Te and Ge in quartz ampoules evacuated to 5–105 Torr. The melting was
performed at 900 C. The ampoules were rotated around the longitudinal axis at a
velocity of seven to eight rotations/min and were agitated for homogenization during
the synthesis time (24 h) and then quenched on a copper refrigerator with running
water. Two quaternary compositions As2Te13Ge8S3 and As2Te130Ge8S3 with
increasing concentration of Te were synthesized as well as pure polycrystalline
tellurium.
The chalcogenide based thin films have been prepared by thermal “flash”
evaporation of pre-synthesized materials from tantalum boats onto either glass
31 Impedance Characterization of Gas Sensitive Chalcogenide Films 319
(Pyrex) or ceramic Al2O3 substrates at a working pressure of 105 Torr. The ceramic
Al2O3 substrates were equipped with previously deposited interdigital platinum
electrodes with an electrode width of 15 μm and interelectrode distance of 45 μm.
The growth velocity of the film was in the order of 30 nm/s, and the area of
deposition around 5 mm2. The thickness of the films was about 60 nm, being
determined using a microinterferometer MII – 4. Structural investigations of the
grown films were carried out by X–ray analyses and scanning electron microscopy
(SEM). The films were encapsulated in standard TO–16 sockets, their contacts were
thermally bonded to socket pins by means of copper wires.
Impedance measurements were carried out in the frequency range from 5 Hz to
13 MHz using a HP4192A impedance analyzer. For these experiments the thin film
sensing devices were put into a test cell (of 10 ml volume) in which the gases were
injected parallel to the film surface. Constant flow (100 ml/min) was maintained by
mass flow controllers (MFC, Wigha, Germany). NO2 vapor with a concentration of
1.5 ppm was obtained by using a calibrated permeation cylinder (Vici Metronics,
USA) which was incorporated into the experimental set–up. In this work, the a.c. gas
sensitivity is defined as relative variation of the impedance for a selected frequency
in a mixture of the carrier gas with a target one (Zg) and the pure carrier gas (Za),
divided by target gas concentration C in percent/ppm:

Z a Z g
η¼ 100% ð31:1Þ
ZaC
31.3 Surface Morphology and Phase/Structure
The surface morphology of the films was made visible with a VEGA TESCAN TS 5130
MM scanning electron microscope at an acceleration voltage of 30 kV. X-ray analyses
using a DRON – YM1 diffractometer with FeK α radiation was applied for structural
investigations of the grown films. The rotation velocity of the scintillation counter was
2 (or 4) degrees/min. Figures 31.1 and 31.2 shows SEM images of the quaternary
As2Te13Ge8S3 and As2Te130Ge8S3 chalcogenides along with films of elemental Te,
Fig. 31.1 SEM images of (a) As2Te130Ge8S3, (b) As2Te13Ge8S3 and (c) pure tellurium thin films
grown on Pyrex glass substrates
Fig. 31.2 SEM images of (a) As2Te130Ge8S3, (b) As2Te13Ge8S3 and (c) pure tellurium thin films
grown on sintered alumina (Al2O3) substrates
Te
a b c
Te
Te
Te
60 50 40 30 20 50 40 30 20 44 40 36 32 28 24 20
2Q 2Q 2Q
Fig. 31.3 XRD diffraction pattern of (a) As2Te130Ge8S3, (b) As2Te13Ge8S3 and (c) pure tellurium
thin films grown on Pyrex glass substrates
grown on different substrates, using the same deposition rate (~30 nm/s). As can be seen,
the films grown on glassy (Pyrex) substrates are continuous layers, but the films grown
on sintered alumina consists of agglomerated islands, resulting in films with a great
surface roughness. In all cases no crystallite traces are observed.
Figure 31.3 shows the XRD patterns of the films deposited on the Pyrex sub-
strates. It can be seen that the film with the enhanced Te concentration (91 at.%)
(Fig. 31.3a) contains diffraction peaks, which indicate the existence of a crystalline
phase. On the other and, no peaks of crystalline Te are observed in both the
As2Te13Ge8S3, and the pure tellurium films, which means that these films are in
the vitreous state.
The XRD patterns of quaternary As2Te13Ge8S3, As2Te130Ge8S3 and pure Te,
films deposited on alumina substrates are shown in Fig. 31.4. It is evident that the
As2Te13Ge8S3 film (Fig. 31.4b) is in the amorphous state. The quaternary films with
the higher Te concentration as well as pure films show very small peaks
corresponding to crystalline Te phases (Fig. 31.4a, c), indicating their nearly amor-
phous nature. No peaks corresponding to oxides of tellurium are discernable in the
XRD patterns. These results are in agreement with SEM observation.
a b c
Alumina
Te
Te Te
Te
38 36 34 32 30 28 40 38 36 34 32 30 28 26 40 38 36 34 32 30 28 26
2Q 2Q 2Q
Fig. 31.4 XRD diffraction pattern of (a) As2Te130Ge8S3, (b) As2Te13Ge8S3 and (c) pure tellurium
thin films grown on sintered alumina substrates
31.4 Impedance Characterization
31.4.1 Effect of Material Composition
It is well known that impedance measurements allow to calculate the equivalent

circuit of a film system and to distinguish between contributions from the surface,
bulk or contacts to the overall film conductivity [11]. For this purpose, the imped-
ance of the thin film device is usually considered in complex form:
1
Z ð ωÞ ¼ ¼ ReðZ Þ þ iImðZ Þ ð31:2Þ
Y ð ωÞ
R
where ReðZ Þ ¼ ð31:3Þ
1 þ ðω C RÞ2
ω C R2
and ImðZÞ ¼ ð31:4Þ
1 þ ðω C RÞ2
Then Im(Z) is plotted vs. Re(Z) in a Nyquist diagram.

Figure 31.5 shows the Nyquist diagrams obtained from data measured in pure dry
air for thin film devices based of all chalcogenide materials studied in this work, at
room temperature (22 C). The diagrams are quite different. The diagram of the pure
Te film shows a slightly depressed semi-circular arc with the center placed below the
real axis owing to the presence of different circuit elements in the thin film device
[11]. It seems that the complex impedance diagram of the As2Te13Ge8S3 film,
calculated from the measured values of the real and imaginary parts show the
semi-circular arc as well, although the diameter of the semicircle is so large that it
could not be plotted completely due to the lack of data, due to device limitation.
Thus, for these two compositions a simplified equivalent circuit as shown in
Fig. 31.5 (a) Nyquist diagrams of thin film devices based on As2S3Ge8 – Te alloys in dry air at
22 C and (b) suggested equivalent circuit
Fig. 31.5b can interpret the Nyquist plot. The frequency independent serial resis-
tance R0 is due to the sum of the Ohmic resistances of the electrical connections, but
the resistance Rω and the capacity Cω are due to other contributions, among them
contact resistance and capacity seem to be the most important. The circles on these
diagrams are depressed due to the dependence of both Rω and Cω on frequency. The
complex impedance diagram of the As2Te130Ge8S3 film does not resemble a semi-
circular arc. This means, the equivalent circuit is much more complicated than a
simple RC parallel one.
From simple analysis of the equivalent circuit the values of Rω and Cω of the film
can be evaluated as:
Im2 ðZÞ þ Re2 ðZÞ

Rω ¼ ð31:5Þ
ReðZÞ
ImðZ Þ
Cω ¼ 2 ð31:6Þ
ω Im ðZ Þ þ Re2 ðZ Þ
Equations (31.5) and (31.6) allows an estimation of the resistance and capacitance
of the film at any frequency entire the spectrum, including the characteristic fre-
quency fm, at which the imaginary part Im(Z) reaches its maximal value.
Calculated from Eqs. (31.5) and (31.6), resistance Rω and capacity Cω of the films
at the characteristic frequency Rm and Cm, as well as the film impedance Zm and the
time constant calculated as [12]:
Table 31.1 Impedance and R-C values at the characteristic frequency

Composition Te As2Te13Ge8S As2Te130Ge8S
Environment Dry air 1.5 ppm NO2 Dry air 1.5 ppm NO2 Dry air 1.5 ppm NO2
fm, [kHz] 450 950 – 140 1000 800
Zm, [kΩ] 13.3 6.6 – 120 0.48 0.42
τm107 s 3.5 1.7 – 11.4 1.6 2.0
Rm, [kΩ] 18.5 9.3 – 167 0.49 0.43
Cm, [pF] 18.3 17.8 – 6.8 8.7 8.1
Fig. 31.6 Impedance of

chalcogenides
semiconductors As2S3Ge8 –
Te vs frequency of the
applied voltage at room
temperature (22 C)
1
τm ¼ ω1
m ¼ ¼ Rm C m ð31:7Þ
2πf m
are listed in Table 31.1. Note that the respective values for the high resistive
As2Te13Ge8S3 film could not be calculated due to the reason mentioned above. On
the other hand, we have assessed the characteristic frequency fm of the low resistivity
films with the composition As2Te130Ge8S3 as the frequency, at which the imaginary
part of the impedance reaches the maximal value, in spite of the not semicircular
form of its Nyquist diagram. Further, we have applied the value of fm to calculate Zm,
Rm and Cm of the films as well, which also are listed in Table 31.1. It is noticeable
that in spite of the low concentration of other elements introduced in this alloy
(2.1 at.% S; 1.4 at% As and 5.6 at % Ge), both the impedance and the electrical
resistance decrease dramatically in comparison with the pure Te film by two and
three orders of magnitude, respectively.
As far as the regular impedance spectra are concerned, they also strongly
depend on the material composition. Figure 31.6 illustrates the frequency
dependent impedance of the chalcogenides examined in this work. It can be
seen that the impedance of pure Te and As2T13Ge8S3 films strongly decrease
with increasing frequency. On the other hand, the variation of the impedance
with increasing frequency in As2T130Ge8S3 films is neglegible. This behavior can

be due to different mechanisms of charge transport in these materials as will be
considered below.
31.4.2 Effect of NO2 Adsorption
Figure 31.7a–c shows the complex impedance diagrams in the Cole-Cole presenta-
tion (Nyquist diagram) of thin film devices discussed in this study measured both in
dry air and upon exposure to NO2 at room temperature (22 C). The addition of
nitrogen dioxide to dry air does not change the general shape of the impedance
spectra of pure tellurium (a) and As2T130Ge8S3 (b) films; that is, the NO2 influences
Fig. 31.7 Nyquist diagrams of (a) Te, (b) the quaternary As2Te130Ge8S3 and (c) As2Te13Ge8S3
films in both dry air and a mixture with NO2, at room temperature (22 C). The picture inserted in
(c) shows separately the diagram obtained under the application of NO2.only
all elements of the equivalent circuit. The values of the characteristic frequency, the
impedance and the time constant τm of the films at this frequency for a concentration
of NO2 of 1,5 ppm, at room temperature are summarized in Table 31.1.
From this table it is seen that if the environment is changed from dry air to this
mixture the resistance Rm is strongly influenced while the capacitance Cm does not
vary essentially.
The complex impedance diagram of devices based on the highly resistive
As2Te13Ge8S3 film (Fig. 31.7c) show in the presence of NO2 vapor the typical
semicircular arcs. The resistance Rω and capacity Cω of the film at characteristic
frequency, i.e. Rm and Cm as well as the film impedance in this environment,
calculated from Eqs. (31.5) and (31.6), are listed in Table 31.1. It can be seen that
under application of 1,5 ppm NO2, the impedance and electrical resistance of the
As2Te13Ge8S3 film are about 20 times higher than the respective values of pure
tellurium films, but the capacity is twice smaller.
The change of frequency dependent impedance of the chalcogenides in question
upon exposure to a low concentration of NO2, make their abilities to be used in
sensor development evident. In a first approximation, the data given in Table 31.1
allow assessing the effect of nitrogen dioxide on the device impedance and its
sensitivity. However, this assessing is valid only at the characteristic frequency,
which in turn becomes essentially influenced by gas adsorption. More complete
information concerning the gas sensing properties of the films can be obtained by
investigating their full impedance spectra, both in dry air and its mixture with a target
gas. Furthermore, using relation (31.1) the spectra of gas sensitivity can be
evvaluated, and the frequency, at which the maximum sensitivity occurs, can be
determined. Figure 31.8 shows the frequency dependent sensitivity of the films in
question towards NO2, at room temperature.
It is observed that the frequency most strongly influences the gas sensitivity of the
Te and As2Te13Ge8S3 films, while that of As2Te130Ge8S3 remains nearly
Fig. 31.8 Sensitivity

spectra of chalcogenide
As2S3Ge8-Te thin films to
1,5 ppm NO2 in dry air at
room temperature. The inset
show a comparison of the
maximum sensitivities at the
respective frequencies for
the materials in question
independent of the applied frequency. The essential difference in the velocity of the
decrease of the sensitivity for As2Te13Ge8S3 and pure tellurium film is also notice-
able. The sensitivity of the As2Te13Ge8S3 film decreases sharply with increasing
frequency but tends to saturate already at approximately 500 kHz. On contrary, the
sensitivity of Te film diminishes quite slowly and tends to saturation only at
approximately 3 MHz. The inset in Fig. 31.8 reports for each composition the
maximal value of the sensitivity, while the abscissa indicates the frequency at
which this maximum sensitivity occurs.
31.4.3 Cross Sensitivity to Other Gases
Thus, the chalcogenide films in question show remarkable sensing properties to NO2
and are suitable for the development of sensors operating at room temperature. In
this context the interfering effect of the other accompanying gases in the environ-
ment becomes important, as well as the cross sensitivity to water vapor.
Figure 31.9 reports the complex impedance spectra of the tellurium film upon
exposure to different test gases: NO2, H2, and H2S. It is seen that addition of these
gases to dry air does not change the general shape of the curve, i.e. they influences all
elements of the equivalent circuit.
From these diagrams both the characteristic frequency and the impedance of the
film at this frequency have been determined. The values (Table 31.2) shows that the
addition of NO2 to dry air leads to a decrease of the impedance, while the addition of
H2 or H2S results in its increase.
In this context it becomes interesting to analyze the frequency dependences of the
sensitivity to different target gases through the impedance change. Figure 31.10
shows the sensitivity spectra of pure tellurium films toward nitrogen dioxide,
hydrogen sulfide and molecular hydrogen at room temperature. Although the
Fig. 31.9 Nyquist diagrams

of the tellurium thin film in
different environmental
conditions at room
temperature
Table 31.2 Impedance of Environment fm [kHz]] Z [kΩ]

tellurium based films at
Dry air 900 13,3
characteristic frequency in
different environments 1,5 ppm NO2 1500 7,5
H2 1% by volume 600 19,8
50 ppm H2S 400 29
Fig. 31.10 Sensitivity of tellurium thin films toward different gases vs. frequency
sensitivity towards these gases differs very much, there is always a frequency
dependent edge of sensitivity, which also depends of the nature of the adsorbed
species.
At this edge, the sensitivity increases with decreasing frequency, reaching satu-
ration at low frequencies (dependent of gas species). A comparison of the saturation
sensitivity towards the gases in question shows that the sensitivity to NO2 is more
than ten times higher than that towards H2S and by four orders of magnitude higher
than that towards molecular hydrogen.
The interfering effect of humidity on NO2 detection has been investigated using
the quaternary As2Te13Ge8S3 based films. Figure 31.11 shows the influence of
humidity on the impedance spectra of the As2Te13Ge8S3 film during NO2 detection
at 22 C. It can be observed that at room temperature, the interfering effect of water
molecules is not so essential. The frequency dependent effect of water vapor consists
in increasing the impedance by (30–200 kΩ) at 58% RH. This impedance increase
diminishes the sensor sensitivity to NO2 by approximately 15%/ppm, independent of
the applied frequency.
31.5 Discussion
The chalcogenide materials considered in this work belong to the disordered

so-called lone-pair semiconductors. The states of lone-pair (unshared) p – electrons
of the chalcogen atoms in these materials form a band which overlaps with the
Fig. 31.11 Effect of

humidity on the impedance
spectra of a As2Te13Ge8S3
film during detection of
nitrogen dioxide at room
temperature
b
Ec
a
C10(d.b.) C20 C10(d.b.) C1- C3+ C20 C 3+
Ef
C 1-
Ev
e-
Fig. 31.12 (a) Model of the dangling bond lone-pair electrons interactions and (b) the band-
bending at the surface
valence band, forming its upper part. The interaction between lone-pair electrons of
chalcogen atoms as well as their interaction with “dangling” bonds create the specific
charge defects C3+ and C1 (Fig. 31.12a) which operate as localized states in the
forbidden gap, pinning the Fermi level close to the valence band, i.e. determining the
p-type conductivity [13]. The interaction of lone-pair electrons with “dangling”
bonds will be maximal at the film surface, as at the surface the maximum concen-
tration of dangling bonds occurs. This interaction means capturing of electrons from
the valence band, which results in the formation of a hole enriched (accumulation)
region adjacent to the surface, so that the bands bend up as shown in Fig. 31.12b. In
this context, the surface phenomena caused by gas adsorption can be considered as
an external control of the band-bending at the surface, owing to a variation of the
hole density in the accumulation region in the presence of gaseous media.
For instance, the sensing properties of the materials in question toward nitrogen
dioxide originate from the odd electrons (single unpaired electrons) of the NO2
molecules [14]. Being adsorbed on the surface of the chalcogenide semiconductor,
the NO2 molecule acts as a dangling bond, that can accept a lone-pair electron to
form an electron pair, that is chemisorption occurs. Capture of a lone-pair electron
means the transition of an electron from the upper part of the valence band to a NO2
acceptor level, accompanied by releasing an additional hole. Thus, the adsorption of
nitrogen dioxide leads to an increase of the concentration of majority carriers
adjacent to the surface layer, which results in both further bands – bending and
increasing the electrical conductivity of the film. The high sensitivity, as well as the
large frequency range of response to NO2 support this mechanism of “strong”
chemisorption, owing to interaction between the odd electrons of the NO2 molecules
and lone-pair electrons of chalcogen atoms of the films.
Elemental hydrogen occurs only as biatomic gas molecules at normal conditions.
These molecules do not comprise unpaired (dangling) electrons, i.e. a strong chem-
isorption of hydrogen on the surface or within the chalcogenide film cannot be
expected. Perhaps, the very low sensitivity (Fig. 31.10b) to H2 is due to the reducing
effect of oxygen already absorbed on the surface of the film from the carrier (dry air)
gas. In our previous paper [15] it was shown that the “weak” chemisorption of
symmetric O2 molecules from the carrier gas is accompanied by localization of lone-
pair electrons near the surface, which leads to a decrease the film resistance. Besides,
the high concentration of oxygen in carrier gas promotes the formation of a catalytic
gate [16], which can be removed by other gases. Thus, assuming that the molecular
hydrogen removes already adsorbed oxygen, the decrease of the surface conductivity
of the film can be expected.
Hydrogen sulfide leads to an increase of the impedance of the film (Fig. 31.9).
The sensitivity of the tellurium films to H2S is by three orders of magnitude higher
than that to H2 but remains almost ten times smaller than the sensitivity to NO2
(Fig. 31.10). Besides, the edge of sensitivity to H2S is shifted to 1 MHz, being the
same as that of the sensitivity to hydrogen. These peculiarities indicate that interac-
tion of H2S with chalcogenide films can be attributed neither to “strong” chemisorp-
tion of H2S molecules nor to a reduction of existing “weak” chemisorbed oxygen
from the carrier gas. Taking into consideration that the electron configurations of
water and hydrogen sulfide molecules are similar, the interaction of chalcogenude
films with H2S is likely to take place similar to the mechanism proposed in [17] the
interaction of water vapor with these films. This mechanism assumes orientational
polarization of polar gas molecules physically adsorbed on the film surface, followed
by the formation of weak bonds of electrostatic origin, which can localize the free
holes at the surface and therefore diminishes the electrical conductivity.
Another factor that can affect the gas sensing is structural and compositional
disorder. Disorder creates a random potential, which results in the formation of both
tails of extended bands and a finite value of localized states close to the Fermi level N
(Ef) [18] This means that the a.c. conductivity can be realized by three mechanisms:
band-to-band conduction with an activation energy Eg (forbidden gap of the con-

sidered material), hopping between localized states in the extended band tails or
tunneling (variable range hopping) between localized states situated close to the
Fermi level. The contribution of each mechanism depends on material composition,
frequency range and temperature regime. As all experiments were performed at
room temperature, only the effect of frequency on impedance can somewhat eluci-
date the predominant mechanism of current flow. The negligible variation of imped-
ance with frequency increase in As2Te130Ge8S3 (Fig. 31.6) indicates that
conductivity via extended states, i.e. band-to-band mechanism is the main effect.
On the other hand, the strong decrease of the impedance in the pure Te and
As2Te13Ge8S3 films with frequency increase shows that the hopping mechanism
of conductivity through localized states is dominant. In order to distinguish between
hopping via localized states of the extended bands tails and variable range hopping
over localized states near Fermi level, an additional investigation of the effect of
temperature on the a.c. conductivity is required, which constitutes a subject of a
future study.
As far as the effect of the material composition is concerned, we assume that the
basic interaction mechanism discussed early for pure Te layers [19] also occurs in
the Te based alloys studied in this work, but addition of As, S and Ge atoms can
result in structural/phase transformations, the appearance of new mechanisms of
current flow and obviously, in a modification of the gas sensing peculiarities. Indeed,
as shown by the X ray diffraction measurements, addition of only 5.6 at% Ge, 2.1 at
% S and 1.4 at% As (alloy As2Te130Ge8S3) diminishes the fraction of crystalline
tellurium, but leads to a dramatic decrease of the impedance by two orders of
magnitude, followed by a fourfold decrease of the gas sensitivity. In contrast,
addition of higher concentrations of these elements (30.8 at% Ge, 11.6 at% S and
7.6 at% As, alloy As2Te13Ge8S3) transforms the film into an amorphous state with a
dramatic increase of the impedance by at least two orders of magnitude, followed by
an more than twofold increase of gas sensitivity. As has been mentioned above, these
results shows how the composition and phase/structural state of the film control not
only the mechanism of current flow but also their gas sensing properties and finally,
their abilities to be used in the development of gas sensing devices operating at room
temperature.
31.6 Conclusions
Glassy chalcogenides can be used for the development of effective impedance

operating gas sensitive devices. The sensors can operate at room temperature with
a good sensitivity in the ppm and sub-ppm concentration range.
The phase/structural state of the As2Ge8S3-Te, film grown onto both glassy and
sintered alumina substrates via high speed thermal deposition in vacuum, is pre-
dominantly amorphous. Material composition and the phase/structural state of the
chalcogenide films, as well as the gaseous environment strongly influence the
impedance spectra of the films and their sensitivity to target toxic or pollutant gases.
Addition of NO2 decreases the impedance, whereas addition of H2 or H2S increases
it in a large range of frequencies due to the different mechanisms of interaction
between these gases with the films in question. The NO2 sensing mechanism
involves “strong” chemisorption, which results in an increase of band bending and
surface electrical conductivity. The impedance sensitivity, being maximal for amor-
phous As2Te13Ge8S3 is assumed to be controlled also by the competition of several
transport mechanisms.
Acknowledgements This work was financially supported by the Technical University of Moldova
through the Institutional Grant 15.817.02.29A. The authors express gratitude to Dr. M. Enache from
NCMST of TUM for SEM analysis and Dr. G. F. Volodina from IAP ASM for XRD analysis.
References
1. Marian S, Tsiulyanu D, Liess H-D (2001) High sensitive tellurium based NO2 gas sensor. Sens
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2. Marian SI, Tsiulyanu DI, Marian TI, Liess H-D (2001) Chalcogenide – based chemical sensors
for atmospheric pollution control. J Pure Appl Chem 73:2001
3. Koleva K, Popov C, Petkova T, Petkov P, Mihailescu IN, Reithmaier J-P (2009) Complex
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4. Popescu M, Velea A, Sava F, Lorinczi A, Tomescu A, Simion C, Matei E, Soco G, Mihailescu
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7. Tsiulyanu D, Mocreac O, Ciobanu M, Enachi M, Volodina G (2014) Peculiarities of ultrathin
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detection, information and energy security. Springer, Dordrecht, p 535
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on quaternary chalcogenides. Phys Status Solidi B 253:1046
18. Mott NF, Davis EA (1979) Electron processes in non –crystalline materials. Clarendon Press,
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properties. In: Petkov P et al (eds) Nanoscience advances in CBRN agents detection, informa-
tion and energy security. Springer, pp 389–408
Chapter 32
Swelling Behavior of Organic-Inorganic
Ureasil-Based Polymers
T. S. Kavetskyy, H. Švajdlenková, Y. Kukhazh, O. Šauša, K. Čechová,

I. Mat’ko, N. Hoivanovych, O. Dytso, T. Petkova, V. Boev, and V. Ilcheva
Abstract The swelling behavior of pure ureasil and ureasil-chalcogenide glass

composites of different history (fresh, aged and thermally heated) was examined
using ethyl alcohol. Swelling experiments showed the structure of the network of
samples aged for 1 year after preparation has a lower swelling ability compared with
pure ureasil as well with the composite, but the effect is more expressed for the pure
polymer. In the cases of a thermally heated pure ureasil sample and a more than
5 years after preparation aged sample of the composite, the structure network has
practically the same swelling ability as the fresh pure ureasil and the composite
samples. It is suggested that one of the factors influencing the swelling is the change
of the basic ureasil network due to aging and/or thermal heating.
Keywords Swelling · Organic-inorganic hybrid · Polymer · Composite · Ureasil
T. S. Kavetskyy (*)
H. Švajdlenková
Polymer Institute, Slovak Academy of Sciences, Bratislava, Slovak Republic
Y. Kukhazh · N. Hoivanovych · O. Dytso
O. Šauša · K. Čechová · I. Mat’ko
Institute of Physics, Slovak Academy of Sciences, Bratislava, Slovak Republic
T. Petkova · V. Boev · V. Ilcheva
Institute of Electrochemistry and Energy Systems, Bulgarian Academy of Sciences, Sofia,
Bulgaria

32.1 Introduction
Nanocomposite materials containing glass [1], glass-ceramics [2], metal alloys [3]
and polymers [4] are of increasing interest due to a variety practical application.
Urea-silicates or ureasils are well-known representatives of organic-inorganic hybrid
polymer nanocomposite materials successfully examined as dispersion media for
luminescent Eu3+ salts, ion conducting Li+ salts, organic dyes, semiconductors and
metal nanoparticles [5, 6]). For the first time, ureasil-based composites were also
tested for the immobilization of commercial laccase from Trametes versicolor
(a common polypore mushroom) and the construction of amperometric biosensors
[7]. It has been found that the biosensor based on the ureasil-chalcogenide glass
composite was characterized by very high sensitivity, 38.3 times higher in compare
with pure ureasil. On the other hand, application of the ureasil-chalcogenide glass
composite with incorporated silver nanoparticles synthesized by high-dose 30 keV
Ag+ ion implantation results in decreasing the biosensor sensitivity up to 2390 times.
In the present work, the swelling behavior of pure ureasil and ureasil-chalcogenide
glass composites of different history (fresh, aged and thermally treated) was exam-
ined using ethyl alcohol (EtOH). Numerical parameters such as the bulk density of
the polymeric sample ρp and the molecular weight between two crosslink points Mc
are considered.
32.2 Experimental
The pure ureasil matrix was synthesized as follows [8–10]: O,O0 -bis
(2-aminopropyl)-polypropylene glycol-block-polyethylene glycol-block-polypro-
pylene glycol-500 (Jeffamine ED-600) was dried under vacuum for 30 min;
3-isocyanatepropyltriethoxysilane (ICPTES), tetraethoxysilane (TEOS, 98%) and
n-butyl amine were used as received; Jeffamine and ICPTES were mixed in a
stoichiometric ratio of 1:2 in order to obtain a liquid ureasilicate monomer; thereaf-
ter, TEOS (1.12 mmol) and n-butylamine were added to the mixture, which was kept
under stirring for more than 20 min. The mixture was then transferred into a plastic
Petri dish and jellified under appropriate conditions; the obtained gels were heated in
a vacuum furnace at 333 K at ambient conditions; and a non-rigid, homogeneous and
highly transparent xerogel in form of a disk with a diameter of 40 mm and a
thickness of 0.25 mm was obtained within 1 day. At the same time, the ureasil-
chalcogenide As2S3 glass composite matrix was synthesized as follows [8–10]: the
As2S3 ingots were synthesized by melt quenching method from As (5 N) and S (5 N)
in sealed quartz ampoules at 923 K; the melt was quenched to room temperature, and
the obtained glassy samples were finely grounded in powder form and dissolved in
an organic solvent (3 ml n-butylamine) to the 0.4 M concentration; and the As2S3/
ureasil composite was obtained by mixing the ureasilicate monomer with the
solution of chalcogenide clusters. The stiff gel was obtained as described above.
32 Swelling Behavior of Organic-Inorganic Ureasil-Based Polymers 335
The investigated samples were swollen in anhydrous ethyl alcohol (EtOH) during
8 days at room temperature (301 K). At first, the initial weight of the samples (m0)
was determined, then that of the samples after 24 h for 8 days; the maximum weight
observed is called mswollen. An equilibrium was achieved after 6–7 days. On the 8th
day the weight did not change, i.e. the maximum saturated weight (mswollen) was
achieved. After that the room temperature samples were dried at 333 K in argon
atmosphere by using the thermo gravimetric analysis (TGA) method where the
weight of dry sample (mdry) was obtained as the minimum saturated mass. The
percent equilibrium mass swelling (S) was determined as:

S¼ mswollen mdry =mdry 100 ð32:1Þ
The molecular weight between two crosslink points Mc was calculated based on
the Flory-Rehner equation [11, 12] as
h i
ν ¼ 1=M c ¼ V r þ χV r 2 þ ln ð1 V r Þ = ρp V 0 V r 1=3 V r =2 ð32:2Þ
where ν is the crosslinking density, ρp is the bulk density of the polymeric sample,
and Vr is the volume fraction of the polymer in the swollen state given by
V r ¼ 1=ð1 þ QÞ ð32:3Þ

Q ¼ ðmswollen m0 Þρp = m0 ρliquid ð32:4Þ
where ρliquid is the density of the liquid and V0 is the molar volume of the liquid (for
EtOH, V0 is 57.62 cm3/mol); the parameter χ is the Flory-Huggins interaction
parameter between the polymer and the liquid (the values of χ for polymer-solvent
interactions were calculated via the cohesive energy of the atomic groups). The
density of the investigated polymeric samples was determined using the gravimetric
method (Archimedean principle). The samples were immersed into EtOH at room
temperature. The bulk density of individual samples was calculated by
ρ ¼ ρEtOH ½m0 =ðm0 m1 þ mwire Þ ð32:5Þ
where ρEtOH is the density of EtOH at 301 K, mwire is the weight of the wire on which
the sample is hanged in EtOH, and the values of m0 and m1 are the sample weights in
air and after immersion into EtOH.
Figure 32.1 shows the images of investigated samples used for this research. It can
clearly be seen that the physical aging of sample leads to decreasing of its optical
transparency, while heating of the sample up to 420 K does not change visibly its
optical properties.
Fig. 32.1 Photos of the investigated polymer samples used for the research: 1 K0-fresh: pure
ureasil polymer, fresh (2 months after preparation); 2 K0-heated: pure ureasil polymer, fresh and
thermally heated up to 420 K; 3 K0-aged: pure ureasil polymer, aged during 1 year after prepara-
tion; 4 K4-fresh: ureasil-glass composite, fresh (2 months after preparation); 5 K4-aged: ureasil-
glass composite, aged during 1 year after preparation; 6 K4-very aged: ureasil-glass composite,
aged more than 5 years after preparation
Fig. 32.2 The swelling values as a function of time for the pure ureasil polymers (K0: fresh, heated,
and aged) and the ureasil-glass composites (K4: fresh, aged, and very aged) in EtOH at room
temperature. The samples are labeled as shown in Fig. 32.1
Figure 32.2 shows the results of the swelling experiments for the investigated
samples in EtOH. The numerical parameters such as the bulk density of the poly-
meric sample ρp and the molecular weight between two crosslink points Mc are
presented in Table 32.1.
Higher Mc values mean a lower crosslinking density and higher swellability.
Thus, swelling experiments using EtOH showed that the structure of the network of
samples aged for 1 year after preparation (K0-aged) has a lower swelling ability
compared with pure ureasil (K0-fresh) as well with the composite (K4-fresh), but the
effect is more expressed for the pure polymer. In the cases of a thermally heated pure
ureasil sample (K0-heated) and a more than 5 years after preparation aged sample of
the composite (K4-very aged), the structure network has practically the same
swelling ability as the fresh pure ureasil and the composite samples (K0-fresh and
K4-fresh, respectively). It is suggested that one of the factors influencing the
swelling is the change of the basic ureasil network due to aging and/or thermal
heating. Further experiments with the construction of biosensors based on ureasil
polymer matrixes [7] using the investigated polymers would be useful to examine
32 Swelling Behavior of Organic-Inorganic Ureasil-Based Polymers 337
Table 32.1 Density of the polymeric sample ρp, molecular weight between two crosslink points Mc
and comparative analysis of crosslinking density or swellability for the investigated polymers in the
group of K0 and K4
Sample ρp (g/cm3) Mc Comparative analysis in the group
K0: pure ureasil polymers
K0-fresh 1.1778 0.0021 92.47 Lower swellability
K0-heated 1.2080 0.0163 106.37 The highest swellability
K0-aged 1.1814 0.0012 44.0 The lowest swellability
K4: ureasil-glass composites
K4-fresh 1.2015 0.007 99.22 The highest swellability
K4-aged 1.2170 0.003 76.52 The lowest swellability
K4-very aged 1.1986 0.010 89.50 Lower swellability
The samples are labeled as shown in Fig. 32.1
the relationship between the network properties and the bio-functionality of amper-
ometric biosensors.
32.4 Conclusion
Swelling behavior of the pure ureasil and ureasil-chalcogenide glass composite

samples of different history has been examined using EtOH. It is suggested that
one of the factors influencing swelling is the change of the basic ureasil network due
to aging and/or thermal heating.
Acknowledgments This work was financially supported by the Ministry of Education and Science
of Ukraine (projects Nos. 0116U004737, 0117U007142 (for Young Scientists) and 0117U007143;
to TK and YK), by the Slovak Grant Agency VEGA (project No. 2/0157/17; to OS and project
No. 2/0127/17; to IM), by the Slovak Research and Development Agency (project No. APVV-16-
0369; to HS, OS, KC and IM) and by the National Science Fund of the Bulgarian Ministry of
Education (project No. FNI-DN09/12-2016; to TK, TP, VB and VI).
References
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nanomultilayer structures. Nanoscale Res Lett 11:39
2. Duriagina Z et al (2017) Comparative estimation of the structure and electrical properties of
functional layers based on PbO-ZnO-B2O3 glass-ceramic sealant. Powder Metall Met Ceram
55:580
3. Cherepova TS, Dmytrieva HP, Dukhota OI, Kindrachuk MV (2016) Properties of nickel
powder alloys hardened with titanium carbide. Mater Sci 52:173
4. Rajesh AT, Kumar D (2009) Recent progress in the development of nano-structured conducting
polymers/nanocomposites for sensor applications. Sensors Actuators B 136:275
5. Boev VI et al (2004) Flexible ureasil hybrids with tailored optical properties through doping
with metal nanoparticles. Langmuir 20:10268
6. Sa Ferreira RA et al (2001) Energy-transfer mechanisms and emission quantum yields in Eu3+-
based siloxane-poly(oxyethylene) nanohybrids. Chem Mater 13:2991
7. Kavetskyy T et al (2017) Laccase-containing ureasil-polymer composite as the sensing layer of
an amperometric biosensor. J Appl Polym Sci 134:45278
8. Kavetskyy T et al (2011) In: Riethmaier JP, Paunovic P, Kulisch W, Popov C, Petkov P (eds)
Nanotechnological basis for advanced sensors. Springer, Berlin, p 103
9. Kavetskyy T et al (2012) New organic-inorganic hybrid ureasil-based polymer and glass-
polymer composites with ion-implanted silver nanoparticles. Phys Status Solidi C 9:2444
10. Kavetskyy T et al (2013) New organic-inorganic hybrid ureasil-based polymer materials studied
by PALS and SEM techniques. Mater Sci Forum 733:171
11. Flory PJ, Jr RJ (1944) Effect of deformation on the swelling capacity of rubber. J Chem Phys
12:412
12. Flory PJ (1950) Statistical mechanics of swelling of network structures. J Chem Phys 18:108
Chapter 33
Synthesis and Characterization of
Organically Modified Silicates Obtained
by Co-condensation of Two Organic –
Inorganic Ureasilicate Monomers
V. Ilcheva, V. Boev, D. Tatchev, G. Avdeev, G. Zamfirova, V. Gaydarov,

V. Lilova, and T. Petkova
Abstract Transparent organic-inorganic ureasilicate materials (ureasils) were syn-

thesized by hydrolysis and co-condensation of two organic – inorganic precursors,
obtained by reactions between 3-isocyanatepropyltriethoxysilane (ICPTES) and
double terminated polyetheramine (Jeffamine), and between ICPTES and
3-aminopropyl triethoxysilane (APTES), respectively. The prepared samples were
characterized by optical UV – VIS spectroscopy, small-angle X-ray scattering
(SAXS), FTIR spectroscopy and the depth sensing indentation method (DSI). It is
shown that the molar ratio between the initial components influences on the mechan-
ical and optical properties of the materials in the investigated range.
Keywords Ureasilicate materials · Sol-gel · Organic-inorganic hybrids ·

Microhardness
V. Ilcheva (*) · V. Boev · T. Petkova

Institute of Electrochemistry and Energy Systems “Academician Evgeni Budevski”, Bulgarian
Academy of Sciences, Acad. G. Bonchev str., bl. 10, 1113 Sofia, Bulgaria
D. Tatchev · G. Avdeev
Institute of Physical Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl.11,
1113 Sofia, Bulgaria
G. Zamfirova · V. Gaydarov
Transport University “T. Kableshkov”, Geo Milev str., 158, 1574 Sofia, Bulgaria
V. Lilova
University of Chemical Technology and Metallurgy, 8 Kliment Ohridski Blvd., 1756 Sofia,
Bulgaria

340 V. Ilcheva et al.
33.1 Introduction
Research in sol-gel derived organic/silica hybrids and investigation of the structure-

property-performance relations is a rapidly growing area. The most attractive feature
of organic-inorganic hybrids is the possibility to combine the initial components in a
way, which can provide fine tuning of the properties of the final material (mechan-
ical, optical, etc.) as well as unique design opportunities [1–7]. Subject of intense
study are the so-called ureasilicates, characterized by high optical transparency in the
visible region, a good flexibility and a long term stability of the optical and
mechanical properties.
Basically, the synthesis of a organic-inorganic ureasilicate matrix consists of the
reaction between double functionalized polyetheramines (Jeffamines) with
3-(isocyanatepropyl) triethoxysilane acting as a crosslinker agent [8, 9]. The struc-
ture of these materials can be represented as reticulated siliceous backbone cova-
lently bonded to polyether-based segments by urea (-NHCONH-) linkages. The
hybrid structure consists of hard siliceous nanodomains connected with soft polyoxy
(ethylene)/polyoxy (propylene) (POE/POP) chains. The hard, rigid segments segre-
gate into a glassy domain, and the polyoxyalkylene soft segments form an amor-
phous or rubbery matrix in which the hard segments are dispersed [10]. Addition of
different fillers derived from an in situ hydrolysis and condensation reaction of
different silica alkoxides (TEOS, TMOS, APTES, MTEOS) can reinforce the
relative weakness and influence the surface properties of the materials. It was proven
that organic-inorganic sol-gel derived hybrids can be used as an interface material,
which improves the contact between human skin and electrodes and makes them less
prone to fluctuations due to skin to electrode interfacial impedance [11]. Also, in our
previous work, the possibility for using ureasil-chalcogenide glass composites as a
support for the immpobilization of laccase on the transducer surface of a biosensor
was reported [12]. It was found that the biosensor demonstrates a high sensitivity for
monitoring the level of pollution of xenoestrogen containing wastewater. The
sensitivity of the sensor could also depend on the composition of the ureasilicate
matrix used as host medium for embedding different types of guest materials.
The present work is focused on the preparation of ureasilicate materials with
addition of the silica alkoxide APTES. The influence of the molar ratio between the
components on the optical and mechanical properties is studied. By variation of the
composition we expect to acquire new scientific facts about the correlation between
composition, structure and properties in order to obtain modified materials with
desired parameters for biosensors or optical application.
O,O0 -bis(2-aminopropyl)-polypropylene glycol-block-polyethylene glycol-block-

polypropylene glycol-500 (Jeffamine ED-600, Sigma – Aldrich), 3-(isocyanate
propyl)triethoxysilane (ICPTES, Sigma – Aldrich), 3-(aminopropyl)triethoxysilane
33 Synthesis and Characterization of Organically Modified Silicates 341
Table 33.1 Molar ratios between the reagents used for the preparation of ureasilicate samples
Sample Molar ratio ICPTES/Jeffamine Molar ratio APTES/Jeffamine
A1t 2 1
A2t 2.5 1
A3t 3 1
A4t 3.5 1
A5t 4 1
(APTES, Sigma – Aldrich), ethanol (96%, Alfa Aesar), and ammonia solution (25%,
Alfa Aesar) were used as received. Distilled water was used for the preparation of
diluted aqueous ammonia solutions.
Sol – gel derived ureasilictate monoliths were obtained as follows: ICPTES and
APTES were mixed in an appropriate molar ratio under stirring at 200 rpm for
10 min, so that rapid formation of the first ureasilicate precursor took place (the
molar ratios are summarized in Table 33.1). Thereafter, Jeffamine was added to the
reaction mixture, and stirring was continued for another 20 min. During this period
of time, the reaction between an excess supply of ICPTES and Jeffamine occurred,
resulting in formation of the second precursor. Ethanol (EtOH) was used as a
homogenizing agent and added after that. Subsequent addition of 4.1 M aqueous
ammonia solution led to a catalyzed hydrolysis/condensation reaction under basic
conditions, resulting in the formation of siloxane groups. After 10 min of stirring, the
final mixture was poured into polystyrene cells sealed with Parafilm, which was
pin-holed after gelling. The gelling time varied from 24 to 48 h depending of
composition. Drying of the sample was carried out at room temperature within
2 weeks. It led to a sample shrinkage of about 30%. During the final step the cell
with the obtained gel was kept in an oven for 24 h at 40 C. As a result, monoliths
with polygonal shape with a base of 7 7 mm2 were obtained. Also samples with the
same composition were prepared with a round shape with a diameter ca. 30 mm and
a thickness about 0.5 mm for SAXS measurements.
UV-visible transmission spectra of the samples were measured in the wavelength
range from 350 to 500 nm at room temperature using a double-beam computer-
controlled JASCO spectrophotometer with an accuracy of 0.5 nm. Small-angle
X-ray scattering (SAXS) studies were performed with a Panalytical Empyran XRD
device equipped with SAXS accessory with a slit collimation system. Infrared
(IR) spectra were recorded on a Bruker Tensor 27 FT spectrometer by accumulating
64 scans with 2 cm1 resolution. The spectra were measured in the solid state by
directly applying the sample on a diamond ATR crystal and referencing to an air
background. Depth-sensing indentation method (DSI) was applied for the measure-
ments of the mechanical characteristics of the samples. The measurements were
performed on a Dynamic Ultra Micro Hardness Tester DUH-211S from Shimadzu
(Japan) according to ISO 14577-1. The Martens hardness (HMV) was determined
after reaching the specified maximum test force Fmax, by dividing by the surface area
As of the indenter penetrating beyond the zero-point of the contact. The tests were
made in the “load – hold – unload” mode with a holding time at load of 30 s, a
loading speed of 0.2439 mN/s and a preset controlled indentation depth of 10 μm.
All measurements were performed at room temperature using a Vickers pyramidal
intender. Average microhardness values based on at least ten indentations on every
sample were determined. The calculated percent error is in the frame of 3%, which
indicates relatively good sample homogeneity.
The visual aspect of the round sample is shown in Fig. 33.1. It demonstrates a high
transparency in the visible range and high flexibility of the prepared material.
Sample A1t (ICPTES/Jeffamine ¼ 1/2, APTES/Jeffamine ¼ 1/1) was obtained in
a solid form but exibited some inhomogeneity expressed in the appearance of
viscous liquid droplets on its surface. For this reason, the properties of this sample
are not described in the present study.
The optical transmission spectra are shown in Fig. 33.2. The transmission curves
of the samples with higher ICPTES/Jeffamine ratio (A3t, A4t) exhibit transmittances
about 56% at 400 nm. When the ICPTES/Jeffamine ratio is lower (A2t, A3t), the
transmission curves slightly shift to longer wavelengths, reaching transmittances
about 53% at 400 nm. This change in transmittance could be explained by a native
pale yellow coloration, inherent to polyetheramines and associated with the process
of degradation of oxyethylene/oxypropylene chains, accelerated by the oxidation of
the amino groups. This observation proves the excitation of some unreacted amino
groups in the material, prepared at lower ICPTES/Jeffamine ratios.
Figure 33.3 shows the SAXS curves as measured for four ratios of ICPTES to
Jeffamine. The data for ICPTES/Jeff ¼ 2.5 4.0 were fitted with slit-smeared
Gaussian peak. The correlation distance between the silica nanoparticles was derived
from the fitting parameters, according to the procedure described in [13].
Figure 33.4 shows the correlation distance in the polymer matrix as a function of
ICPTES/Jeffamine molar ratio at constant molar ratio of APTES/Jeffamine ratio.
Distances are calculated from the peak positions, so they are reliable. There is
obvious decreasing trend, which means that the scattering entities are getting closer.
Fig. 33.1 Photograph of

sample A2t with a diameter
ca. 30 mm and a thickness
about 0.5 mm
Fig. 33.2 UV-VIS transmission spectra of the samples with optical path length of about 7 mm
Fig. 33.3 SAXS curves with a constant Jeff/APTES ratio of 1:1 and different ICPTES content
This result suggests the formation of a greater number of the siliceous nanoclusters
with the increase of the ICPTES concentration.
Samples with different ICPTES to Jeffamine molar ratios and an APTES to
Jeffamine ratio equal to 1 were investigated by FTIR spectroscopy. The vibrational
spectra are presented in Fig. 33.5. The region between 1700 and 1500 cm1 is
attributed to the urea (-NHCONH-) linkages, where the peak around 1656 cm1 is
Fig. 33.4 Correlation

distances related to the
microphase separation
between the hard segments
(clusters of siloxane,
chemically bonded by urea
bridges) to the soft segments
(polymer chains)
Fig. 33.5 IR spectra of polymers with a constant APTES/Jeffamine ratio and different ICPTES
amounts
assigned to the C¼O stretching band (amide I region); the peak at 1565 cm1
belongs to a combination of N-H in-plane bending and C-N stretching vibrations
(amide II region). In the higher frequency range the spectra demonstrate vibrational
modes attributed to νa (CH2) and νs (CH3) [9]. The increase in the intensity of the
bands, associated with the amide I and amide II regions proves the higher concen-
tration of urea bonds with increase of the ICPTES/Jeffamine ratio. The existence of
Si-OH groups is supposed, due to vibrations in the low frequency region at 920 cm1
. The presence of a Si-OH band is difficult to confirm because it could be masked by
vibrations attributed to the molten state of oligopoly (oxyethylene) implying a high
level of disorder in the structure. C-C stretching vibrations and CH2 rocking modes,
which are characteristic for the IR spectra of Jeffamine, are identified at 947 cm1
[9]. Si-O-Si stretching vibrations in the polyoxyethylene/poly-oxypropylene
containing hybrid materials are also obscured by the strong band arising from C-O
stretching vibration of polyether groups.
Figure 33.6 demonstrates the changes of the Martens hardness with the increase
of the ICPTES/Jeffamine ratio. A drastical decrease is evident.To explain this
change in mechanical behavior it is necessary to look for the reason at the structural
level. The obtained results from the SAXS measurements indicate that with an
increase of the ICPTES/Jeffamine ratio the distance between the hard segments
(clusters of siloxane) decreases or, in other words, their concentration increases. It
is logical to expect that hardness will grow with the increase of the concentration of
the harder phase but actually a rapidly decrease is observed. Evidently this is a case
where the additive law can not be applied. According this law the hardness of
systems can be determined as the sum of the hardnesses of the components of the
system taking in account their relative fraction. According to the theory reported in
[14], the additive law is not valid when there is a large difference in the hardness of
the phases, because the harder particles only sink in the softer matrix under the
penetrating indenter and do not contribute to the system’s hardness. Thus the
Fig. 33.6 Martens hardness

as function of the ICPTES/
Jeffamine ratio at APTES/
Jeffamine ¼ 1
hardness measured depends only on the resistance of the structure of the softer
phase. In the case of the present system and according to the model presented by
Dahmouche et al. [15] the clusters formed are the harder phase. The softer phase is
represented by the molecular binding segments between the siloxane clusters,
consisting of easily movable polyethylene oxide and polypropylene oxide blocks.
During the penetration, the flexible blocks are subjected to conformation changes,
which signify elastic deformation on the micro-level scale. The greater the distant
between the cluster groups are, the more stretched the molecular binding segments
will be, and therefore they will have a stronger resistance against penetration. This
means a higher value of HMV.
The closer the clusters are, the more corrugated are the binding segments, which
allows them to transit easily to more stretched conformation shapes during the
penetration. This means a lower value of HMV. The indentation curves show that
about 90–95% of the deformation is reversible, which confirms the above discussed
idea that at the supramolecular level mainly conformational transformations take
place.
33.4 Conclusions
Urea silicate materials with different ICPTES/Jeffamine and constant APTES/

Jeffamine ratios were synthesized and characterized optically and mechanically.
The transparency of the samples is affected by the composition and slightly increases
at higher ICPTES/Jeffamine ratios. It has been found that the mechanical properties
are easily controllable by variation of the silicon ethoxide concentration. All inves-
tigated samples demonstrate a high level of elasticity. It has been established that at
higher ICPTES/Jeffamine ratios the material becomes softer. We assume this is
because of the decrease in the distance between the silica cluster groups. The high
flexibility of the hybrid materials could be very useful in practical applications such
as coating on non-planar substrates, host medium for embedding optically active
functionalities and enzymes and for biocompatible thin film manufacturing.
Acknowledgments The authors are grateful for the financial support of this work by the Bulgarian
Ministry of Education and Science (NSF DN09/12).
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Chapter 34
Sr-Substituted Barium Titanate Glass
Ceramics from Oxide Glasses As Potential
Material for Sensor Preparation
Ruzha Harizanova, Liliya Vladislavova, Christian Bocker, Georgi Avdeev,

and Christian Rüssel
Abstract The present work reports on the synthesis of glasses in the system Na2O/
Al2O3/BaO/SrO/TiO2/B2O3/SiO2/Fe2O3 from which, after appropriate thermal treat-
ment, barium titanate and strontium-substituted barium titanate glass-ceramics are
crystallized. The characteristic temperatures of the glasses are determined by differ-
ential scanning calorimetry DSC and show that higher alumina concentrations result
in the stabilization of the glass network while an increasing Sr-concentration at
constant alumina concentrations leads to a decrease of the glass transition temper-
ature. The phase composition of the prepared materials was analysed by X-ray
diffraction and shows precipitations of cubic barium titanate, BaTiO3 and
strontium-substituted barium titanate, Ba1-xSrxTiO3. For isothermal treatments and
longer annealing times, an additional crystalline phase occurs, i.e. fresnoite
(Ba2TiSi2O8). The microstructure investigations of the glass ceramics by scanning
electron microscopy witness the occurrence of globular bright crystals enriched in
the heavier elements, here Ba, Sr and Ti.
Keywords Barium-strontium titanate · Glass-ceramics · Phase separation ·

Crystallization · Sensors
R. Harizanova (*)
L. Vladislavova
Otto Schott Institute, University of Jena, Jena, Germany
C. Bocker
j-fiber GmbH, Jena, Germany
G. Avdeev
C. Rüssel

350 R. Harizanova et al.
34.1 Introduction
The synthesis and investigation of the properties of barium titanate containing oxide
glass-ceramics with additions of 3d-transition metals is motivated by their potential
for application as part of resistive sensors, multilayered capacitors and optoelec-
tronic devices [1–7]. Barium titanate is a promising dielectric material as a substitute
of lead-containing dielectrics [7]. It was discovered in the 1950s of the last century
and is known to possess several allotropic modifications – orthorhombic, rhombo-
hedral, tetragonal, and cubic – as well as a very high melting temperature of about
1600 C [8]. The modification of BaTiO3 which is stable at room temperature
depends on the preparation method and the size of the precipitated BaTiO3 crystals
[3]. Also, the substitution of Ba2+ against different ions, i.e. Sr, Ca or Mg, and that of
Ti4+ by nominally Zr4+ ions is reported [9–12]. Pure SrTiO3 has also a high dielectric
constant and a high refractive index, and possesses good insulating properties and
chemical stability. It has two allotropic modifications, cubic and tetragonal, as the
transition to cubic manifests above 105 K. It has different applications such as phase
shifters, filters, tunable oscillators, tunable microwave electronics, etc. At 1 K it may
exhibit superconductivity when doped. The melting temperature of strontium tita-
nium oxide is 2100 C [13]. This prevents it from a wide use and also makes the
production of devices expensive. However, by using the classical technology of
melting, a glass with high concentration of oxides of the alkaline earth and
3d-transition metals and less than 30% of glass forming oxide, can be obtained
which melts at the significantly lower temperature of 1250 C [5, 14, 15]. Using
appropriate heat treatment schedules further enables to prepare crystals of BaTiO3
and mixed crystals of the type Ba1-xSrxTiO3 from this glass. Depending on the
degree of substitution, such solid solutions could find applications as electroceramics
for piezoelectric transducers, pyroelectric detectors and as part of some electro-
optical devices [9, 10].
Barium titanate-based materials are often prepared by using sintering of carbonate
powders as raw materials, by sol-gel method [7] and subsequently, the electrical
properties of the resulting materials were studied. Another approach to obtain glass
ceramic materials containing BaTiO3 is to crystallize it from oxide glasses [14–
16]. The crystallization of dielectric phases from oxide glasses allows the controlled
precipitation of the desired crystalline phase with tailorable size, a narrow-size-
distribution and a large volume fraction as already observed also in our work for
compositions similar to those reported here [15].
The synthesis of glasses and glass-ceramics derived hereof with advantageous
dielectric properties is studied for the following series of compositions 20.1Na2O/
3Al2O3/(23.1-y)BaO/ySrO/23TiO2/7.6B2O3/17.4SiO2/5.8Fe2O3 with y ¼ 0.5, 1, 2
and 3 mol %. The resulting phase compositions and microstructures are
investigated.
34 Sr-Substituted Barium Titanate Glass Ceramics 351
34.2 Experimental
34.2.1 Preparation of the Glasses
Reagent grade raw materials: Na2CO3, SiO2, Fe2O3, BaCO3, B(OH)3, Al(OH)3 and
TiO2 were used for the preparation of the glasses. The batches (60 g) were homog-
enized and melted in Pt-crucibles using a silicon carbide furnace and a melting
temperature of 1250 С for 1 h in air. Some of the melts were quenched on a
Cu-block and after quenching transferred into a pre-heated graphite mould. The
glasses cast into the graphite mould were transferred to a muffle furnace and kept at

450 С for 10 min. Then, the furnace was switched off and the samples were allowed
to cool to room temperature with a velocity of approximately 2 K/min. All glassy
samples were heat treated at temperatures above Tg for different times.
34.2.2 Characterization Methods
The phase compositions were analyzed by X-ray diffraction (XRD) on powdered

samples, using CuKα-radiation with the 2θ-values in the range from 10 to 60
(Rigaku MiniFlex and Siemens D 5000). The densities of the obtained glasses
were determined by a helium pycnometer (Micromeritics, AccuPyc 1330 V3.00).
The glass transition temperatures were determined by differential scanning calorim-
etry DSC (DSC 822 Mettler Toledo) using a heating rate 10 K/min, powdered
samples with fractions between 100 and 250 μm and Al2O3 as reference material.
The microstructure was investigated by scanning electron microscopy (SEM) using
backscattered electron (BSE) and secondary electron (SE) detectors (JEOL 6510LV
and JSM-7001F). The samples for SEM imaging were cross-fractured, immobilized
in epoxy resin and polished to optical quality. Then they are covered with a thin
carbon layer to avoid charging of the surface during interaction with the
electron beam.
Previous work had been carried out in the system (23.1-z)Na2O/zAl2O3/23.1BaO/

23TiO2/7.6B2O3/17.4SiO2/5.8Fe2O3 for z ¼ 0, 3, 7 and 11 mol% [14], where the
ratio of Na2O to Al2O3 was varied in order to trace its influence on the glass
formation ability in the system mentioned. This revealed best glass forming abilities
for the compositions with 3 and 7 mol% Al2O3. However, additionally to the glass-
forming ability in the system studied, also the possibility to precipitate, during
appropriate thermal treatment, barium titanate as sole crystalline phase with a large
volume fraction and crystallite size, leading to a high dielectric constant of the
Table 34.1 Glass transition № SrO [mol%] Tg [ C] Tc [ C]

(Tg) and crystallization
1 0 – parent glass 450 550
temperature (Tc) of the parent
glass and the Sr-substituted 2 0.5 433 567
glasses 3 1 439 574
4 2 435 574
5 3 435 570, 580
prepared glass-ceramics, is important for potential applications. The investigation of

the phase composition and the microstructure of the glass-ceramics with 3 and 7 mol
% alumina showed that the compositions with 7 mol% have a very fine
interpenetrating crystalline structure corresponding to barium titanate. However, in
this composition also nepheline (NaAlSiO4) occurs as a secondary crystalline phase
[15] which is not desired. Further thermal treatment of the as chosen composition
with 3 mol% alumina by applying different time-temperature schedules resulted in
the formation of barium titanate as the only crystalline phase for a broad temperature
and time interval range. Only after increasing the annealing temperature above
600 C and the annealing time above 3 h, the occurrence of an additional crystalline
phase (fresnoite, Ba2TiSi2O8) was observed [14]. The micro-computed tomography
investigation of the glass-ceramic samples showed that the barium titanate phase is
crystallized in a large volume fraction of 58 1% [15] which is important for
potential practical applications. Also, by SEM imaging and according to the prelim-
inary information gathered about the studied system [17], the system of choice is
prone to phase separation which results in the formation of droplet-like structures
enriched in Ba and Ti where later BaTiO3 is precipitated [14, 15]. Thus, the
composition with 3 mol% Al2O3 was chosen and further modified by substituting
BaO with SrO, in order to see which influence this substitution will have on the
phase composition, microstructure and eventually practical applications. The series
of compositions 20.1Na2O/3Al2O3/(23.1-y)BaO/ySrO/23TiO2/7.6B2O3/17.4SiO2/
5.8Fe2O3 with y ¼ 0.5; 1; 2 and 3 mol % is melted as described above. The
quenching of the melts for all SrO concentrations results in amorphous products,
only for the sample with 3 mol% SrO a slight crystallization on the surface is
observed. To achieve higher mechanical stability and to release the mechanical
stresses in the glasses they were transferred to a graphite mould and annealed around
the glass-transition temperature. The Tg and Tc values determined by DSC are given
in Table 34.1 and show that the Sr-substituted glass compositions have lower
Tg values than the parent glass without strontium oxide. Actually, a slight increase
of Tg of the Sr-containing glasses occurs up to 1 mol% SrO, then Tg decreases and
remains constant up to 3 mol % SrO. The crystallization temperatures as peak
maximum positions are also very similar though higher than that of the parent
glass. For the composition with 3 mol% SrO, a second crystallization peak can
clearly be resolved at about 580 C.
Fig. 34.1 Densities of the Sr-substituted glasses as function of the SrO concentration
The densities of the obtained glasses were determined pycnometrically; as seen in

Fig. 34.1, they do not significantly vary compared to the density of the parent glass
with 0 mol% SrO up to 2 mol% SrO. However, for 3 mol% SrO, a decrease of the
density of the respective Sr-substituted glass is observed. This could be attributed to
the fact that the strontium concentration is initially too small to lead to some
significant structural changes in the glass, but for 3 mol% already the presence of
Sr would lead to structural changes in the glass network due to the smaller ionic
radius of Sr2+ (0.118 nm) compared to that of Ba2+ (0.135 nm).
The stabilized glasses obtained were subjected to thermal treatments at different
temperatures near the crystallization peak maximum (from the DSC-thermograms)
for different time intervals. The result, as shown for different Sr-concentrations in
Figs. 34.2, 34.3, 34.4, and 34.5 is the crystallization of a solid solution of the type
Ba1-xSrxTiO3 with the peaks slightly shifting with increasing concentration of SrO to
higher 2θ values. Actually, the X-ray diffraction patterns show that for the glass-
ceramics with 0.5 mol% SrO, the composition of the mixed crystals formed is
Ba0.592Sr0.408TiO3 (JCPDS 96-152-2091), while for higher concentrations of stron-
tium, the formed solid solutions possess the composition Ba0.5Sr0.5TiO3 (JCPDS
96-151-2124). Longer annealing times result in a slight shift of the crystallization
peak maxima to Ba-richer solid solutions for the 3 mol% SrO glass-ceramics, as can
be seen in Fig. 34.5. Also, longer annealing times as well higher annealing
temperatures lead to the precipitation of a second phase – fresnoite, Ba2TiSi2O8
(JCPDS 96-100-7235) – which might lead to a Ba deficiency in the growing barium-
strontium titanate crystals. The increase of annealing time or temperature also results
Fig. 34.2 XRD patterns of samples with 0.5, 1, 2 and 3 mol% SrO annealed at 550 C for different
times: crystallization of Ba1-xSrxTiO3
Fig. 34.3 XRD pattern of a sample with 2 mol% SrO annealed at 550 C for different time intervals
– crystallization of Ba0.5Sr0.5TiO3 (BS) and fresnoite Ba2TiSi2O8 (F)
Fig. 34.4 XRD pattern of a sample with 2 mol% SrO annealed at 580 C for different times –
crystallization of Ba0.5Sr0.5TiO3 and fresnoite even for shorter annealing times
in crystal growth, and the volume fraction of the formed crystals increases as
witnessed by the narrower and more intense peaks of the X-ray diffraction patterns.
Some authors working with similar systems report the precipitation of Fe3O4 and
BaTiO3 in the glass and the occurrence of core-shell structures [5]. We do not have
evidence from our analyses in the present set of compositions that Fe is incorporated
in the crystalline phases as detected by X-ray diffraction. The results from the
qualitative X-ray analyses are confirmed by microstructural characterization by
means of scanning electron microscopy. In Fig. 34.6, the typical microstructure for
all annealed samples is shown, droplet-like bright crystals which are formed in the
phase separated glass after applying the respective annealing programs. It is assumed
[14, 15, 17] that in the glass, two phases are formed, one enriched in Ba, Ti and Sr
where later the Ba1-xSrxTiO3 solid solution or/and pure BaTiO3 will crystallize, and
a second phase, which contains all other constituents of the glass composition. After
annealing above Tg, in the droplet-like regions, BaTiO3 [14, 15] or in the present
case, Ba1-xSrxTiO3 crystallizes. The isothermal annealing for longer times will lead
to aggregation of the liquid droplets into larger formations, as shown in Figs. 34.7,
34.8, and 34.9. The volume fraction of the crystalline phase, as seen from the SEM
micrographs will also increase for longer annealing times. However, due to very
close average atomic numbers and thus similar contrasts, the standard SEM analysis
could not really differentiate between the formed barium-strontium titanate and the
second precipitated phase fresnoite.
Fig. 34.5 XRD pattern of a sample with 3 mol% SrO annealed at 550 C for different time intervals
– crystallization of Ba1-xSrxTiO3 and fresnoite and shift of the peaks to smaller 2θ values with
increasing annealing time
Fig. 34.6 Uniform

crystallization of a sample
with 0.5 mol % SrO
annealed for 3 h at 550 C
Fig. 34.7 Sample with

0.5 mol% SrO (24 h/
550 C): crystal growth for
longer annealing times

3 mol% SrO annealed for
30 min at 550 C: growth of
droplet-like structures

3 mol% SrO annealed for
100 h at 550 C: further
growth of the formed
particles
34.4 Conclusions
Glasses in the system Na2O/BaO/SrO/TiO2/B2O3/SiO2/Al2O3/Fe2O3 with up to

3 mol % SrO substitution of BaO were synthesized. The glass transition temperature
and the density of the respective glasses decrease with increasing strontium concen-
tration. Annealing of the glasses always results in the crystallization of a solid
solution of the type Ba1-xSrxTiO3 as the first phase. Higher concentrations of SrO
in the glass lead to a shift of the solid solution compositions to the Sr-richer ones. For
longer crystallization times also as second crystalline phase fresnoite crystallizes. In
all annealed glasses, the microstructure initially consists of droplet-like structures
which with increasing annealing time grow together. The addition of Fe to the
composition stabilizes the glasses mechanically and chemically but does not lead
to the precipitation of Fe-containing crystalline phases.
Acknowledgments This work is financially supported by contract NIS 11 663, Scientific sector of
UCTM, Bulgaria and contract DN08/13, Bulgarian National Scientific Fund.
References
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polar liquids. J Mater Sci 46:5385–5393
3. Capsal JF et al (2010) Nanotexture influence of BaTiO3 particles on piezoelectric behaviour of
PA 11/BaTiO3 nanocomposites. J Non-Cryst Solids 356:629–634
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tetragonal barium titanate nanowires: a structural investigation. J Phys Chem B 110:12249
5. Maiti RP, Basu S, Bhattacharya S (2009) Multiferroic behavior in silicate glass nanocomposite
having a core–shell microstructure. J Non-Cryst Solids 355:2254–2259
6. Du G (2010) P et al, Effects of niobium donor doping on the phase structures and magnetic
properties of Fe doped BaTiO3 ceramics. J Alloys Compd 492:L79–L81
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II. Sci Sinter 40:235–244
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(2008) Crystal structure and the paraelectric-to-ferroelectric phase transition of nanoscale
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9. Ridha NJ, Mahmood W, Yunus M, Halim SA, Talib ZA (2009) Effect of Sr substitution on
structure and thermal diffusivity of Ba1-xSrxTiO3 ceramic. Am J Eng Appl Sci 2(4):661–664
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behavior in Sr1-xBaxTiO3. Phys Rev 54(5):3151–3157. 0163-1829/96/54
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(2015) Crystallization behaviour of the systems Na2O/BaO/TiO2/SiO2/B2O3/Al2O3 and Na2O/
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Chapter 35
BaO/SrO/ZnO/SiO2 Glass System:
Influence of Different Nucleation Agents:
Bulk Versus Surface Crystallisation
Liliya Vladislavova, Christian Thieme, Tilman Zscheckel, Christian Patzig,

Thomas Höche, and Christian Rüssel
Abstract In the present study, detailed investigations on the crystallisation behav-

iour for the recently discovered Ba1-xSrxZn2Si2O7 phase were performed. This solid
solution may possess zero to negative thermal expansion. In contrast to many other
phases with negative thermal expansion, this phase can be crystallised from glasses
and hence should be suitable for the preparation of cooking panels, telescope
mirrors, and other mass production materials, where the thermal expansion proper-
ties have to be tailored exactly. Due to the high anisotropy of the phase, inducing
volume crystallisation and reducing the crystal size is of main interest. The influence
of ZrO2 and Pt as nucleating agents in the glass system BaO/SrO/ZnO/SiO2 was
studied by calculating the Avrami parameter (n). The microstructure was investi-
gated with scanning electron microscopy.
Keywords Nucleation · Glass-ceramics · Platinum-ZrO2 · Activation energy ·

Avrami parameter
35.1 Introduction
The Ba1-xSrxZn2Si2O7 phase is a new and challenging solid solution which has a
similar structure as the high-temperature (HT) modification of BaZn2Si2O7. The new
solid solution possesses negative or close to zero thermal coefficients which make it
suitable for fabrication of materials such as cooking panels, telescope mirrors and
L. Vladislavova (*) · T. Zscheckel · C. Rüssel

Otto Schott Institute, Chair of Glass Chemistry I, Jena University, Jena, Germany
C. Thieme
Otto Schott Institute, Chair of Glass Chemistry I, Jena University, Jena, Germany
Fraunhofer Institute for Microstructure of Materials and Systems IMWS, Halle, Germany
C. Patzig · T. Höche
Fraunhofer Institute for Microstructure of Materials and Systems IMWS, Halle, Germany

362 L. Vladislavova et al.
others [1, 2]. Using single-crystal X-ray diffraction (XRD), the thermal expansion
was determined as a function of temperature and crystallographic directions, com-
bined with a Rietveld refinement [3]. The thermal expansion varies significantly in
the different crystallographic directions which causes a high anisotropy in the system
and may lead to crack formation in the obtained materials. Reducing the crystal size
and provoking volume crystallisation is one of the most commonly applied methods
to overcome crack formation [1]. Both ZrO2 and Pt are well-known nucleation
agents used in the past e.g. for the Li2O2SiO2 system [1, 4]. This paper describes
the effect of Pt and ZrO2 as nucleating agents in glasses from the system BaO/SrO/
ZnO/SiO2/ZrO2.
35.2 Experimental
35.2.1 Preparation of the Glasses
The glass batch was prepared from the following chemically pure raw materials:
BaCO3, SrCO3, ZnO, SiO2, ZrO2, and PtCl4. For the platinum containing glass,
0.01 mol% PtCl4 was dissolved in acetone and then given to the glass batch,
thoroughly mixed for 2 h and subsequently dried. The batch (for 400 g glass) was
melted at 1300–1350 C for 1 h in a platinum crucible using an induction furnace.
Then, the temperature was increased to 1450 C for 2 h. During this time, the melt
was stirred with 60 min1. Then, the stirrer was removed and the glass was soaked
for 10–15 min. The glass was cast in a preheated steel mould and transferred to a
muffle furnace preheated to 700 C. The furnace was switched off allowing the
sample to cool to room temperature. The base chemical compositions of the glasses
is 8BaO/8SrO/34ZnO/44SiO2/6ZrO2.
35.2.2 Characterization Methods
Differential Scanning Calorimetry (DSC) was carried out using a Linseis DSC Pt
1600. Characteristic temperatures such as the glass transition temperature (Tg), the
onset of the crystallisation peak (Ton), the offset of the crystallisation peak (Toff) and
the crystallisation maximum (Tp) were determined. Bulk samples were used in order
to minimise the effect of surface crystallisation; samples with a mass of 0.15 g were
remelted in a DSC platinum crucible at 1450 C and then quenched in air. The
measurements were performed up to a temperature of 1200 C, using heating rates of
2, 5, 10, 15 and 20 K/min.
Scanning Electron Microscopy was carried out using an (SEM) JEOL 7001
F. The samples were mounted using Ag paste; a carbon coating was applied at
about 105 Pa in order to avoid surface charging.
35 BaO/SrO/ZnO/SiO2 Glass System 363
Fig. 35.1 DSC profiles: glasses with 6 mol% ZrO2 with and without platinum, using a heating rate
of 10 K/min
The produced glasses appear to be without bubbles, crystals, and striae. The sample
which contained only ZrO2 is transparent. However, adding platinum to the system
led to the formation of small platinum particles with a mean size of 1 μm in the non–
thermally treated glass which causes a greyish colouration [5].
Figure 35.1 shows the DSC profiles of the glasses prepared with (Z6Pt) and
without (Z6) addition of platinum recorded with a heating rate of 10 K/min. The
platinum addition does not affect Tg which for both systems is equal to 697 C. The
onset and peak temperatures of the Pt-containing and the Pt-free glass vary
significantly. The Pt-containing glass has an onset at 894 and a peak temperature
at 908 C, whereas the Pt-free glass shows these characteristics at 943 and 985 C,
respectively. Also, a significant change in the shape of the crystallisation peaks can
also be seen. The platinum-containing glass has a sharp and narrow peak whose
intensity is much higher compared to that of the ZrO2 containing glass, where the
intensity is significantly lower and the peak is broader. As already reported in the
literature, this is a significant indication for a change in the crystallisation mech-
anism [5–7].
Figure 35.2 presents Ozawa plots for the determination of the Avrami parameter
for the studied glasses. The plots are obtained according to Eq. (35.1) where (ln(-ln
(1-x))) is plotted versus ln (β) and the parameter value is determined from the slope
using a linear regression [8, 9]. To obtain statistically significant data, the measure-
ments were performed using five different heating rates.
Fig. 35.2 Ozawa plot of

(ln-(ln(1-x))) versus ln (β)
used to calculate the Avrami
parameter for Z6: 955 C
and Z6Pt: 874 C
Fig. 35.3 Avrami

parameter versus
temperature for Z6Pt

d½ln ð ln ð1 xÞÞ
n ¼
ð35:1Þ
dðln βÞ T
In this equation, n is the Avrami parameter and x ¼ At/A where A is the total area
under the exothermic peak, At is the area under the exothermic peak up to a chosen
temperature, and β is the heating rate.
The calculated Avrami parameter for the glass with 6 mol% ZrO2(Z6) for 955 C
is approximately equal to 2 which is an indication of a mix between surface and
volume crystallisation [8]. The glass composition with platinum (Z6Pt) has an
Avrami parameter equal to 4 at 874 C. This is an indication of 3D bulk
crystallisation [8, 9]. As can be seen from Fig. 35.3, the Avrami parameter versus
the temperature can vary slightly depending on the chosen temperature. In order to
35 BaO/SrO/ZnO/SiO2 Glass System 365
Fig. 35.4 SEM-

micrographs of different
samples: (a) Z6Pt thermally
treated in the first step at
720 C for 48 h and then at
780 C for 5 h; (b) Z6
thermally treated in a first
step at 720 C for 48 h and
then at 840 C for 1 h
obtain more accurate Avrami parameters, the following should be taken into
account: The heating rates should be chosen in a way that the area under the peak
is the range from 0.2 0.8. As seen from Fig. 35.3, the Avrami parameter for
the platinum containing glass varied between 4.42 and 3.85 which is close to
4. Despite the fact that the Ozawa method is quite accurate in the prediction for
the crystallisation mechanism regarding the Ba1-xSrxZn2Si2O7 phase, additional
microstructural studies are necessary for a complete overview of the crystallisation
processes.
Figure 35.4 shows SEM micrographs of the studied glass ceramics. Figure 35.4a
presents the platinum containing sample nucleated at 720 C for 48 h and then
thermally treated at 780 C for 5 h. A significant amount of volume crystals is
observed in the micrographs. From statistical analyses made on the samples, the
mean particle size of the volume crystals was determined to be around 11 μm. The
bright spheres in the middle of the crystals are platinum particles with a mean size of
1 μm which are formed during cooling of the glass [5]. All volume crystals should
have a platinum particle in their centres which, however, in many cases are not
visible in the SEM micrographs, due to the different cut planes and the limited
information depth of SEM. This is a good example of a heterogeneous nucleation
where the metal particles act as a precursor of the crystal phase. Figure 35.4b shows
the ZrO2 containing sample nucleated at 720 C for 48 h and then thermally treated
at 840 C for 1 h. In this case, the mean size of the volume crystals is 180 μm and the
number of the crystals is significantly reduced. Also, crack formation is visible from
the centre of the crystal which in combination with the surface crystallisation leads to
a brittle material [7]. From this observation it can be concluded that ZrO2 alone is not
a sufficient nucleation agent.
35.4 Conclusions
Using DSC and applying the Ozawa method in order to determine the Avrami
parameters proved to be suitable to predict the crystallisation behaviour and also
the microstructure. The addition of 6 mol% ZrO2 induces predominantly surface and
besides, a small amount of volume crystallisation. The mean crystallite size is
180 μm which is too large for overcoming the crack formation in the samples.
Adding small quantities of Pt significantly increases the volume crystallisation and
reduces the mean crystallite size to 11 μm. Nevertheless, some cracks still occur
inside the samples, but they are localised and do not lead to a destruction of the
material.
References
1. McMillan PW (1979) Glass-ceramics, 2nd edn. Academic, London

2. Bach H, Krause D (2005) Low thermal expansion glass ceramics, 2nd edn. Springer, New York
3. Thieme C, Görls H, Rüssel C (2015) Ba1xSrxZn2Si2O7-A new family of materials with negative
and very high thermal expansion. Sci Rep 5:18040
4. Rindone G (1962) Further studies of the crystallization of a lithium silicate glass. J Amer Ceram
Soc 45:7–12
5. Vladislavova L, Thieme C, Zscheckel T, Patzig C, Höche T, Rüssel C (2017) Heterogeneous
nucleation of Ba1-xSrxZn2Si2O7 from a BaO/SrO/ZnO/SiO2 glass using platinum as nucleation
agent. J Eur Ceram Soc 37:4801–4808
6. Massera J, Fagerlund S, Hupa L, Hupa M (2012) Crystallization mechanism of the bioactive
glasses, 45S5 and S53P4. J Am Ceram Soc 95:607–613
7. Vladislavova L, Thieme C, Rüssel C (2017) The effect of ZrO2 on the crystallization of a glass in
the system BaO/SrO/ZnO/SiO2: surface versus bulk crystallization. J Mater Sci 52:4052–4060
8. Guedes M, Ferro AC, Ferreira JMF (2001) Nucleation and crystal growth in commercial LAS
compositions. J Eur Ceram Soc 21:1187–1194
9. Donald IW (2004) Crystallization kinetics of a lithium zinc silicate glass studied by DTA and
DSC. J Non-Cryst Solids 345:120–126
Chapter 36
Bismuth-Titanate Bi2Ti2O7 Crystallization
in the Bi2O3/TiO2/SiO2/Nd2O3 System
Stanislav Slavov and Zheng Jiao
Abstract Electronic devices for high frequency applications become more and
more useful in recent years. The general aim of this study is to demonstrate a way
to synthesize compositions from the system Bi2O3/TiO2/SiO2/Nd2O3 in which only
one crystalline phase is present: bismuth-titanate pyrochlore (Bi2Ti2O7). Synthesis
was performed in two successive steps: a starting oxide homogenization in 15 min
and melting at temperatures of 1100 C and 1450 C, respectively. The free cooling
was carried out to room temperature with about 100 K/min. The phase composition
of selected samples was determined by X-ray diffraction (XRD) analysis. The
microstructure was observed by scanning electron microscopy (SEM). Infrared
spectroscopy (FTIR) was applied in order to identify the structure and microcrystals
distribution in the matrix. Thorough control of the initial amounts of the starting
composition leads to obtain monophase polycrystalline glass-ceramics and ceramics
containing the phase Bi2Ti2O7.
Keywords Pyrochlore oxides · Bismuth-titanates · Glass-crystalline materials
36.1 Introduction
Ferroelectric materials are the subject of a vast number of studies published in

recent years. The Aurivillius phase is the most popular of bismuth titanate [1–3],
but it is well-known that pyrochlore titanate with the chemical formula A2Ti2O7
(A¼La, Nd, Ca) are very promising for high frequency (microwave) applications
[4–6]. In one excellent work Hector and Wigin [7] discuss the synthesis of a
stoichiometric cubic structure of pyrochlore by low-temperature methods such as
S. Slavov (*)
Z. Jiao
School of Environmental and Chemical Engineering, Shanghai University, Shanghai, People’s
Republic of China

368 S. Slavov and Z. Jiao
sol-gel or CVD with the idea of obtaining low cost electro-ceramics. Based on the
above-mentioned scientific results, the present work is motivated by the practical
necessity of: (1) synthesis of a monophase perovskite material (pyrochlore
Bi2Ti2O7); (2) use of a method which avoids high cost of precursors (as sol-gel)
or costly equipment (as CVD), and (3) the production of material (ceramics and
glass-ceramics) with an oriented microstructure. The most popular synthesis
methods for ceramics are sol-gel, CVD, solid-state reaction, co-preparation, mol-
ten salt synthesis, and mechanochemical synthesis. In the present work we use
melting, free cooling to room temperature and a combination of different pre-
cursors in order to control precisely the phase formation. Additionally, adding a
glass phase between crystalline materials is due tothe production of new materials
with fine-granded, pore-free and nano-structured materials [8]. Typically, in some
high frequency applications, bulk materials are used, so their dielectric properties
are strongly influenced by phase composition, grain size, the glass phase content,
and grain boundary effects [9]. This work shows one possibility to control the
phase formation and texturing ability in ceramic and glass ceramic materials from
the system Bi2O3-TiO2-SiO2-Nd2O3. Their synthesis from well-known readily
available and inexpensive starting materials, and the used equipment is available
in any electro-ceramics laboratory.
36.2 Experimental
For bulk materials synthesis in the system Bi2O3-TiO2-SiO2-Nd2O3 two successive

procedures were used: starting oxide homogenization in 15 min and melting at
temperatures of 1450 C and 1100 C, in dependence of the batch composition.
Melting was done in a SiC tube furnace KTM-GSL1700X using alumina crucibles;
the melts were freely cooled to room temperature in graphite crucibles (Table 36.1)
with a rate around 100 K/min.
By the X-ray diffraction the phase composition was determined using a XRD
Ridacu D/MAX2500V, using CuKa radiation (a ¼ 1.5406 Å); by scanning electron
microscopy the microstructure was observed using a SEM Hitachi SU1510. The
infrared spectra of selected samples was examined with a FTIR Thermo Nikolet –
Avatar 370 FT-IR.
Table 36.1 Starting, phase composition and melting conditions of selected samples in the system
Bi2O3-TiO2-SiO2-Nd2O3. The composition is given in mol%
No Name Bi2O3 TiO2 SiO2 Nd2O3 tm [ C] t [min] Phases according to XRD
1 A 19 66 8 7 1450 20 Bi2Ti2O7
2 B 23 66 4 7 1450 20 Bi2Ti2O7
3 C 45 0 50 5 1100 15 Glass + Bi2Ti2O7
36 Bismuth-Titanate Bi2Ti2O7 Crystallization 369

samples a, b and c
According to the X-ray patterns the samples haves the same mono-phase composi-
tion, i.e. Bi2Ti2O7 (Fig. 36.1). There are no different phases, but in sample C an
amorphous halo is hinting at a possible amorphous structure. The SEM image in
Fig. 36.2c shows that an amorphous glass structure is observed with addition of a
small amount of crystals, in contrast to the other two examined samples A and B
having a dense crystalline microstructure (Fig. 36.2a, b). In these samples well-
defined boundaries between crystalline structures are formed. For sample B the cubic
pyrochlore microstructure (according the XRD data) is ordered on a separated layer,
while the structure in sample A is randomlike.
More details of the structure can be discovered by infrared spectra (FTIR from
400 to 1400 cm1). The spectra of selected samples (Fig. 36.3) include the vibra-
tional frequencies of the phases detected by X-ray and also of the units of the
amorphous network between them.
In a number of studies Kojima et al. [9–13] defscribed a series of bismuth layered
compounds with bands about 820 cm1, 537 cm1 at 615 cm1 which we observed
Fig. 36.2 SEM observations of samples: a, b and c
in all the three studied samples (Fig. 36.3). In parallel the band around 830 cm1 can
be associated with the symmetric vibrations, that around 600 cm1 to asymmetric
and deformation vibrations of the Ti-O linkages in TiO6 octahedrona [14], typical for
the same type of compounds. In sample A the bands near 832 and 1112 can,
according to Roy [15] be assigned to an appearing of antisymmetric stretching
vibrations of the Si-O-Si networks and also of deformed SiO4 polyhedral units
(broken Si-O-Si – linkages with a band around 906 cm1); in contrast the vibration
of Si-O-Al can be found for sample B. The reduction of the Si-O-Si bands in sample
B compared to sample A may be due, on the one hand, to the reduction of the SiO2
content in the starting composition and, on the other hand, to the reaction of the Si-O
groups with Al of the crucible. For all three compositions, the band at 480 cm1 is
associated to TiO6 and BiO6; both are typical of the cubic pyrochlore blocks.
Increasing the amount of SiO2 to 50 mol% in the starting composition without any
quantity of TiO2 in sample C initiates the formation of a multi-component amor-
phous matrix containing BiO6 (480 cm1), Bi-O-Bi linkages (463 cm1, 448 cm1)
as well as depolymerized SiO4 groups (811 cm1, 892 cm1) which is confirmed in
the works of Todea and Simon [16]. In our previous work [17] we have prepared
glass with elements of crystalline phases with a controlled TiO2 content by super-
cooled melts. In the glass-ceramic sample C (with the participation of a crystaline
pyrochlore Bi2Ti2O7 phase) the nontraditional glass formers with absence or mini-
mal content of expected Si-O-Si-linkages (1034 cm1, 1098 cm1) forms solid
36 Bismuth-Titanate Bi2Ti2O7 Crystallization 371
Fig. 36.3 IR spectra of samples a, b and c
solutions (as is described in a few works [18, 19]) of polyhedral BiO6 and tetragonal
polymerized SiO4 groups. The samples thus described are a good start for future
dielectric studies and future applications due to the combination of the mono-
crystalline phase – the bismuth-titanate pyrochlore with different compositions –
and a quantity amorphous phases.
36.4 Conclusions
As a result from this work, the following conclusions can be drawn:

1. We were managed to synthesized pure Bi2Ti2O7 phases in the investigated
system Bi2O3-TiO2-SiO2-Nd2O3 using free cooling from the melt;
2. Bonding of cubic pyrochlore blocks structures in line-stacked layers of the phase
Bi2Ti2O7 was obtained;
3. A glass-crystalline sample was obtained with the participation of a Bi2Ti2O7

phase and non-traditional glass former such as Bi2O3 and polymerized SiO4
octahedrals.
Acknowledgments This work was financially supported by Swap and Transfer, Erasmus Mundus
Action 2 Mobility Lot 12, Grant ID number SAT-2542.
References
1. Pineda-Flores JL, Chavira E, Reyes-Gasga J, Gonzalezc AM, A. (2003) Huanosta-Tera,

synthesis and dielectric characteristics of the layered structure Bi4-xRxTi3O12 (Rx¼Pr, Nd,
Gd, Dy). J Eu Ceram Soc 23:839–850
2. Buhay H, Sinharoy S, Kasner WH, Francombe MH, Lampe DR, Stepke E (1991) Pulsed laser
deposition and ferroelectric characterization of bismuth titanate films. Appl Phys Lett 58:1470
3. Huanosta A, Alvarez-Fregoso O, Amano Mexico E, Tabares Munoz C, Mendoza-Alvarez ME,
Mendoza-Alvarez JGME (1991) AC impedance analysis of crystalline layered and polycrys-
talline bisnuth titanate. J Appl Phys 69:404
4. Yamamoto JK, Bhalla AS (1991) Microwave dielectric properties of layered perovskite
A2B2O7 single-crystal fibers. J Matt Lett 10(11, 12):497–500
5. Lee CK, Kim WS, Park H-H (2004) Structural and electrical properties of Nd2Ti2O7/Y2O3/Si
structures through interface treatment. Thin Solid Films 155–159. https://doi.org/10.1016/j.tsf.
2004.06.020
6. Bian JJ, Song GX, Yan K (2008) Structure and microwave dielectric properties of Nd(2-x)/
3LixTiO3. Ceram Int 34:893–896. https://doi.org/10.1016/j.ceramint.2007.09.054
7. Hector AL, Wiggin SB (2004) Synthesis and structural study of stoichiometric Bi2Ti2O7
pyrochlore. J Solid State Chem 177:139–145. https://doi.org/10.1016/S0022-4596(03)00378-5
8. Murugan GS, Subbanna GN, Varma KBR (1999) Nanocrystallization of ferroelectrics bismuth
unstated in lithium borate glass matrix. Mater Sci Lett 18:1687–1690
9. Kojima S, Hushur A, Jiang F, Hamazaki S, Takashige M, Jiang M, Shimada S (2001)
Crystallization of amorphous bismuth titanate. J Non-Cryst Sol 293–295:250
10. Kojima S, Shimada S (1996) Soft mode spectroscopy of bismuth titanate single crystals.
Physica B 219–220:617
11. Kojima S, Tsumura N, Takeda M, Nishiava S (2003) Far-infrared phonon-polariton dispersion
probed by terahertz time-domain spectroscopy. Phys Rev B 67:035–102
12. Kojima S, Imaizumi R, Hamazaki S, Takashige M (1995) Raman study of ferroelectric bismuth
layer-oxides ABi4Ti4O15. J Mol Struct 37:348
13. Kojima S, Imaizumi R, Hamazaki S, Takashige M (1994) Raman scattering study of bismuth
layer-structure ferroelectric. Jpn J Appl Phys 33:5559
14. Du Y, Zhang M, Chen Q, Yin Z (2003) Investigation of size-driven phase transition in bismuth
titanate nanocrystals by Raman spectroscopy. Appl Phys A Mater Sci Process 76:1099
15. Roy J, Bandyopadhyay N, Das S, Maitra S (2011) Studies on the formation of mullite from
diphasic Al2O3-SiO2 gel by fourier transform infrared spectroscopy. Iran J Chem Chem Eng 30:1
16. Todea M, Simon S (2007) Vibrational spectroscopic study on iron doped silica-bismuthate
glasses and glass ceramics. J Optoelectron Adv Mater 9(3):621
17. Slavov S, Dimitriev Y (2016) Glass formation in the system Bi2O3-TiO2-SiO2. J Chem Technol
Metall 51(5):536–546
18. Stanek CR, Minekviki Z, Grimes RW (2002) Nonstoihiometry in A2B2O7 pyrochlores. J Am
Ceram Soc 85(11):792–798
19. Minekvini Z, Grimes RW (2008) Disorder in pyrochlore oxides. J Am Ceram Soc 83
(8):1873–1878
Part IX
Applications: Sensors and Detectors
Chapter 37
Application of Sm Oxide Doped Oxyfluoride
Glasses for the Development of Extrinsic
Fibre Optical X-Ray Sensors
T. Eftimov, D. Tonchev, I. Kostova, G. Patronov, and T. Pashova
Abstract The fabrication and optical properties of Sm oxide doped oxyfluoride

glasses and their spectral response to X-ray radiation are presented. We report on the
observation of a spectrally dependent, radiation induced attenuation of the radio and
photo luminescence spectra which follow a power law with different fitting param-
eters. The spectral maxima in the visible attenuate differently during irradiation
which permits the development of extrinsic sensors in which scintillation responses
and fluorescence from laser excitation are observed separately using time
multiplexing. Due to substantially different time scaling parameters lower doses
can be measured using fluorescence while larger doses can be measured using the
spectrally differentiated scintillation responses.
Keywords Sm oxide · Oxyfluoride glasses · Optical fibre · X-ray sensors
37.1 Introduction
Optical fiber radiation sensing technology has developed significantly in the last two
decades, and a variety of sensing principles and fibre-based radiation sensors have
been proposed [1, 2]. The application areas are absorbed dose measurement in
radiotherapy, spatial dose distribution in linear accelerators, radiation dosimetry in
computed tomography, remote monitoring of radioactive contamination and
radioactive waste, radiation protection and monitoring of nuclear installations,
T. Eftimov (*)
Université du Québec en Outaouais, 101 St. Jean Bosco St., Gatineau, QC J8X 3X7, Canada
D. Tonchev
University of Saskatchewan, Saskatoon, SK, Canada
I. Kostova · G. Patronov · T. Pashova

376 T. Eftimov et al.
neutron or mixed gamma-ray neutron dosimetry, sterilization of medical instrumen-

tation, measurement of gamma radiation in food industry, etc. [1, 2].
The advantages of using of both silica and plastic optical fibers in sensing
technology has been widely recognized; optical fibers in radiation sensing have
been used both as sensing elements and/or light-guiding medium to a radiation
sensing element. In the former case we have intrinsic, in the latter extrinsic fiber
optic sensors (see Table 37.1). In both of them sensing is based on radiation induced
effects in materials based on the interaction of highly energetic radiation and matter,
either fibers or other materials. Highly energetic radiation includes: (i) uncharged
particles such as UV photons, gamma- and X-rays; (ii) charged particles (electrons,
positrons, ions) and (iii) constituents of the nucleus (neutrons, protons).
Intrinsic fiber optic sensors are based on changes in the transmission (losses) or
on light emission from fibers [3–9]. The effects are: (i) radiation induced attenuation
(RIA) which depends on the fiber dopants, glass type, thermal stresses, fabrication
technology, type of radiation and irradiation conditions, etc.; (ii) Cerenkov radiation
in the UV caused by charged particles travelling at a velocity greater than the phase
velocity in the medium; (iii) radiation induced luminescence (RIL) in the visible
superimposed on the Cerenkov radiation [1]; and (iv) refractive index changes under
ionizing radiation [1], which also affects the fiber Bragg grating (FBG) spectrum
[5]. Specially doped fibers can be made to exhibit increased transmission spectrally
dependent losses (color changes) [5], or to scintillate by embedding a Gd2O2S:Tb
phosphor in PMMA (polymethyl methacrylate) plastic fibres [8]. The advantages of
intrinsic sensors are that they can measure radiation at single or multiple points and
also for an arbitrary spatial distribution by making use of optical time domain
reflectometers (OTDR) [4].
Extrinsic fibre optic sensors are based on the use of an external transducer
converting high energy alpha, beta and gamma radiation into optical radiation
[1, 10–16]. Although optical fibers are used only as lead-in and lead-out compo-
nents, depending on the application field, the length of the lead fibers and the
particular installation, and radiation effect characteristics of optical fibers can
influence the performance of extrinsic sensors.
Extrinsic sensors are based on the use of scintillation, thermoluminescence or
optically stimulated luminescence in specific materials. Scintillation is a process in
Table 37.1 Comparative table between intrinsic and extrinsic fiber optic sensors
Fiber optic sensors
Intrinsic sensors Extrinsic sensors
Radiation induced absorption (RIA): Scintillation:
Point sensors Organic
Distributed sensing (OTDR) Inorganic
Radiation induced luminescence (RIL) Thermolunimescence (TL)
Cerenkov radiation Optically stimulated luminescence (OSL)
Refractive index changes
Fiber Bragg gratings
37 Application of Sm Oxide Doped Oxyfluoride Glasses 377
which high energy radiation is converted into an optical radiation in the UV-visible
spectral range by a material called a scintillator. Optically stimulated luminescence
(OSL) is observed when a material pre-exposed to ionizing radiation and then further
subjected to an appropriate optical stimulation, emits a light signal proportional to
the absorbed dose at a wavelength characteristic of the OSL material. OSL is
analogous to thermo-luminescence (TL) process in which the stimulation is carried
out thermally rather than optically. The principles of operation of both types of
sensors are compared in Table 37.1.
In this paper we consider the application of Sm oxide doped oxyfluoride glasses
for the development of extrinsic fibre optical X-ray radiation sensors.
37.2 Extrinsic Fiber Optic Radiation Sensors
37.2.1 Overview and Classification
As outlined above extrinsic fiber optic sensors are offering specific advantages
compared to intrinsic sensors, and a large variety of them has been proposed
depending on the type of application, sensing principle, material, construction etc.
One classification can be by the type of scintillating material which can be
organic as BSF-60 [1] or inorganic like La2O2S:Eu, La2O2S:Tb, Y3Al5O12:Ce,
Gd2O2S:Eu, Gd2O2S:Pr, CaWO4, ZnS:Ag, Tb used in combination with phosphorus
[8, 10, 11, 14].
Extrinsic FO sensors can also be grouped according to the type of radiation
measured as single radiation and combined sensors. The former are basically
intended to detect a particular type of high energy radiation. For example electron
detection based on absorption and fluorescence has been studied [3], or a gamma
sensor using higher efficiency BGO (Bismuth Germanate – Bi4Ge3O12) with a
plastic optical fiber [1], X-ray detection [8–12], and also UV radiation [16]. Com-
bined radiation sensors, on the other hand, allow for the separate measurement of
different types of radiation. Gamma-ray was detected with a BCF-20 Saint Gobin
scintillating material, and thermal neutrons were separately detected using 6Li
converters [1]. Also a combined extrinsic fiber optic sensor for the measurement
of gamma and UV radiation has been proposed [15].
The extrinsic sensors can be configured as a single sensor and as multichannel
devices [13] with up to 80 accessible scintillations, or multiple sensors (coherent
bundles); or scintillating fiber optic gamma endoscopes [15].
A grouping by the principle of operation can subdivide them in those which
mostly employ a single type of phenomenon, and those using a combination of
sensing principles so as to improve performance. Thus radioluminescence in a
scintillating fiber providing a fast signal for timing and radiation induced absorption
in a Ge-doped silica fiber have been used [4] to develop an X-ray burst detector for
space applications [9].
We describe here the performance of Sm oxide doped oxyfluoride glasses when

irradiated by X-rays and the possibilities they offer to develop combined compact
extrinsic fiber radiation sensors using spectrally selective X-ray induced attenuation
of radioluminescence and fluorescence.
37.2.2 Synthesis and Properties of Sm Oxide Doped

Oxyfluoride Glasses
The base system ZnO-ZnF2-P2O5-B2O5 was investigated by varying the composi-

tion, doping with different amounts of samarium (Sm) and other rare earth
(RE) elements with examination of the obtained materials using a combination of
techniques such as:
• X-ray powder diffraction
• Thermal analysis (DSC and TMDSC)
• UV fluorescence
• X-ray fluorescence.
For the realization of this study ZnO – ZnF2 – P2O5 – B2O3 compositions were
synthesized. In the first stage, the approach is the introduction of equal amounts of
zinc oxide and zinc fluoride by keeping their total molar content constant, and
variation of the content of samarium oxide (Sm2O3) and samarium fluoride (SmF3)
with a progressive increase of their contents in the zinc – boro – phosphate system
(samples 1–7 of Table 37.2). In the second stage, after determining the appropriate
amount of Sm system only the influence of zinc fluoride is monitored (samples 8–11
in Table 37.2). Thus nine samples with the compositions given in Table 37.2 were
synthesized. In addition, two more samples are given for comparison. For the
synthesis of the first only ZnF2 was used, for the synthesis of the second only ZnO.
Table 37.2 List of the samarium doped zinc phosphate samples [17]

№ ZnO ZnF2 B2O3 P2O5 Sm2O3 SmF3 Тg, C
1 – 71.81 18.00 9.69 – 0.500 –
2 71.81 – 18.00 9.69 – 0.500 537
3 36.03 36.03 18.00 9.69 0.125 0.125 505
4 35.90 35.90 18.00 9.69 0.250 0.250 500
5 35.60 35.60 18.00 9.69 0.175 0.175 531
6 36.08 36.08 18.00 9.69 0.075 0.075 499
7 36.13 36.13 18.00 9.69 0.025 0.025 528
8 64.85 7.21 18.00 9.69 0.125 0.125 533
9 57.65 14.41 18.00 9.69 0.125 0.125 531
10 50.44 21.62 18.00 9.69 0.125 0.125 518
11 43.24 28.82 18.00 9.69 0.125 0.125 504
All concentrations are given in mol%
According to lines 3–7 Table 37.2, the first composites examine the content of
samarium compounds. The resulting compositions provide information on the
optimum content of rare earth elements in terms of transparency. It has been found
that composition 3 containing 0.125 mol% of both dopant components is a trans-
parent and homogeneous glass as evidenced in Fig. 37.6. For this reason, the second
compositional series (8–11) is based on this Sm2O3/SmF2 (Fig. 37.1) content. The
glass transition temperatures of the first set of samples (3–7) shown in the table were
determined by thermal analysis; as can be seen, they are in the range 485–514 C
without a linear correlation to the content of rare earth ions.
37.2.3 Optical Properties
The set-up consists of a light source, a sample and a detection system. The light
source is a combination of a Deuterium and a Halogen lamp, providing a spectrum in
the 200–2500 nm range for transmission and absorption measurements, and semi-
conductor light emitting diodes (LEDs), emitting at 370 nm, 395 nm, 420 nm and
450 nm to pump directly the sample under study for fluorescence measurements.
The basic element of the experimental set-up is the correctly positioned sample of
the Sm3+: ZnO-ZnF2-P2O5-B2O3 glass. The sample is placed in a special holder with
its parallel polished planes in the direction of the transmission and the side polished
plane at 90 to pick up fluorescence. The holding jig allows manipulation and
orientation of the sample for the different regimes of measurements.
The photoluminescence spectra were measured by optical CCD Avantes spec-
trometer Avaspec 2048.
Representative emission and absorption spectra of the synthesized sample are
illustrated in Figs. 37.2 and 37.3. All Sm-doped samples display photoluminescence,
in contrast to undoped samples (not shown). Typical photoluminescence of Sm3+
ions is observed with three emission bands corresponding to the following
transitions:
Fig. 37.1 The high content

of Sm2O3 changes the
appearance of the samples
due to occurring structural
rearrangements
Fig. 37.2 Representative emission spectrum for sample 8
Fig. 37.3 Absorption spectrum for sample 8
564 nm – 4G5/2 ! 6H5/2

600 nm – 4G5/2 ! 6H7/2
645 nm – 4G5/2 ! 6H9/2
The band at 600 nm corresponding to orange emission is the most intense.
The amorphous nature of composition 3 is indicated by X-ray diffraction analysis
performed (Fig. 37.4). In the pattern of this sample the presence of an amorphous
state with low intensity peaks is observed. These peaks are also clearly visible in the
X-ray diffraction pattern of the sample with composition 4 which has a crystalline
structure (Fig. 37.5).
3500
3000
2500
Intensity. a.u.
2000
1500
1000
500
0
0 20 40 60 80
2Q
Fig. 37.4 X-ray diffraction pattern of sample 3
4500
4000
3500
Intensity. a.u.
3000
2500
2000
1500
1000
500
0
0 20 40 60 80
2Q
Fig. 37.5 X-ray diffraction pattern of sample 4
37.3 Application of Sm Oxyfluoride Glasses

for the Development of Extrinsic X-Ray Fibre Sensors
37.3.1 Spectrally Dependent X-Ray Induced Attenuation
in Sm Oxide Doped Oxyfluoride Glasses
For the purpose of developing X-ray sensors, the behaviour of Sm ions on the emission
spectra during and after X-ray irradiation has been studied. Sample 3 was irradiated at
the Canadian Synchrotron (CLS Canadian Light Source) for different time intervals
(15 μs, 30 μs, 120 μs, 300 μs and 600 μs) with a dose rate of 110 Gy/min. Overall
attenuation and spectral changes were observed. X-radiation causes a darkening of the
sample caused by increased absorption as is evidenced in Fig. 37.6.
Fig. 37.6 A Darkening of Sm doped oxyfluoride glasses (sample 3) under X-ray exposure
Fig. 37.7 Fluorescence spectra (a) and integrated signals (b) of sample 3 for different irradiation
durations
Photoluminescent spectra of the sample after exposure for different time durations is
shown in Fig. 37.7a. A blue laser with a wavelength of 460 nm was used as an excitation
source. From this figure a reduction of the intensity of the photoluminescence under
continuous irradiation with X-ray radiation is seen. Figure 37.7b shows a double
logarithmic plot of the total integrated photoluminescence signal reduction with
irradiation time. Based on these results the so-called constant attenuation B was
calculated, which provides information on the stability of the test substance against
X-ray radiation. The value of B for the sample with the composition 3 is B ¼ 0.535,
indicating that the sample is relatively resistant to radiation.
The X-ray luminescence spectra of sample 3 during irradiation with X-rays are
presented in Fig. 37.8a. Figure 37.8b shows the integrated X-ray luminescence signal
vs. irradiation duration. The dose at which the sample was irradiated is 1.3 Gy/s. The
curve shows good stability of the sample under irradiation (B ¼ 0.171).
In Fig. 37.8a there is a splitting of the peak at about 700 nm, unlike in Fig. 37.7a,
where it is slanting. This effect is an indication of the formation of samarium ions of the
second valence during irradiation, which are not present any more after removal of the
X-ray source.
Fig. 37.8 Luminescence spectra (a) and integrated signals (b) of sample 3 for different irradiation
durations
During X-ray exposure During X-ray exposure

50 1,2
564 nm 564 nm
600 nm 600 nm
1 645 nm
40 645 nm y =1,467x-0,14
y = 80,07x -0,20 R2 = 0,992
Intensity, I (a. u.)
Intensity, I (r. u.)
0,8
R2 = 0,998
30
0,6
-0,20
y = 1,763x
20 y = 33,61x-0,14
R2 = 0,998
R2 = 0,992 0,4
10 y = 1,997x-0,27
0,2
R2 = 0,985
y = 31,35x-0,27
2
R = 0,985 0
0
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
Exposure duration, t (s) Exposure duration, t (s)
Fig. 37.9 Plots (experimental data in points) and power law fits (lines) for X-ray irradiation. (a)
Intensity attenuation curve; (b) normalized to unity attenuation curves
Figures 37.7b and 37.8b definitely suggest a power law decrease of the spectrally
integrated overall intensity for both photoluminescence (fluorescence) and X-ray
induced luminescence (scintillation) with different characteristic parameters. Nev-
ertheless, a closer inspection of the spectral fluorescence changes in Fig. 37.7 and of
the X-ray induced scintillation in Fig. 37.8 provides reasons for an application of
these glasses for the development of extrinsic optical fiber X-ray sensors.
A plot of the intensity decrease with time for the scintillation is shown in
Fig. 37.9a. It clearly reveals a spectrally dependent attenuation of for each of the
fluorescence peaks at 564 nm, 600 nm and 645 nm during X-ray exposure. To
compare the different rates of attenuation increase a normalized plot is shown in
Fig. 37.9b. The decrease of scintillation proves to follow a power law dependence.
Excitation at 460 nm Excitation 460 nm

60 1,2
560 nm 560 nm
600 nm 600 nm
50 650 nm 1 650 nm
Normalized intensity,
-0,65
y = 6,159x
Intensity, / (a. u.)
-0,65
40 y = 136,7x 0,8 R2 = 0,996
2
R = 0,996
30 y = 325,1x
-0,69 0,6
R2 = 0,998 -0,69
y = 6,773x
20 -0,74 0,4 R2 = 0,998
y = 129,2x
2
R = 0,997 y = 7,975x-0,74
10 0,2 R2 = 0,997
0 0
0 100 200 300 400 500 600 700 0 200 400 600 800
Exposure duration, t (s) Exposure duration, t (s)
Fig. 37.10 Plots (experimental data in points) and power law fits (lines) for the decrease of the
fluorescence intensity of each peak for blue light irradiation at 460 nm: (a) intensity attenuation
curves; (b) normalized to unity attenuation curves
Analogously, the spectral attenuation for each peak shown Fig. 37.10b for a
460 nm laser exposure is also wavelength dependent but develops faster in time, and
the differences are far less pronounced.
37.3.2 Possibility of Developing Extrinsic Fiber Optic X-Ray

Sensors
The intensity and the normalized intensity curves are found to be best fitted by a
power law in the form
I ¼ I 0 t α ð37:1Þ
where I0 is the initial intensity.

This equation can be rewritten in a normalized form as:
t α
I¼ ð37:2Þ
τ
where the time scaling parameter τ is related to the initial intensity I0 and the power α
as:
1=α
τ ¼ I0 ð37:3Þ
The values of the fitting parameters parameter I0 and α and the time scaling
parameter τ are given in Table 37.3.
Table 37.3 Values of the λ (nm) α I0 τ

parameters α, I0 and the time
645 0.1488 1.4679 13.1908 s
scaling parameterτ in the case
of X-ray irradiation 600 0.2079 1.7637 15.3216 s
564 0.271 1.997 12.8353 s
Table 37.4 Values of the λ (nm) α I0 τ

parameters α, I0 and the time
650 0.6522 6.1592 16.2388 s
scaling parameterτ in the case
of 460 nm irradiation. 600 0.6899 6.7734 16.0045 s
560 0.7461 7.9753 16.1664 s
Fig. 37.11 Double logarithmic plot of the power law plots in Fig. 37.9
Using the values for τ and α we used (37.2) and (37.3) for each spectral
component and plot the theoretical fit and compare with the experimental data
shown in Fig. 37.9 and in Fig. 37.10. The power and time scaling fitting parameters
for the from Fig. 37.8 and Fig. 37.10 are provided in Table 37.3 and Table 37.4
respectively.
The normalized curves in Figs. 37.9 and 37.10 show that the loss of transparency
is wavelength dependent, both the power α and the time-scaling parameters τ are
wavelength dependent and hence α(λ) and τ(λ). A log-log plot for scintillation
decrease is shown in Fig. 37.11. These plots are the spectral components of the
integrated signal drop shown in Fig. 37.9b.
We first note that as a whole the scintillation intensity, measured over a 15 s time
period, is considerably weaker than that of fluorescence. Second, we note that the
fluorescence intensity drops much faster compared to scintillation intensity. The time
scaling parameters for the three spectral components of fluorescence are all around
16 s vs. 12.83–15. 32 s for scintillation.
Third we note that the spectral differences in the attenuation behaviour for
scintillation vary much more compared to fluorescence. Thus, the power parameter
α for fluorescence reduction during X-ray exposure varies by a factor of almost 2 for
564 nm and 645 nm.
This temporal behaviour means that the observation of the spectrally differential
reduction in fluorescence can be used to measure X-radiation over a large range of
time intervals.
For example, it takes about 40 s for the fluorescent signal to drop to the 0.6 level
from the initial intensity while for scintillation it takes about 85 s at 564 nm, about
180 s at 600 nm and about 400 s at 645 nm. This practically means that if both the
scintillation and the fluorescence spectra are monitored, the faster responses of
fluorescence can be used to track X-ray doses over shorter intervals of time while
the two to ten times slower responses of scintillation decrease can be used to measure
larger doses accumulated over longer periods of time with the same accuracy. For
such longer durations, further changes of intensity drop of fluorescence will be too
weak for measurements with the same accuracy.
A suitably shaped Sm doped glass sample can be attached to the extremity of a
large core glass or plastic optical fiber which is both a lead-in fiber for laser induced
fluorescence and a lead-out fiber for both spectral scintillation and fluorescence
measurements. The sensor tracks spectral scintillation changes and the laser
(or LED) is switched on over shorter intervals of time to track faster occurring
changes. Scintillation and fluorescence measurements are thus time multiplexed in a
combined fiber optic extrinsic sensor.
37.4 Conclusions
We have analyzed the structural and optical properties of Sm doped oxifluoride

glasses and studied their fluorescence and X-ray luminescence spectra. It has been
found the fluorescence intensity decreases faster in time with irradiation while
scintillation decreases with a slower rate. It has also been found that X-ray induced
scintillation reduces at different rates for the different spectral maxima. Both fluo-
rescence and scintillation attenuation follow a power law time dependence which is
strongly wavelength dependent. These observations allow the development of
extrinsic optical fiber sensors in which both scintillation and fluorescence spectra
are analyzed, and the signals are time multiplexed. Fast fluorescence attenuation
allows for smaller doses to be measured while the slower spectrally dependent
scintillation attenuations allow for larger doses to be measured with the same
accuracy.
Acknowledgments Acknowledgments The authors are grateful to Professor Safa Kasap, DSc,
George Belev, PhD and Go Okada, PhD from University of Saskatchewan and CLS, Saskatoon,
Canada.
References
1. Sporea D, Sporea A, O’Keeffe, McCarthy D, Lewis E (2012) Chapter 23: Optical fibers and
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2. Woulfe P, Sullivan FJ, O’Keeffe S (2016) Optical fibre sensors: their role in in vivo dosimetry
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radiation induced attenuation in P-doped fiber: suppression of post-irradiation fading by using
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8. Sporea D, Mihai L, Vâţă I, McCarthy D, O’Keeffe S, Lewis E (2014) Characterization of
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Chapter 38
MWCNT/PANI Screen Printed Electrodes
for Gas Sensors
Gorazd Chepishevski, Aleksandar Petrovski, Anita Grozdanov,

Perica Paunović, Aleksandar T. Dimitrov, Gennaro Gentile,
and Maurizio Avella
Abstract During the last 10 years, CNT based nanocomposites belong to a group of
new materials that have intensively been tested for gas sensing, and great efforts have
been spent for the development of gas sensors. The construction of SOx sensors is an
important task because SOx containing oxides are dangerous having a negative influence
on the environment and humans. Most of the literature data are related to MWCNTs
based sensors for gases such as water vapors, NH3, CO2 and CO. In the present work, a
promising application of screen printed electrodes with MWCNT/PANI
nanocomposites prepared by a direct electro-polymerization method as a gas sensor
was tested. Resistivity variations were found for different acid concentration. Surface
changes of the SPE sensors before and after acid exposure, were followed by SEM.
Polymer/CNTs interactions and their changes due to the acid vapors were studied by
FTIR-ATR spectroscopy. The obtained results confirmed polymer/CNT – SO42 inter-
actions and their characteristic band-shifting. SEM photos show the formation of typical
oxid nanorods.
Keywords Nanocomposites · PANI · Multiwalled carbon nanotubes · Gas sensor
38.1 Introduction
In the last decade, gas sensors were in the focus of the researchers due to their
extensive applications in industry and environmental monitoring. Gas-sensing mate-
rials mainly include semiconducting metal oxides, vapor sensitive polymers, porous
silicon, etc. Based on the gas-sensing principle of adsorption/desorption of target gas
G. Chepishevski · A. Petrovski · A. Grozdanov · P. Paunović (*) · A. T. Dimitrov

Faculty of Technology and Metallurgy, University “Ss Cyril and Methodius”, Skopje,
Macedonia
G. Gentile · M. Avella
Institute for Polymers, Composites and Biomaterials, IPCB-CNR, Naples, Italy

390 G. Chepishevski et al.
molecules on the sensor surface, significant enhancement in sensitivity could be

achieved by increasing the interfacial contact among the sensor surface and the target
gases. Due to their excellent electron transport properties, multi wall carbon
nanotubes (MWCNT) have proven their ability to be used as sensing material in
conductometric gas sensors [1, 2].
Polyaniline (PANI) belongs to the group of the most important organic
conducting polymers today due to several facts such as its facile synthesis and
processing, environmental stability and low cost. Because of these advantages,
PANI was selected for this study as a polymer matrix for nanocomposite sensors
with MWCNTs. State-of-the-art literature has shown that PANI was widely applied
as new sensitive layer for various gas sensors in chemiresistors and optical sensors
since it exhibit significant electrical reesponses [3]. The tested gases include NH3
[3], NOx [4], H2S [5], SO2 [4], CO2 [5], chloroform [6] and humidity [7]. It was also
found that compared to other inorganic sensor materials (specially SnO2), PANI
films as gas sensitive material possess the advantage of high sensitivity to analytes at
room temperature. He et al. [8] prepared polyaniline-coated MWCNTs via in situ
polymerization for the detection of ammonia. They demonstrated a fast response and
a good reproducibility at room temperature. A linear response was obtained for
ammonia concentrations in the range from 0.2 to 15 ppm [8]. Zhang et al. [9]
performed an electrochemical functionalization of CNTs with polyaniline. On-line
detection of NH3 was obtained by the PANI-CNT network based sensors. Its
sensitivity ΔR/R was up to 2.44% per ppm NH3, which was 60 times more than
for pristine CNTs. The recovery time was in hours, the response time in minutes,
while its sensitivity was high when the temperature was low. Lim et al. [10]
investigated electrical and gas sensing properties of single-walled carbon nanotube
networks functionalized with polyaniline (PANI–SWNTs) in order to understand the
gas sensing mechanisms and to optimize the sensing performance. The temperature-
dependent electrical resistance and field-effect transistor (FET) transfer characteris-
tics indicated that the electrical properties of PANI–SWNTs were dominated by the
PANI coating. The transfer characteristics of FETs exposed to different NH3 con-
centrations indicated that the dominant sensing mechanism was the deprotonation of
PANI by NH3. Sensing experiments with different gas analytes revealed that PANI–
SWNTs responded positively to NH3, and negatively to NO2 and H2S with sensi-
tivities of 5.8% per ppmv of NH3, 1.9% per ppmv of NO2, and 3.6% per ppmv of
H2S.
The aim of this work is to produce and test a gas sensor based on MWCNT/PANI
nanocomposite SPE electrodes using resistivity changes.
38 MWCNT/PANI Screen Printed Electrodes for Gas Sensors 391
38.2 Experimental
Nanosensors based on screen printed electrodes (SPE) were prepared by direct

electro-polymerization of polyaniline and MWCNT on the gold wires of the elec-
trodes. Electro-polymerization was performed in an electrochemical cell using an
electrolyte of 0,1 M aniline and 0,5 M H2SO4. A SPE was used as a working
electrode, a saturated calomel electrode (SCE) as a reference one. MWCNT (3%
wt) were dispersed into the electrolyte by ultra-sonication for 30 min.
Characterization of the SPE nanosensors, before and after the acid vaporization,
was done by SEM and FTIR-ATR spectroscopy. FTIR-ATR spectra were collected
by a Perkin Elmer-Spectrum 100 machine at 64 scans. The surface morphology of
the electrodes was analyzed by FEI Quanta 200 scanning electron microscope, using
a secondary electron detector and an acceleration voltage of 30 kV. The gas
sensitivity was tested using resistivity measurements of the electrodes vaporized
with different concentrations of H2SO4 (50%, 25%, 12.5%, 6% and 3%).
Fig. 38.1 Change of current density during electro-polymerization of PANI and PANI/MWCNT
nanocomposites
Fig. 38.2 SEM images of the studied 3%wt MWCNT/PANI sample: (a) 80, (b and c) 20,000
1.3 PANI/MWCNTs 10 PANI/MWCNTs

6.25% wt. H 2SO4 50% wt. H2SO4
1.2
9
Resistivity, MW
Resistivity, MW
1.1
1.0 8
0.9 7
0.8
6
0.7
0.6 a) 5 b)
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
Time, sec. Time, sec.
Fig. 38.3 Resistivity changes of the tested SPE sensors: MWCNT/PANI SPE exposed to (a) 6%
H2SO4; (b) 50% H2SO4
Electrochemical synthesis of MWCNT/PANI nanocomposites was performed

directly on the gold wires of the screen printed electrodes at a working potential of
0.75 V. The presence of the carbon nanotubes in PANI increased the electro-
polymerization rate versus pure PANI, as shown in Fig. 38.1. The characteristic
morphology of the obtained nanocomposites is shown in Fig. 38.2.
The gas sensitivity of the obtained MWCNT/PANI nanocomposite SPE elec-
trodes were tested by exposure the SPEs to vapors originated from different con-
centration of H2SO4 using resistivity measurements. Characteristic responses of the
performed measurements are shown in Fig. 38.3. Generally, the tested electrodes
Fig. 38.4 SEM images of the acid treated SPE samples: (a) 3% H2SO4 (30,000); (b) 6% H2SO4
(30,000); (c) 25% H2SO4 (20,000); (d) 50% H2SO4 (30,000)
demonstrated a non-linear response. For all tested acid concentrations, it was found
that in the first 100 s the resistivity decreased, i.e. the conductivity increased which is
in agreement with literature data for PANI-based gas sensors [11]. This trend
continued for the response to 6 and 50% H2SO4, while for 12,5% and 25% H2SO4
it was found that after the first 100 s the resistivity increased and conductivity
decreased.
Due to the acid treatment of the SPE electrodes, morphological changes occurred
on the nanocomposite surface. Some of the characteristic microphotographs are
shown in Fig. 38.4. Due to the acid treatement, typical nanorods of salt structures
were found in all tested samples. Actually these salt nanorods are responsible for the
increased conductivity. Due to the acid vaporization, also smaller voids and fractures
were found in all treated SPE nanosensors (Fig. 38.5).
Fig. 38.5 SEM images of the acid treated SPE samples: (a) 3% H2SO4 (8000); (b) 6% H2SO4
(8000); (c) 25% H2SO4 (4000); (d) 50% H2SO4 (8000)
Structural changes of the acid-treated electrodes were studied by FTIR-ATR

spectroscopy. The obtained spectra are shown in Fig. 38.6. The main peaks at
1568 and 1480 cm 1 were assigned to the stretching vibrations of quinone and
benzene rings, respectively. The peaks at 1292 and 1236 cm 1 correspond to C-N
stretching vibration. The peaks at 1131 and 800 cm 1 were attributed to in-plane out-
of-plane bending of C-H, respectively. These suggest that PANI was polymerized in
the conductive emeraldine salt form during the polymerization. Due to the acid
vaporization, by increasing the acid concentration the intensity of the peaks at
1137 cm 1, 1296–1300 cm 1, 1580 cm 1 decreased, while that of the peaks at
1460 cm 1 and 1750 cm 1 increased, and some peak shifting of the characteristic
bands occurred.
38.4 Conclusions
This work presents a method for the production of gas sensor based on MWCNT/
PANI SPE electrodes using resistivity changes.
120
115
PANI/MWCNT treated with 50% H2SO4
110
105
100
95
90
PANI/MWCNT not treated
85
80
75
CNI-3 1000 1500 2000 2500 3000 3500
100
95
90
85
Transmission
80
75
70
65 PANI/MWCNTs traeted in:
60
3 % H2SO4
55 25 % H2SO4
50 50 % H2SO4
500 1000 1500 2000 2500 3000 3500 4000

–1
Wave number, cm
Fig. 38.6 FTIR-ATR spectra of SPE nanocomposite before and after acid exposure
• SEM images have shown that in the vaporized samples nanorod structures of the
salts were found. Because of the aggressive acid vaporization, also smaller voids
and fractures were found in all treated SPE-nanosensors
• Using the FTIR-ATR spectroscopy, it was shown that PANI was polymerized in
conductive emeraldine form. Because of the acid treatment some structural
changes were found which induced peak shifting of the characteristic bands.
Acknowledgments This research was done within FP7 Project “Cost-effective sensors, interop-
erable with international existing ocean observing systems, to meet EU policies requirements”
(Project reference 614155).
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9. Zhang T, Nix MB, Yoo B-Y, Deshusses MA, Myung NV (2006) Electrochemically
functionalized single-walled carbon nanotube gas sensor. Electroanalysis 18:1153
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Electrical and gas sensing properties of polyaniline functionalized single-walled carbon
nanotubes. Nanotechnology 21:7
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composites of nanostructured carbonized polyaniline and Nafion. J Solid Sate Electrochem
20:3061
Chapter 39
Synthesis of RGO/SiO2 and Ag/RGO/SiO2
Nanocomposites and Study of Their
Sensitivity Towards Humidity
A. S. A. Shalaby, Sh. Safwat-Mansour, Ahmed S. Afify, M. Hassan,

and A. Staneva
Abstract In recent years, many interesting researches published on the study of new
nanocomposite materials involves active components such as reduced graphene
oxide (RGO), silver nanoparticles (Ag-NPs), and silica, which indicated very inter-
esting properties and applications. The present work demonstrates the preparation of
nanocomposite powders with the participation of Ag-NPs, RGO and tetraethyl-
orthosilicate (TEOS) using the sol-gel technique. The phase formations are verified
by X-ray diffraction analysis. The thermal behavior was studied using differential
thermal analysis (DTA/TG) in air. The sensitivity against humidity was tested in a
laboratory apparatus made of a thermostatic chamber operating at 25 C, in which
the RH could be varied between 0% and 96%.
Keywords Reduced graphene oxide · Silver nanoparticles · Sol-Gel technique ·

Humidity sensor
39.1 Introduction
In recent years, nanocomposites as new applicable materials have captured and held
the attention and imagination of scientists and engineers in order to satisfy the
requirements of society. There are significant efforts to prepare new nanocomposites
A. S. A. Shalaby (*)
Science and Technology Center of Excellence (STCE), Cairo, Egypt
S. Safwat-Mansour · A. Staneva
A. S. Afify
Department of Applied Science and Technology (DISAT), Politecnico di Torino, Torino, Italy
M. Hassan
Department of Natural Science, Obour Institute of Engineering and Technology, Cairo, Egypt

398 A. S. A. Shalaby et al.
based on graphene which are considered as very promising material with large
surface area and specific electrical, optical and mechanical properties [1–3]. A
graphene/silica nanocomposite shows an interesting property due to the local atomic
configuration, and the binding sites between them. Silica acts as a carrier and
considered an excellent supporting material because of their large surface area,
flexible pore size and thermal stability. In addition, silica matrix improved the degree
of dispersion which reduces the agglomeration of nanoparticles [4]. The
nanocomposites containing reduced graphene oxide, silver nanoparticles and silica
exhibit unique physical, chemical, and biological properties [5]. Ag/RGO/SiO2
nanocomposites have an exceptional catalytic activity toward the reduction of
4-nitrophenol [6], are used as anode material in lithium-ion batteries [7], and show
a surface-enhanced Raman scattering (SERS) performance for the detecting traces of
organic colorants compared with graphene/Ag nanocomposites [8].
The present work demonstrates the preparation of nanocomposites with partici-
pation of Ag, RGO and SiO2 nanostructures by the sol-gel technique in order to
study their structure formation, phase transformations, thermal stability, and their
sensitivity against humidity.
39.2 Experimental Procedure
39.2.1 Synthesis of Reduced Graphene Oxide (RGO)
RGO has been prepared by chemical exfoliation of purified natural graphite (Graph-
ite flaks, 99.9%, Alfa Aesar) as described in our study [9]. Briefly, the preparation in
three steps can be summarizes as follow:
1. Graphite was oxidized by strong acid to obtain graphite oxide.
2. Graphite oxide solution was ultrasonicated for 2 h to prepare dispersion solution
of graphene oxide;
3. This dispersion solution was reduced using the strong reducing agent sodium
borohydride (NaBH4, 98%, Alfa Aesar) to obtain reduced graphene oxide.
39.2.2 Synthesis of Silver Nanoparticles (Ag-NPs)
Silver nanoparticles were synthesized by a chemical reduction method [10, 11] by

adding an excess of the reducing agent sodium borohydride to silver nitrate (AgNO3,
Fluka AG) following the chemical equation:
AgNO3 þ NaBH4 ! Ag þ 1=2 H2 þ 1=2 B2 H6 þ NaNO3
A specific volume of AgNO3 (1 mM) solution was added to a cooled volume of

NaBH4 (2 mM) solution in the ratio 1:3 dropwise. The color of the solution
39 Synthesis of RGO/SiO2 and Ag/RGO/SiO2 Nanocomposites 399
converted from yellow at the beginning of addition to yellowish brown due to

increase of silver content. Finally, few drops of NaCl (1.5 M) were added in order
to precipitate the colloid. The solution was settled for 2 h before the filtration. The
filtrated nanopowder was washed with destilled water many times, then dried at
80 C for 2 h.
39.2.3 Synthesis of RGO/SiO2 Nanocomposite
RGO/SiO2 nanocomposites (20 RGO:80 SiO2 (wt %)) were prepared using the sol-
gel technique due to the surface hydroxyl groups of the RGO sheets acting as
nucleation sites for the hydrolysis step, which facilitates chemical bonding with
the surrounding materials. The method of preparation of this type of nanocomposite
followed our previous study [12] Briefly, we can summarize the steps of preparation
as follows: A dispersed mixture of as prepared RGO (20 wt %) in deionized water
was prepared as above and then added to the TEOS (Si (OC2H5)4, >99%, Aldrich)
solution which was prepared by ethanol under stirring for 1 h at 100 C. Thus, the gel
was obtained.
39.2.4 Synthesis of Ag/RGO/SiO2 Nanocomposite
Following the scheme in Fig. 39.1 we successfully obtained a nanocomposite

powder with the nominal composition 10 Ag*20 RGO*70 SiO2 (wt%).
Fig. 39.1 Scheme of preparation of Ag/RGO/SiO2 nanocomposites using sol-gel technique

39.2.5 Sensing Film Preparation and Sensing Mechanism
The sensing films were prepared as expressed previously in [13]. An apparatus made
of a thermostat chamber, operating at RT, was used to perform the humidity sensing
measurements in which the relative humidity could be varied between 0% and 96%
[14]. An external alternating voltage (V ¼ 3.6 V at 1 kHz) was applied on each tested
sensor, acting as a variable resistance in the above-mentioned electrical circuit. A
2000 series Keithley digital multi-meter was used to measure the voltage VDC at the
output of the circuit [14]. Determination of the sensor resistance was realized by a
calibration curve drawn substituting the sensors, in the circuit by known resistances.
The sensor response SR, expressed in %, was defined as the relative variation of the
starting resistance, compared with the resistance measured under gas exposure
(Eq. 39.1):
jR0 Rgj
SRð%Þ ¼ 100 : ð39:1Þ
R0
where R0 and Rg are the starting resistance (in the absence of the test gas) and the
measured resistance of the sensors under exposure, respectively.
39.3 Results
The X-ray diffraction patterns of samples with the nominal compositions

20 RGO*80 SiO2 and 10 Ag*20 RGO*70 SiO2 (wt %) heated up to 100 C are
shown in Fig. 39.2. The diffraction curve of sample RGO/SiO2 show the amorphous
nature of the composite which is related to the amorphous or glassy nanoscale silica,
which is the major component of the composite while, the RGO appeared as very
small peaks at positions 2θ ¼ 26.3 and 2θ ¼ 42.9 which are hardly detectable.
In the diffraction curve of sample Ag/RGO/SiO2 different phases appeared
such as amorphous silica, RGO with a very small peak at 2θ ¼ 26.3 , Ag-NPs
(Ref. code: 00-004-0783) and AgCl (Ref. code: 00-031-1238). Silver chloride
(AgCl) appeared due to the preparation method which used a few drops of
concentrated HCl acid to accelerate the gelation reaction in the sol-gel technique.
Some metallic Ag-NPs reacted with the acid and formed AgCl nanocrystal. The
average of the crystal size calculated from the broadening of the diffraction line
using Sherrer’s equation for Ag-NPs inside the composite was about 33 nm while
for the AgCl nanocrystal it was about 41 nm.
The phase transformation of the sample with the nominal composition 10 Ag*20
RGO*70 SiO2 (wt%) was studied after heating at 100 C, 350 C, and 600 C. The
diffraction curve of the sample heated up to 100 C shows that the nanocomposite
Fig. 39.2 XRD patterns of samples with nominal compositions 20 RGO*80 SiO2 (wt %) and
10 Ag*20 RGO*70 SiO2 (wt%) heated up to 100 C
contains an amorphous hump at 2θ ¼ 22.6 which is connected to the existence of

amorphous silicate; there are different crystal phases such as RGO nanoparticles,
Ag-NPs and AgCl nanocrystals. The average crystal size calculated from Sherrer’s
equation is 70 nm as shown in Fig. 39.3.
At higher temperatures (350 C) the amorphous hump decreased in intensity with
increasing heating temperature; the peak at 2θ ¼ 26.2 which is connected to the
existence of RGO became clearer than before. At a temperature of 600 C, the
diffraction curve showed that the peak at 2θ ¼ 26.2 connected to the existence of
RGO almost disappeared. It is well known that all carbon phases start to burn in air
above 400 C. Furthermore, there are no significant effects of increasing the tem-
perature up to 600 C on the Ag-NPs and AgCl phases as shown in Fig. 39.3.
According to the DTA/TG curves shown in Fig. 39.4 both samples showed
significant weight loss above 100 C. This is attributed to the elimination of water
as well as removal of the weak oxygen-containing functional groups (CO, CO2 and
H2O vapors).
As one can see for the sample RGO/SiO2, a strong exothermic effect appeared
at 565 C due to strong combustion of carbon. The total mass loss after heating up
to 800 C was about 41% of the mass of the obtained nanocomposite as shown in
Fig. 39.4. In the sample Ag/RGO/SiO2, the endothermic effect appears at 150 C;
it may be related to the thermal dehydration; there are many exothermic effects
apparent at 340 C, 440 C and 580 C possibly due to the gradual combustion of
carbon of the organic precursors and carbon of RGO. The mass lost gradually
Fig. 39.3 XRD patterns of samples with the nominal composition 10 Ag*20 RGO*70 SiO2 (wt%)
heated up to 100 C, 350 C and 600 C
increases during the heating up to 800 C. It was about 58% from the mass of the
obtained nanocomposite as shown in Fig. 39.4.
39.4 Sensitivity Towards Humidity
Figure 39.5 illustrates the sensor response towards RH. Samples RGO/SiO2 and
Ag/RGO/SiO2 showed a significant response towards RH at room temperature,
starting from 33% RH.
39.5 Conclusions
We successfully prepared novel nanocomposite materials containing Ag-NPs, RGO

and SiO2 using the sol-gel technique. The structure formation and phase transfor-
mations were confirmed by XRD analysis. According to DTA/TG analysis the
thermal stability of RGO/SiO2 composite was better than that of Ag/RGO/SiO2
nanocomposites. The as prepared nanocomposites have significant sensitivity
response towards humidity but the RGO/SiO2 composite was better. This could
open a channel to use the Ag/RGO/SiO2 samples as NOx or COx sensors.
Fig. 39.4 DTA/TG patterns of the samples RGO/SiO2 and Ag/RGO/SiO2

Fig. 39.5 Sensor response toward relative humidity changes
References
1. Machado BF, Serp P (2012) Graphene-based materials for catalysis. Catal Sci Technol 2(1):54
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Soc Rev 39(1):228
3. Mwakikunga BW, Hillie KT (2011) In: Gong J (ed) Chapter 5: Graphene synthesis, catalysis
with transition metals and their interactions by laser photolysis. Graphene – synthesis, charac-
terization, properties and applications. InTech, p 59
4. Pham DP, Huynh KK, Tran CV, Vu VQ, Tran TTV (2014) Preparation and structural charac-
terization of Sol-gel-derived silver silica nano composite powders. Int J Mater Sci Appl 3
(5):147
5. Tran QH, Nguyen VQ, Le A-T (2013) Silver nanoparticles: synthesis, properties, toxicology,
applications and perspectives. Adv Nat Sci Nanosci Nanotechnol 4:033001
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posite microspheres with high aqueous dispersity and excellent catalytic activity. ACS Appl
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rGO@SiO2@FeOOH@Ag nanocomposite as efficient surface enhanced Raman scattering
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9. Shalaby A, Yaneva V, Staneva A, Aleksandrov L, Iordanova R, Dimitriev Y (2014) Thermal
stability of RGO and RGO/SiO2 nanocomposite prepared by sol-gel technique. Nanosci
Nanotechnol, (Sofia, Bulg) 14:120
10. Mavani K, Shah M (2013) Synthesis of silver nanoparticles by using sodium borohydride as a
reducing agent. IJERT 2(3):1
11. Mozghan B (2008) Synthesis of noble metal nanoparticles. Dissertation, Drexel University,
USA
12. Shalaby ASA, Staneva AD, Aleksandrov LI, Iordanova RS, Dimitriev YB (2016) Preparation,
characterization and thermal stability of reduced graphene oxide/ silicate nanocomposite. Bulg
Chem Commun 48(1):38
13. Afify AS, Hassan M, Piumetti M, Peter I, Bonelli B, Tulliani J-M (2015) Elaboration and
characterization of modified sepiolites and their humidity sensing features for environmental
monitoring. Appl Clay Sci 115:165
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based humidity sensors. Ceram Int 31:507
Chapter 40
Preparation of Nanoporous Hybrid
Materials with Bridged Tetra Sulfide
Functional Groups and Determination
of Their Sensing Characteristics Towards
Relative Humidity
M. Abdallah, N. Velikova, Y. Ivanova, Ahmed S. Afify, M. Ataalla,

and M. Hassan
Abstract Nano porous hybrid materials were synthesized by co-condensation

of organically bridged tetra sulfide bis [3-(triethoxysilyl) propyl] tetra sulfide
(BTPTS) and tetra ethoxylsilane (TEOS) in the presence of the non-ionic
surfactant triblock copolymer poly(ethylene glycol)-block-poly (propylene gly-
col)-block-poly (ethylene glycol) (EO20PO70EO20) in acidic media as revealed
by the measurement of nitrogen adsorption. The structure and chemical state of
the materials were characterized by chemical analysis, Fourier–transform infra-
red spectroscopy (FTIR), 29Si MAS NMR, and thermo-gravimetric analysis
(DTA/TG), revealing the integrity of organic groups inside the framework.
The synthesized powders were prepared as sensors using the screen-printing
technique and then evaluated on view of their sensing characteristics in the
M. Abdallah (*)
Research and Development Department, MEPACO-MEDIFOOD, Cairo, Egypt
Department of Silicate Technology, University of Chemical Technology and Metallurgy, Sofia,
Bulgaria
N. Velikova · Y. Ivanova
Department of Silicate Technology, University of Chemical Technology and Metallurgy, Sofia,
Bulgaria
A. S. Afify
M. Ataalla
Faculty of Engineering and technology, Badr University in Cairo (BUC), Badr City, Egypt
M. Hassan

408 M. Abdallah et al.
range from 0.0% to 96% relative humidity (RH) at room temperature. Sensors
with a higher content of BTPTS show a better response towards RH.
Keywords Hybrid materials · Nanoporous materials · Porosity · Relative humidity ·

Screen-printing · Sensors
40.1 Introduction
Since the first synthesis of mesoporous silica [1, 2] there has been a tremendous
amount of effort dedicated to the development of organic–inorganic mesoporous
hybrid materials particularly with regard to some potential applications such as
adsorption, biotechnology, host–guest chemistry, chromatography, catalysis,
sensor technology, and gas storage [3–7]. The organic groups can be placed
selectively on internal and/or external pore surfaces or even within the pore
walls. The organic modification in principle permits a fine tuning of materials
properties, including surface properties such as hydrophilicity/hydrophobicity or
potential interactions with guest molecules. In addition, the surface reactivity can
be altered and protected by organic groups with respect to chemical attacks; bulk
properties, e.g. mechanical or optical properties can also be changed. This
flexibility in choosing organic, inorganic or even hybrid building blocks allows
one to control the materials properties [8]. According to IUPAC the pores of
solids are classified according to their size, pore sizes in the range of 2 nm and
below are called micropores, those in the range of 2–50 nm are denoted as
mesoporous, and those above 50 nm are called macropores. The distribution of
size, shape and volume of the void spaces in porous materials is directly related to
their ability to perform the desired function in a particular application. The need
to create uniformity of the pore size, shape and volume has steadily increased
over recent years as it could be optimized for the desired application
[9]. Recently, we reported the synthesis of tetra sulfide-functionalized materials
by co-condensation of bis[3-(triethoxysilyl)propyl]tetra sulfide (BTPTS) and
tetraethoxylsilane (TEOS) [10]. There is a great demand for humidity sensors
which can be used for several applications in different fields under certain
conditions [11–14]. Many materials have beeb developed as humidity sensors
such as ceramics, electrolytes, and organic polymeric materials [11]. The aim of
this research was to study the influence of high concentrations of BTPTS on the
structure and morphology characteristic of the final hybrid materials and to
determine their sensing properties towards relative humidity.
40 Preparation of Nanoporous Hybrid Materials with Bridged Tetra Sulfide. . . 409
40.2 Experimental
40.2.1 Materials Synthesis
The tri-block copolymer Pluronic (P123), 1,4-bis (triethoxysilyl) propane tetra

sulfide (BTPTS), (CH3CH2O)3Si(CH2)3S– S–S–S(CH2)3Si(OCH2CH3)3), xylene,
hydrochloric acid (HCL) and tetraethyl ortho silicate (TEOS) (all Sigma Aldrich)
were used without further purification. All other chemicals were analytical grade.
The precursor solutions were prepared by the following procedures: A total of 1.2 g
of P123 and 3.5 g of potassium chloride were dissolved in 10 g of distilled water and
52 ml of 2M HCL, then magnetically stirred at room temperature until complete
dissolution to obtain a homogenous solution. Thereafter, 2.64 ml of xylene were
added into the surfactant solution accompanied by stirring for 1 h, followed by the
addition of 2.64 ml of TEOS and continue stirring for 1 h. Then, different amounts of
the organosilane precursor (BTPTS) were added as seen in Table 40.1 with contin-
uous stirring at 40 0.1 C for 1 h. Finally, the resultant slurry was dried at 100 C
for 24 h, the surfactant was extracted by soaking 1.0 g of the solid in 150 ml ethanol,
containing 1.7 ml of concentrated HCl at 50 C for 24 h.
40.2.2 Materials Characterizations
Thermo gravimetric analysis (TGA) was performed with a PT1600 TG-DTA/DSC

(STA Simultaneous Thermal Analysis, LINSEIS Messgeräte GmbH, Germany). The
working conditions were a heating rate of 10 C min1 under a flow of air. Fourier
transform infrared spectroscopy (FTIR) of KBr powder-pressed pellets was recorded
with a Varian 660-IR spectrometer. The sulfur content of the extracted samples was
analyzed quantitatively by elemental analysis (Elemental analyzer SPA Euro Vector
EA 3000). 13C cross-polarization magic angle spinning (CP MAS, 100.61 MHz) and
29
Si MAS solid-state NMR experiments (79.49 MHz) were recorded on a 9. 4T
BrukerAvance 400 spectrometer. The experimental parameters for 13C CP MAS
NMR experiments were 9 kHz spin rate, 5 s pulse delay, for 29Si MAS NMR
experiments 5 kHz spin rate and 60 s pulse delay. Nitrogen adsorption/desorption
analysis was carried out with an ASAP 2020 system in the static measurement mode;
Table 40.1 Sample compositions

Sample BTPTS mol TEOS mol P123 Water KCl 2M HCl Xylene
ID % % [g] [ml] [g] [ml] [ml]
S3 50 50 1.2 10 3.5 52 2.6
S4 57 43
S5 62 38
then pore size distributions were determined based on Barrett-Joyner-Halenda (BJH)

desorption curves.
40.2.3 Preparation and Testing of Humidity Sensor
Sensors were prepared and tested starting from the preparation of the interdigitated
platinum electrodes where a platinum conducting paste (ESL 5545, from Electro-
Science, King of Prussia, PA, USA) was deposited manually by the screen-printing
technique onto planar α-alumina substrates (ADS-96 R, 96% alumina, Coors Tek,
USA, 0.85 5 cm) by using a rubber squeegee through a 270 mesh steel screen;
after drying overnight, these devices were heated at 980 C for 20 min with a 2 C/min
heating/cooling ramp according to the ink’s manufacturer recommendations in order
to optimize the electrical conductivity of the electrodes. Then a screen-printable ink
was prepared by dispersing the synthesized powders in a suitable amount of the
organic solvent ethylene glycol mono butyl ether (Emflow 227, Emca-Remex
products, England) to reach an appropriate rheological behavior, adherence to the
substrate, and to achieve correct thermal shrinkage properties during the process of
screen-printing to obtain a good film. The third step was the preparation of the
sensing film manually by depositing the screen-printable ink onto the interdigitated
platinum electrodes by screen-printing technique using a rubber squeegee through
the abovementioned steel mesh screen; once these films were dried, the sensors were
heated at 500 C for 1 h with a 2 C/min heating/cooling ramp. The formed films had
thicknesses of about 30–40 μm and areas of about 1 cm2; scotch tests on the dried
films revealed a good adhesion on the substrates. Finally, the sensors were
electrically characterized using a laboratory apparatus made of a thermos stated
chamber working at 25 C in which the RH could be varied from 0% to 96%. The
experimental details have been reported previously [15]. RH values were measured
by means of a commercial humidity and temperature probe (Delta Ohm DO9406,
Italy). Each tested sensor was alimented by an external alternating voltage
(V ¼ 3.6 V at a frequency of 1 kHz); it constituted a variable resistance of this
electrical circuit. A 2000 Keithley digital multimeter was used to measure the
voltage VDC at the output of the circuit. The sensor resistance was determined by
substituting it in the circuit by known resistances and then plotting a calibrating
curve R ¼ f(VDC). The sensor response SR, expressed in %, was defined as the
relative variation of the starting resistance, compared with the resistance measured
under gas exposure as in Eq. (40.1):
jR0 Rgj
SRð%Þ ¼ 100 ð40:1Þ
R0
where R0 and Rg are the starting resistance (in the absence of the test gas) and the gas
exposed measured resistance of the sensors, respectively.
FTIR spectra of the samples with different BTPTS contents are shown in Fig. 40.1.
The bands around 1070, 800, and 450 cm1 are assigned to the Si–O–Si stretching
and bending vibrations of a condensed silica network [16–18]. The intensity of the
peak around 1240 cm1 attributed to Si-C bonds [19] increased with increasing
BTPTS amount due to high degree of condensed precursors and a higher cross-
linking of the silica framework. The broad band close to 3450 cm1 can be assigned
to OH stretching modes of silanol groups. The bands for -CH2 and -CH3 groups
appeared around 2978–2930; moreover, the Si-CH2 vibration was observed around
1411 cm1 The intensity of these bands increased with increasing BTPTPS amount
confirming the successful incorporation of organofunctional group into the silica
framework [20]. The presence of –S–S– and –S–C– bonds is reflected by vibration
bands around 690 and 565 cm1 [20–23]. The intensity of these bands increases with
increasing BTPTS amount thus confirming the successful incorporation of organo-
functional group after copolymer extraction [24]. This result was confirmed by
elemental analysis (Tables 40.2 and 40.3) as the sulfur content increases from 18%
to 30% for samples S3 and S5, respectively.
Figure 40.2 shows 29Si MAS NMR spectra of the synthesized hybrid materials. They
clearly show both Q and T sites, as expected. The prominent signals at 110 ppm,
101 ppm and 92 ppm, labeled Q4 [Si (OSi)4], Q3 [(OH) Si (OSi)3] and Q2 [(HO)2 Si
(OSi)2], respectively, imply a high degree of condensation and cross linking between the
precursors. Obviously, the Q2 peak disappeared in the samples (S3–S5), but T3, Q3, and
Q4 peaks were present in the spectra from the mesoporous materials, suggesting that the
Fig. 40.1 Infrared spectrum of synthesized S3, S4, and S5

Table 40.2 Wave numbers of the vibration of functional group

Vibration of functional Vibration of functional
group Wave number cm1 group Wave number cm1
νs Si-O-Si 800 -OH 1640
S-S 690 Si-C 1240
S-C 570 νas Si-O-Si 1070
νd Si-O-Si 450 Si-OH 950
Table 40.3 Elemental analysis of samples S3, S4, and S5

Sample ID Weight (mg) C% H% S wt. % Theoretical S%
S3 1.1310 19.7 4.1 18.6 23.69389
S4 2.2650 15.3 3.2 27.6 27.22887
S5 1.8440 20.3 4.2 30.1 29.80844
29
Fig. 40.2 Si MAS NMR Spectra of synthesized samples S3, S4 and S5
condensation degree of the mesoporous framework was significantly increased with

increasing BTPTS amount [25]. These results confirm the results from the FTIR analysis
showing the presence of peaks around 950 and 1240 cm1. The Qn peaks are charac-
teristic for the TEOS precursor. The intensity of the Qn peaks decrease since the ratio
TEOS/BTPTS in the synthesis mixture decreases. The signals stemming from silicon
bridged by organic group can be found in the range from 50 to 66 ppm. The strong
resonances at 57.0 and 66.0 ppm could be assigned to C-Si(OH)(OSi)2 (T2) and C-Si
(OSi)3 (T3) sites, respectively, suggesting the organic moiety is stable at the current
synthesis conditions allowing successful incorporation of BTPTS into the silica frame-
work [17, 21, 26, 27].
It can be seen in Fig. 40.3 that the 13C CP MAS NMR spectra of the synthesized
hybrid materials exhibit three signals corresponding to carbons in different environ-
ments at 12.6, 23.8 and at 42.5 ppm which correspond to carbon atom of bridging
organic group in the direction from a Si atom to a S atom [28]. The two weak signals
13
Fig. 40.3 C CP MAS NMR spectra of synthesized samples S3 and S5
at 17 and 58.6 ppm are assigned to the carbons in the surface ethoxy groups
(Si-OCH2CH3), which were formed during the surfactant extraction by acidified
ethanol. Additionally, these signals could originate from physisorbed/chemisorbed
ethanol as well, especially if the samples were not well dried [29]. The peaks
centered at 70 and 76 ppm are due to the remnant surfactant Pluronic P123 [30].
13
C CP MAS NMR and 29Si MAS NMR show that the synthesized gel materials are
hybrids; they can be classified as class II hybrid materials.
Thermogravimetric analysis is commonly employed to determine the character-
istics of materials such as moisture content, reaction temperatures, stability of
organic groups, etc. TGA and DTA curves of samples S3, S4 and S5 are presented
in Fig. 40.4. The 5 wt% loss at temperatures below 100 C is mainly due to the
removal of physically adsorbed water from the materials. Decomposition of bridging
organic group and residual P123 occurs between 300 and 600 C [31], samples S3,
S4 and S5 show weight losses of 45, 47 and 49 wt% respectively. The weight loss
increases as a result of increasing amounts of tetra sulfide functionalized precursor
which confirm the incorporation of tetra sulfide organic functional group into the
silica framework at high BTPTS content. The weight losses observed above 600 C
may be attributed to the combustion of residual organic material and/or to desorption
of water resulting from silanol condensation [29]. The result implies that the tetra
sulfide-bridged groups can be stable up to 300 C in air [32, 33].
The N2 adsorption/desorption isotherms of the materials are presented in
Fig. 40.5. According to the IUPAC classification [34] the materials are classified
as type IV isotherms which are typical for mesoporous materials (average pore size is
in the range between 2 and 50 nm). Sample S3 and S4 show a hysteresis loop type
H2 according to the IUPAC classification which is typical for ink bottle like pores
Fig. 40.4 DTG profiles of

samples S3, S4 and S5
Fig. 40.5 Nitrogen adsorption/desorption isotherms and BJH pore-size distribution profiles of
samples S3, S4 and S5
[34]. The H2 hysteresis loop has a smoother adsorption and a sharp desorption step.
This is typical for materials with non-uniform pore shapes and/or sizes. The hyster-
esis loop type of sample S5 is H3 characteristic for slit like pores [35]. These results
show that increasing the BTPTS amount lead to changes in the pore shapes.
For the sensitivity towards RH of the samples at room temperature, Fig. 40.6
illustrates the sensors’ response of the samples. Sample S4 shows a significant
response starting from 60% RH, while other samples show a lower sensitivity. It is
well known that controlling of pore size plays a significant role to obtain better
response towards RH in particular in the range of 20–500 nm [36]. Thus, the
investigated samples are mesoporous materials which have pore sizes of 2–50 nm.
Thus they are favorable to capillary condensation and can be implemented as a
sensing material.
Fig. 40.6 Sensor response towards relative humidity
40.4 Conclusion
On the bases of the experiments which have been presented in the previous sections
we can summarize that:
• The synthesized materials are Class II hybrid tetra sulfide-functionalized hybrid
materials.
• Increasing intensity of bands corresponding to Si-C, S-C and S-S bonds in FT-IR
spectra were observed and also increasing intensity of T the peaks in 29Si MAS
NMR. According to DTA/TG analysis the materials are stable up to 300 C taking
into account exo-effect; according to elemental analysis there is no significant
difference of the sulfur content between the theoretical and experimental.
• Successful co-condensation reactions between BTPTS and TEOS at high BTPTS
amount are achieved in the concentration range from 50 to 62 mol%.
• It was determined that BTPTS amount up to 57 mol% lead to formation of
ink-bottle like pores. Above this concentration (62 mol% BTPTS) the pores in
the materials are of slit-like shape. In the whole concentration range the synthe-
sized hybrid materials are mesoporous.
• Pore size distribution curves form a sharp peak at BTPTS concentration up to
50 mol% which shows that the pores in the materials possess the same size.
Above 50 mol% BTPTS concentration the curves form multiple peaks
corresponding to different pore sizes.
• Additives have no influence on the structure of organic bridging groups in the
final materials but they have influence on the condensation degree and pore
shape.
• The sensing properties of the tested samples towards relative humidity show that
a increasing BTPTS concentration leads to mesoporous materials which have
better response towards RH at room temperature starting from 60% RH, com-
pared to the other samples.
Acknowledgments The authors gratefully acknowledge Professor Jean Marc Tulliani from
department of applied science and technology (DISAT), Politecnico di Torino, Turin, Italy, for
working in his laboratory facilities for gas sensors testing and useful discussions.
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Chapter 41
Humidity Sensing Properties of Tungsten
Based Glass Crystalline Materials
in the WO3-ZnO-La2O3-Al2O3 System
M. Ataalla, Ahmed S. Afify, M. Hassan, A. M. Adam, M. Milanova,

and Iskra Piroeva
Abstract Glass crystalline materials from the WO3-ZnO-La2O3-Al2O3 system

containing high WO3 concentrations (60–76 mol%) were prepared by controlling
the glass crystallization and were then employed as humidity based sensors.
According toX-ray analysis, WO3 separates as a crystalline phase from the amor-
phous structures with the nominal compositions 76WO39.5ZnO9.5La2O35Al2O3
and 60WO37.5ZnO7.5La2O325Al2O3 after the heat treatment. Samples were
characterized by scanning electron microscopy (SEM) and energy dispersive
X-ray spectroscopy (EDS) for elemental analysis. Using the screen printing tech-
nique, the synthesized crystalline glass samples were deposited onto interdigidated
Pt electrodes; then the sensors were tested in the range from 0.0% to 96% relative
humidity (RH) at room temperature. It was observed that the increase in the content
of WO3 leads to improve sensor sensitivity towards RH.
Keywords Glass crystallization · Melt quenching · Relative humidity ·

Screen-printing · Sensors
M. Ataalla (*)
Faculty of Engineering and technology, Badr University in Cairo (BUC), Badr City, Egypt
A. S. Afify
M. Hassan
A. M. Adam
Physics Department, Sohag University, Sohag, Egypt
M. Milanova
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria
I. Piroeva
Academician Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of
Sciences, Sofia, Bulgaria

418 M. Ataalla et al.
41.1 Introduction
Humidity is an important factor for operating certain equipment such as high

impedance electronic circuits, electrostatic-sensitive components, high-voltage
devices, fine mechanics, etc. Nonetheless, moisture is a common ingredient of
most manufactured goods and processed materials. Thus, all these applications
emphasize the importance of sensing and detecting the level of the relative humidity
(RH) [1–3]. WO3 is the most widely used transition metal element in sensor
technology, along with non-transition metal elements like ZnO and SnO2 based
materials [4–6]. As the chemical, physical and sensing characteristics of metal oxide
sensors are affected by the method of synthesis, many preparative routes as
electrospinning [7], solvothermal [8], modified thermal evaporation [9], precipita-
tion [10], flame spray pyrolysis [11], and sol-gel [12] have been used for the
preparation of WO3 and WO3-based gas sensing materials. Thus developing new
preparative routes as well as compositional variations are two perspective aspects to
achieve significantly sensitive and selective gas sensing materials. ZnO is an n-type
semiconductor oxide with a large excitation binding energy (60 meV) and wide band
gap energy (3.37 eV). Due to its significant structural, optical and catalytic proper-
ties, it is often used in many applications [13, 14]. Great attention has been paid to
study the sensing properties of ZnO towards RH and different gases such as
methanol, ethanol, propyl alcohol, and methane [15–18]. Having in mind this
abovementioned research as well as our previous results [19, 20], demonstrating
the possibility, by applying melt quenching and crystallization from glasses, to
prepare materials from the WO3-ZnO-Nd2O3-Al2O3 system for application as gas
sensors for RH and ammonia, now we have extended our studies to investigate the
WO3-ZnO-La2O3-Al2O3 system.
The aim of this study is to synthesize glass crystalline materials from the WO3-
ZnO-La2O3-Al2O3 system containing high contents of WO3 by applying controlled
glass crystallization methods and to validate their sensitivity towards RH.
41.2 Experimental
41.2.1 Synthesis of Glass Crystalline Materials
Batches with the nominal compositions 76WO39.5ZnO9.5La2O35Al2O3 and

60WO37.5ZnO7.5La2O325Al2O3 were prepared using reagent grade WO3, ZnO,
La2O3 and Al2O3 as starting compounds. The homogenized batches from the starting
oxides were melted for 20 min at 1240 C in platinum crucibles in an air atmosphere.
The melt was quenched by pouring and pressing between two copper plates (cooling
rates 101–102 K/s). The as-quenched samples were examined by X-ray phase
analysis with a Bruker D8 Advance diffractometer, using Cu Kα radiation in the
10 < 2θ < 60 range. The glass transition (Tg), crystallization (Tp), and melting (Tm)
41 Humidity Sensing Properties of Tungsten Based Glass Crystalline Materials 419
temperatures and the thermal stability of the glasses were determined using differ-
ential thermal analysis (DTA) (Machine STA, PT1600, TG-DTA/DSC). The
as-obtained glasses were subjected to a heat treatment for 6 h at 530 C, then for
3 h at 550 C, and finally for 12 h at 560 C in platinum crucibles in air atmosphere;
by this way glass-crystalline specimens were obtained. The phase formation of the
glass-crystalline samples was established by X-ray diffraction analysis as above. The
glass – crystalline samples were studied by scanning electron microscopy (SEM) and
energy dispersive X-ray spectroscopy (EDS). SEM analyses were performed with a
JSM 6390 electron microscope (Japan) in conjunction with energy dispersive X-ray
spectroscopy (EDS, Oxford INCA Energy 350) equipped with a ultrahigh resolution
scanning system (ASID-3D) in the regimes of secondary electron images (SEI) and
back scattered electron (BEC) images. Before attempting SEM characterization, the
sample must be clean and completely dry. Surface oils or dirt must be removed with
solvents such as methanol or acetone. The sample was mounted on a double coated
conductive carbon tape that holds the sample firmly to the stage surface and can be
used as ground strap from the sample surface to sample holder. The samples were
carbon coated (time of coating ~20 s) as the upper carbon layer at that thickness will
have little or no effect on the elemental analysis. The accelerating voltage was 20 kV,
I ~65 mA. The pressure was on the order of 104 Pa. The obtained glass and glass –
crystalline samples are listed in Table 41.1.
41.2.2 Humidity Sensor Preparation and the Sensing

Mechanism
The sensors were prepared and tested as follows:

1. Preparation of the interdigitated platinum electrodes: Platinum conducting
paste (ESL 5545, from Electro-Science, King of Prussia, PA, USA) was depos-
ited manually by screen-printing technique onto planar α-alumina substrates
(ADS-96 R, 96% alumina, Coors Tek, USA, 0.85 5 cm) by using a rubber
squeegee through a 270 mesh steel screen; after drying overnight, these devices
were heated at 980 C for 20 min with a 2 C/min heating/cooling ramp to
optimize the electrical conductivity of the electrodes, according to the ink’s
manufacturer recommendations.
Table 41.1 Investigated compositions in the system WO3-ZnO-La2O3-Al2O3

Phases before heat Sample Phases after heat Sample
Nominal composition treatment symbol treatment symbol
76WO3-9.5ZnO- Glass A WO3 + glass C
9.5La2O3-5Al2O3
60WO3-7.5ZnO- Glass B WO3 + glass D
7.5La2O3-25Al2O3
2. Preparation of the screen-printable ink: The ink was prepared by dispersing

the prepared powders in a suitable amount of the organic solvent ethylene glycol
monobutyl ether (Emflow 227, Emca-Remex products, England) to reach the
appropriate rheological behavior, adherence to the substrate and to achieve the
correct thermal shrinkage properties during the process of screen-printing to
obtain a good film.
3. Preparation of the sensing film: Thereafter, the screen-printable ink was depos-
ited onto the interdigitated platinum electrodes by the screen-printing technique
using a rubber squeegee through a 270 mesh steel screen; once these films were
dried, the sensors were heated at 500 C for 1 h with a 2 C/min heating/cooling
ramp. The formed thick film has thicknesses of about 30–40 μm and areas of
about 1 cm2, scotch tests on the fired films revealed a good adhesion onto the
substrates.
4. Testing of the humidity sensors: The sensors were electrically characterized
using a laboratory apparatus made of a thermostated chamber working at 25 C in
which the RH could be varied from 0% to 96%; the experimental details have
been reported previously [21]. RH values were measured by means of a com-
mercial humidity and temperature probe (Delta Ohm DO9406, Italy). Each tested
sensor was alimented by an external alternating voltage (V ¼ 3.6 V at a frequency
of 1 kHz) and then constituted a variable resistance of this electrical circuit. A
2000 Keithley digital multimeter was used to measure the voltage VDC at the
output of the circuit. The sensor resistance was determined by substituting them,
in the circuit, by known resistances and then plotting a calibrating curve R ¼ f
(VDC). The sensor response (SR), expressed in %, was defined as the relative
variation of the starting resistance, compared with the resistance measured under
gas exposure as in Eq. (41.1):

R0 Rg
SRð%Þ ¼ 100 ð41:1Þ
R0
where R0 and Rg are the starting resistance (in the absence of the test gas) and the
gas-exposed measured resistance of the sensors, respectively.
According to the XRD data shown in Fig. 41.1, X-ray amorphous samples were
obtained after quenching of the melt with 76WO39.5ZnO9.5La2O35Al2O3 (sam-
ple A) and 60WO37.5ZnO7.5La2O325Al2O3 (sample B) nominal compositions.
The amorphous nature of the as-quenched samples was also confirmed by DTA
analysis. The DTA curves of the synthesized glasses are presented in Fig. 41.2.
Glasses are characterized with a hump, corresponding to the glass transition
temperature (Tg) followed by exothermic effect connected with the
Fig. 41.1 XRD patterns of glass samples obtained by press quenching of the melt with nominal
compositions 76WO39.5ZnO9.5La2O35Al2O3 (sample A) and 60WO37.5ZnO7.5La2O325Al2O3
(sample B)
Fig. 41.2 DTA curves of glass samples obtained by press quenching of the melt with nominal
compositions 76WO39.5ZnO9.5La2O35Al2O3 (sample A) and 60WO37.5ZnO7.5La2O325Al2O3
(sample B)
crystallization temperatures of the glasses (Tx). The calculated ΔT ¼ Tx-Tg

which is 80 C for the glass sample A and 100 C for the glass sample B exhibits
a good thermal stability of the amorphous specimens obtained. Based on the
Fig. 41.3 XRD patterns of glass-crystalline samples obtained by heat treatment of the parent
glasses with nominal compositions 76WO39.5ZnO9.5La2O35Al2O3 (sample C) and
60WO37.5ZnO7.5La2O325Al2O3 (sample D)
thermal parameters established, the glasses were subjected to a heat treatment for
different times at around the crystallization temperatures Tx.
XRD patterns of the calcined samples are shown in Fig. 41.3. The analysis shows that
glass-crystalline specimens, labeled as sample C and as sample D were obtained after the
heat treatment from the parent glasses with 76WO39.5ZnO9.5La2O35Al2O3 and
60WO37.5ZnO7.5La2O325Al2O3 nominal compositions, containing WO3 as a crys-
talline phase.
SEM analysis of the glass-crystalline sample C confirmed the XRD data obtained.
As can be seen from the SEM image present in Fig. 41.4, the specimen is amorphous
in nature. However the EDX elemental analysis of the sample showed that the
content of the WO3 is near 16 mol% which differs much from the initial composition
(see Table 41.1). This difference can be regarded as evidence that part of WO3
crystallizes and separates from the amorphous part of the sample.
Figure 41.5 illustrates the sensors’ response of samples C and D towards
RH. Sample C shows a significant response towards RH at room temperature starting
from 33% RH, while sample D shows a lower sensitivity.
The response times (the time taken by a sensor to achieve 90% of the total
resistance change in the case of gas adsorption) and the recovery times (the time
necessary to reach 90% of the total resistance changes in the case of gas desorption)
are shown in Fig. 41.3 and summarized in Table 41.2. These response and recovery
times are quite fast of both samples although, sample D is quite faster than sample C
(Fig. 41.6).
Fig. 41.4 SEM image of a sample, obtained after heat treatment of a parent glass with the nominal
composition 76WO39.5ZnO9.5La2O35Al2O3 (sample C)
Fig. 41.5 Sensor’s response towards relative humidity
Table 41.2 Response and recovery time of samples C and D

Humidity change Sample 0–60% RH 0–75% RH 0–95% RH
Response time (min) C 4 3.85 3.41
D 3.92 3.1 3
Humidity change Sample 60–0% RH 75–0% RH 95–0% RH
Recovery time (min) C 1.61 1.8 1.93
D 1.36 1.54 1.76
Fig. 41.6 Response and recovery time of the sensors
41.4 Conclusion
A glass crystallization method was used to prepare glass-crystalline samples after

heat treatment of the parent glasses with 76WO39.5ZnO9.5La2O35Al2O3 and
60WO37.5ZnO7.5La2O325Al2O3 nominal compositions near Tx. On measuring
the sensitivity of samples C and D (glass crystalline samples) towards RH, Sample C
shows a significant response towards RH at room temperature starting from 33%
RH, while sample D shows a lower sensitivity. The response and recovery times are
quite fast for both samples.
Acknowledgments The authors greatly acknowledge Professor Jean Marc Tulliani from depart-
ment of Applied Science and Technology (DISAT), Politecnico di Torino, Turin, Italy, for working
in his laboratory facilities for gas sensors testing and for fruitful discussions and Dr. Amr Mohamed,
Chemistry Department, Taibah University, Saudi Arabia, for his valuable comments on the
manuscript.
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Chapter 42
Green Synthesis of Silver Nanoparticles
Using Lantana Camara Leaf Extract
and Their Use as Mercury(II) Ion Sensor
Didem Demir, Nimet Bölgen, and Ashok Vaseashta
Abstract Silver nanoparticles (AgNPs) were successfully synthesized via a bottom-

up approach by using aqueous extract of lantana camara (LC) leaves as reducing
and stabilizing agent. Characterization studies were done using UV-Vis spectros-
copy and Fourier Transform Infrared Spectroscopy (FTIR). The average size, mor-
phology and shape of the nanoparticles were determined by Scanning Electron
Microscopy (SEM) and Dynamic Light Scattering (DLS). A light brown color
indicated the synthesis of AgNPs, caused by a surface plasmon resonance (SPR)
peak at 460 nm. The silver nanoparticles were used to detect mercury (Hg2+) ions. A
color change of the AgNPs solution from light brown to cloudy white due to
oxidation of Ag0 to Ag+1 ions was observed. A good selectivity of the AgNPs
towards mercury ions in water has been obtained. This method was found to be
simple and rapid for detection of Hg2+ ions and demonstrated a potential to be used
in environmental colorimetric sensor applications.
Keywords Green synthesis · Ag nanoparticles · Colorimetric sensor · Mercury ions
42.1 Introduction
Soil, air and water pollution due to heavy metals such as cadmium, mercury, lead,
copper and zinc has been accepted as a global problem because of the adverse effect
on humans, plants and animals [1]. Among the heavy metals, mercury is one of the
most toxic pollutants in the environment. The presence of mercury in the
D. Demir · N. Bölgen (*)

Mersin University, Engineering Faculty, Chemical Engineering Department, Mersin, Turkey
A. Vaseashta
Institute for Advanced Sciences Convergence, and Int’l Clean Water Institute, Herndon,
VA, USA

428 D. Demir et al.
environment may be the result of volcanic eruptions, rock weathering, natural fires,
burning of fossil oils, its usage in cosmetics, dental amalgams, cement production,
and mercury mining. Long-term exposure to mercury ions, even at very low
concentrations, can permanently damage heart, brain, kidneys, lungs, nerves, and
the endocrine system [2]. Therefore, the research related to detection and monitoring
of these toxic metal ions has attracted significant attention in recent years. Many
instrumental methods such as atomic absorption spectroscopy, fluorescence spec-
trometry and gas chromatography have been reported for detection of mercury ions
[3]. However, these methods have disadvantages such as being expensive, needing
long measurement times, and requiring complicated sample pretreatment and highly-
trained operators. To overcome these limitations, the development of new methods
which are fast, easy, simple; and have low cost is a requirement. Silver particles have
been developed and used in many applications including the detection of mercury
ions, due to their rapid, economic and eco-friendly synthesis procedure [4, 5]. In this
study, AgNPs were green synthesized using an aqueous extract of LC leaves. LC is a
vigorous growing plant and can be reached easily in most of the time in a year. The
synthesis of the AgNPs was determined by UV-Vis and FTIR. The size distribution
of AgNPs was demonstrated by the DLS method; their morphology and shape were
determined by SEM. An easy, simple and low-cost synthesis method allows to use
AgNPs as a colorimetric sensor for detection of mercury ions in aqueous solutions.
42.2.1 Chemicals
LC leaves were collected from the gardens of Mersin University, Turkey. Silver
nitrate (AgNO3) was obtained from Sigma-Aldrich, USA. Distilled water was used
for all the experiments. All heavy metal solutions (ZnSO47H2O, CrN3O99H2O,
CdN2O6, HgCl2, FeSO4 and PbN2O6) were prepared at 1.0 mM by mixing the
requisite amount of heavy metal in distilled water.
42.2.2 Preparation of LC Leaf Extract
AgNPs were prepared by an eco-friendly method using an extract solution of LC

leaves. The leaves of the freshly collected plant were washed several times with
distilled water to remove any dirt. Leaves were dried in an oven at 40 C for 48 h.
and subsequently grounded to a fine powder; 10 g of them were boiled in 100 mL
distilled water at 60 C. After 30 min, the extract was cooled to room temperature,
filtered through a cheese cloth and then centrifuged at 45 100 rpm for 5 min. The
resulting LC extract was kept in a refrigerator at 4 C until further usage.
42 Green Synthesis of Ag Nanoparticles from Leaf Extract Used as Hg (II) Ion Sensor 429
42.2.3 Green Synthesis of AgNPs by Using the LC Leaf

Extract
For the synthesis of AgNPs, the LC leaf extract was used as a reducing agent for
AgNO3 salt to reduce the Ag+1 ions to Ag0. Ten milliliter of the extract was added
into 100 ml of 1 mM of AgNO3 solution at room temperature. A magnetic stirrer was
used to mix the solution for 60 min. After mixing, the solution was kept in dark
condition for 48 h. As a result, the color of the solution was changed from yellow to
light brown, indicating the formation of AgNPs. It showed that aqueous silver ions
could be reduced by an aqueous extract of LC leaves.
42.2.4 Colorimetric Sensing of Hg2+ Ions by AgNPs
Green synthesized AgNPs from LC leaf extract were used as a nano colorimetric
sensor probe for the detection of Hg2+ in aqueous solution at room temperature
(Fig. 42.1). To investigate the sensing ability of AgNPs for different heavy metal
ions, selectivity studies were carried out with various metal ions such as
ZnSO47H2O, CrN3O99H2O, CdN2O6, HgCl2, FeSO4 and PbN2O6 in aqueous
media. The color changes in the AgNPs solution after the addition of various
metal ions were examined by using UV-Vis spectroscopy.
42.2.5 Characterization Studies
FTIR (Frontier Spectrometer, Perkin Elmer, USA) was used to determine the
chemical composition of the LC leaf extract and the synthesized AgNPs. FTIR
analysis was performed with a resolution of 4 cm1 in the wavelength range of
Fig. 42.1 Mechanism of synthesis and colorimetric sensing ability of AgNPs

430 D. Demir et al.
450–4000 cm1. The particle size distribution of the synthesized AgNPs was
characterized by DLS (Zetasizer Nano ZS90, Malvern, England). The AgNPs
were dispersed in distilled water. The surface morphology of the synthesized
AgNPs was investigated using SEM (Supra 55, Zeiss, Germany) after coating with
platinum. The UV-Vis absorbance of the AgNPs was measured using UV-Vis
spectroscopy (Chebios Optimum-One UV-VIS Spectrometer, Italy).
42.3.1 Characterization of AgNPs
The synthesis of AgNPs in aqueous solution of AgNO3 was demonstrated by

measuring UV-Vis spectra of the solution in the wavelength range from 300 to
800 nm, after diluting the sample with distilled water (Fig. 42.2a). In the spectrum a
broad peak observed at near 460 nm indicates the formation of AgNPs. The
transparent color of the silver nitrate solution turned to light brown after addition
of the LC extract. The color change of solution was attributed to the excitation of
SPR [6].
The FTIR spectrum demonstrates the presence of phenolic compounds in the LC
extract, interaction of AgNPs with LC leaf biomolecules and functional groups of the
stabilized AgNPs. The FTIR spectra of the LC leaf extract and the synthesized
AgNPs are shown in Fig. 42.2b. The broad band at 3305 cm1 in both spectra is
characteristic for O-H stretching vibration [7]. The peak at 2190 cm1 is due to the
stretching vibration of aliphatic -CH- groups containing compounds present in the
LC leaf extract while the sharp absorption band at 1704 cm1 is due to molecules
Fig. 42.2 (a) UV-Vis absorption spectrum of the LC extract, a silver nitrate solution, and the
synthesized AgNPs after 30 min and after 48 h; (b) FTIR spectrum of the LC leaf extract and
stabilized AgNPs
containing –C¼O group present in the LC leaf extract [8]. New peaks are observed
in the 900–1400 cm1 region after interaction of LC leaf extract with silver nitrate
solution. The strong band at 1072 cm1 is due to ether linkages and suggest the
presence of flavanones adsorbed on the surface of metal nanoparticles. The imme-
diate reduction and capping of silver ion into silver nanoparticles may be due to
flavonoids and proteins. The flavonoids present in the leaf extract are powerful
reducing agents which may play a role in the formation of AgNPs [9].
Dynamic light scattering studies of the colloidal AgNPs were carried out to
investigate the average size of the particles in the solution. The size distribution of
the synthesized AgNPs is shown in Fig. 42.3a. The average size of the AgNPs was
22.95 nm while the polydispersity index (PDI) of the sample was 0.46, which
showed that the synthesized sample was homogeneous and uniform in size.
The shape and morphology of AgNPs were characterized using SEM as demon-
strated in Fig. 42.3b. AgNPs were observed as aggregated spherical particles with
average particle sizes less than approximately 10 nm. The average particle size of
AgNPs obtained by DLS can be larger than the size obtained by SEM, as here the
hydrodynamic size of the nanoparticles is measured, as a result of attachment of
water on particle surface [10].
42.3.2 Colorimetric Sensing of Hg2+ Metal Ions by AgNPs
The ion detection ability of the green synthesized AgNPs was examined separately
for a range of metal ions including Zn2+, Cr3+, Cd2+, Hg2+, Fe2+and Pb2+. 300 μL of
1 104 M ion solution was added to 3 mL of AgNPs solution. UV-Vis absorption
studies demonstrated that only Hg2+ caused a change in color of the solution and
showed a change in SPR band intensity of AgNPs (Fig. 42.4). This selectivity can be
of advantage for the detection of Hg2+ in the presence of other metal ions.
Fig. 42.3 (a) Particle size distribution of AgNPs; (b) SEM image of AgNPs
432 D. Demir et al.
Fig. 42.4 UV-Vis

absorption spectra of green
synthesized AgNPs in the
presence of heavy
metal ions
42.4 Conclusion
A one step green synthesis of AgNPs was achieved by mixing AgNO3 solution with
LC leaf extract. The extract acted as a reducing agent. The biosynthesized
nanoparticles were evaluated for colorimetric detection of heavy metal ions. The
selective sensitivity of the AgNPs for the detection of Hg2+ ions were probed by
changes in the SPR resonance. This selectivity demonstrated the potential use of
AgNPs for colorimetric detection of Hg2+ in the presence of other metal ions.
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Chapter 43
Highly Ordered AAO Layers for Various
Sensor Applications
S. Kozhukharov, Ch. Girginov, and O. Kostadinova
Abstract Automation is applied in continuously extending fields of application in

the modern communities. In this respect, sensors are indispensable elements of
systems for automatic regulation. Besides, the use of multitudes of sensor elements
enables statistical data acquisition from large time and long distance monitoring.
Consequently, the requirements for application of multitudes of sensor elements
impose a need for elaboration of advanced sensor element production. In this context
anodized aluminum oxide (AAO) layers enable the elaboration of relatively simple,
large scale technology for reliable and durable sensor elements. The present review
is devoted to a summary of the basic concepts related to the elaboration of reliable
and durable sensor elements on the basis of anodized aluminum. Furthermore,
various examples are provided regarding the recent research activities in this field.
Keywords Anodization · Sensors · Anodized aluminium oxide · Relative humidity
43.1 Introduction
The anodization is relatively simple procedure that enables formation of highly

ordered oxide layers. Anodized aluminium oxide (AAO) self-assembled mono-
layers (SAM) [1, 2] have various possible industrial applications. This method
can be used for precise texturing of aluminium roll surfaces for ink-printing on
paper and plastic packaging materials [3–5], and even for flexible solar cell
production [6]. Besides, these layers can successfully be used for large series
of metal oxide semiconductor (MOS), metal dielectric semiconductor (MDS),
S. Kozhukharov · C. Girginov
O. Kostadinova (*)
Section “Solid-State Electrolytes”, Institute of Electrochemistry and Energy Systems – BAS,
Sofia, Bulgaria

436 S. Kozhukharov et al.
and metal oxide semiconductor field effect (MOSFE) high performance transis-
tors and integrated micro-schemes, based on these electronic elements [7, 8].
The AAO pore formation is an object of interest for many years. Abdel-Karim
and El-Raghy [1] summarized the basic steps in the theoretical base of this process.
According to them, the basic concepts for pore initiation by barrier layer break-
throughs, followed by further pore growth by local oxide dissolution were proposed
by Baumann in 1939. Afterwards, this concept was further developed by Keller in
1953, who proposed pore formation by enhanced oxide dissolution caused by local
temperature rises. These concepts are completed by Akahori in 1961, who suggests
that these temperature increases could be sufficient to promote simultaneous elec-
trolyte evaporation and partial Al-melting followed by formation of new oxide
beneath the pores.
Stępniowski and Salerno [2] describe the correlation between the applied process
conditions (i.e. preliminary surface treatment, applied voltage or current density,
temperature, duration, electrolyte composition, etc.) and the resulting AAO pores
morphology and ordering (e.g. pores depth and diameter, average distance between
neighboring pores, etc.). Later in the same chapter, the authors propose this method
for template-assisted electrochemical fabrication of metallic nanowires, giving
examples for Al, Ag, Ni, Bi, Co, Fe, Pt, Pd, Sn, Zn, and even metallic mixtures.
Considering the self-assembling capabilities of AAOs during their formation,
Kumeria [9] and Santos [10] propose the use of AAOs as optical diffraction grids
for optical sensor construction. A schematic view of a highly ordered AAO film in a
H2SO4 electrolyte is presented in Fig. 43.1 [11].
The most remarkable advantage of the anodization process is the relatively easy
control of pore morphology (diameter and depth) and distribution, which has been
demonstrated by various authors [1, 2, 12–15]. Besides, in a previous work [16], it
was demonstrated that the formation of AAO layers with a comb-like topology is
also possible via reaching the breakdown potential. This approach is successfully
used for formation of quasi-periodic quantum dots arrays [17].
Fig. 43.1 Illustration of the

formation of porous oxide
films on pure Al surfaces
after anodization in an acidic
medium 1 – anodised
aluminium oxide layer, 2 –
thin dense part of the layer, 3
– thick porous part of the
layer, 4 – channel shape
pores [11]
43 Highly Ordered AAO Layers for Various Sensor Applications 437
On the basis of the above mentioned facts, the present brief review aims to
summarize the possibilities for sensor element design and production on the basis
of aluminium anodization.
43.2 Basic Concepts
In general, the term “sensor element” comprises all the electronic components which
initiate or modify the parameters of electric signals passing through them, according
to the conditions of their environment [18]. Hence, the sensor elements can be
divided into active and passive sensors, regarding whether these elements generate
or modify the measurable signal. In the former case, the sensors usually serve as
galvanic elements, whereas in the latter case, their ohmic resistance and/or the
capacitive resistance changes, modifying the electric signal parameters [19]. In all
cases, the sensor elements should provide a reliable, measurable and linear correla-
tion between the change of the measurable environment parameter (input variable)
and the electrical signal characteristics (output variable). In this sense, the sensor
elements should possess: (1) an acceptable deviation of the output variable values;
(2) a short response delay time; (3) a high sensitivity; (4) a large detection range
(with a definitely linear correlation between input and output values) [18–20]; (5) a
low output signal hysteresis and (6) a significant difference between the maximal
and minimal output signal values (i.e. max/min output signal range). An example for
sensor response characteristics is shown in Fig. 43.2.
Another important feature of sensor elements is selectivity regarding the com-
pounds which are object of detection. In this sense, anodization provides possibil-
ities for elaboration of highly ordered porous “honey comb” interface structures able
to adsorb only one type of molecules, resulting in high sensor selectivity.
Fig. 43.2 Schematic

illustration of the correlation
between the input and
output characteristics of a
sensor element
43.2.1 Chemical sensors
In general terms, chemical sensors are based on chemical conversion reactions

between an active compound from the sensor element and the compound from the
environment, which is object of detection. The functional principle of this group of
sensors is based on heterogeneous chemical conversions on the AAO interface
relying on adsorption and desorption processes. Thus, the sensing mechanism is
multistage and includes (i) adsorption, (ii) chemical conversion, (iii) desorption. The
chemical reactions should be reversible, in order to guarantee long term reliable
service. Otherwise, the sensor elements can only serve as replaceable critical con-
centration detectors for emergency equipment. Various chemical gas-phase detec-
tion [10, 21–25] and liquid phase [26] sensors are developed.
43.2.1.1 Gas Phase Chemical Sensors
These sensors can be used in various fields of the human activities, like energy
production, transport, environment monitoring, etc. as illustrated in Fig. 43.3.
In this aspect, the AAO layers can be easily modified by incorporation of various
chemically active compounds, and particularly metals and transition elements.
Various examples for incorporation of Fe [27], Ag [28], Cu [29, 30], Co [31–33],
Ni [34], mixed Ni-Cu systems [35] have been demonstrated.
43.2.1.2 Liquid Phase Chemical Sensors
The basic fields of their applications are related to detection of heavy metals or
organic contaminants in drinking and industrial water. Heavy metal detection is
important for the industrial sector, because it enables to quantify the corrosion rate of
Fig. 43.3 Fields of applications of gas-phase chemical sensors

water delivery pipelines, heat exchange, and cooling equipment. Organic contami-
nants are basic objects of monitoring in the cases of drinking water. Acceptable
organic compound contents in the drinking water are defined by Chemical Oxygen
Demand (COD) and Biological Oxygen Demand (BOD) [36, 37]. The latter criterion
is related to the occurrence of potentially pathogenic microorganisms in the water
sources. Furthermore, Navaza et al. [38] describe membrane indicator electrodes as
an entire class of sensors for biomedical analysis.
In this sense, aluminium anodization provides possibilities for the creation of
semi-permeable membranes, after metallic substrate removal usually by dissolution.
In this aspect, Wooten et al. propose multilayered SiO2 – Al2O3 – SiO2 [39] porous
membranes, suitable for this purpose. Such membranes with exactly defined porosity
can be successfully used for elaboration of indicator electrodes for water quality
analysis.
43.2.2 Physical Sensors
This group of sensor elements is based on physical interactions between the sensor
element and its environment, and can be used for determination of parameters (input
variables) like temperature, pressure, mechanical tensions, etc. Nevertheless, the
present brief review is focussed only on sensors for relative humidity and chemical
compounds determination.
43.2.2.1 Humidity Sensors: The Relative Humidity (RH)
RH affects various areas of human activities, revealing generally detrimental effects,

causing corrosion [40] or being an appropriate medium for the development of
various microorganisms [41, 42] which are able to deteriorate various nutrition
[43] and pharmaceutical [44] products, or even harmful for the human health
[45]. At last, high levels of humidity favor destruction in both electrical conductors
[46] and insulation materials [47–49], thus affecting branches as high voltage energy
supply, microelectronics, automation and communications. Obviously, it damages
composition, structure and properties of various hygroscopic materials, causing
remarkable economic losses when such materials are employed. Nevertheless, the
humidity possesses beneficial effects in some cases, such as greenhouse agricultural
[50, 59] and antibiotics production [51]. Some branches of chemical industry, as the
catalyzed steam-reforming of hydrocarbons [52], and storage of explosive materials
[53, 54] also require elevated levels of humidity. All of the mentioned above
branches of human activity emphasize the tremendous importance of humidity
measurement and control. Table 43.1 summarizes the human activity branches
affected by humidity.
The remarkable importance of the RH levels has generated intensive research
activities for elaboration of advanced humidity sensors on the basis of highly ordered
Table 43.1 Human activity branches affected by humidity

No Detrimental effects Beneficial effects
1. Human health Greenhouse plants growth
2. Transport vehicles corrosion Fungal antibiotics production
3. Building constructions deterioration Storage of explosive soil fertilizers,
4. Microelectronic devices shortcircuits
5. High voltage delivery systems breakdowns
6. Undesirable chemical products hydratation
7. Automatic control systems failures
8. Nutrition products deterioration
9. Pharmaceutical products decomposition
AAO layers with elevated adsorption capabilities [55–58]. In this case, the AAO
films favour water vapour adsorption and subsequent capillary condensation. The
condensed thin water layers serve as conductive pathways which close the electric
circuit between additively deposited electrodes (usually Pt) [59, 60].
Another possible construction is by two parallel Al plates with AAO films
deposited face to face [55]. In this case, the sensors serve as electric capacitors, the
capacitance of which varies with the quantity of adsorbed water. In the former
concept, the measurable output signal is the change of the electrical conductivity
(or resistance, respectively), whereas the latter type of sensors change their capac-
itance. In comparison to the conductivity based sensors, the capacitive humidity
sensor elements enable more precise RH value determination, but require modulated
high frequency AC sources.
43.2.2.2 Optical Sensors and Biosensors
The possibility of self-assembled AAO layers to be used as diffractive gratings

proposed by Kumeria et al. [9] and Santos et al. [10] is already successfully used
for optical sensors and biosensors. The AAO based optical sensors provide possi-
bilities for DNA and protein analysis, which is of particular interest for biochemical
analysis for medical applications.
43.3 Conclusions
The present brief review summarizes the possibilities for sensor element design and
production on the basis of aluminium anodization. Besides, some basic concepts and
terminology related to the sensor element characterization were mentioned, due to
their indispensability, when a new sensor element is being developed. Various
examples for chemical and physical sensors for house-hold, industrial, environment
monitoring, and biochemical analysis are given, emphasizing the versatility of the
AAO based sensors. The literature analysis in the present brief review results in
several basic conclusions:
1. The anodization is a relatively simple procedure that enables the formation of
highly anodised aluminium oxide (AAO) self-assembled monolayers (SAM) with
various possible industrial applications. Although this method is object of interest
for many years, the application of the obtained AAO layers was continuously
extending during the recent years.
2. Among the basic advantages is the possibility for incorporation of various metals,
like Al, Ag, Ni, Bi, Co, Fe, Pt, Pd, Sn, Zn, and even metallic mixtures, which can
serve as active compounds of various chemical sensors.
3. Another advantage of the anodization is that the formation of AAO layers with a
comb-like topology is also possible via applying of breakdown potentials.
4. Finally, it can be concluded that the anodization method provides possibilities for
elaboration of high performance advanced sensor elements with versatile
applications.
Acknowledgments The present review work has been performed by the financial support of the
Bulgarian National Scientific Fund, Project T 02 – 27.
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Chapter 44
Individual Bi2O3-Functionalized ZnO
Microwire for Hydrogen Gas Detection
Vasile Postica, Oleg Lupan, Jorit Gröttrup, and Rainer Adelung
Abstract Individual micro- and nanostructures of metal oxides are known to be

highly sensitive to surface phenomena due to their enhanced surface-to-volume
ratio. In this work, an individual Bi2O3-functionalized ZnO microwire (Bi2O3/ZnO
MW) with a diameter of ~2.2 μm was integrated into a sensing device using its direct
transfer and placement in a focused ion beam (FIB)/scanning electron microscopy
(SEM) equipment. The fabricated device was exposed to H2 gas at room temperature
showing a detectable response. The gas response to 1000 ppm is ~28%.
Keywords Hybrid nanocomposite · ZnO · Hydrogen gas sensor · Bi2O3
44.1 Introduction
Being one of the most abundant elements on the earth, hydrogen gas (H2) is one of the
most promising clean, sustainable and renewable energy source. H2 is a highly explosive
and flammable gas when the concentration exceeds 4% in air [1]. Therefore, fast and
reliable detection of hydrogen gas leakage is very important in order to face safety
challenges in the fields where it is widely used. In this context, metal oxides can provide
fast and highly sensitive detection for a large variety of oxidizing and reducing gases,
including H2 down to low concentrations (in range of ppm) [2]. SnO2 and ZnO
nanostructures are widely used for resistive detection of H2 gas [3].
However, in the case of metal oxides nanostructures the elevated temperatures are
necessary for a rapid and highly sensitive detection of gases [3]. In the case of
individual micro- and nanostructures of metal oxides (ZnO, SnO2, etc.) the detection
V. Postica (*) · O. Lupan

Department of Microelectronics and Biomedical Engineering, Technical University of
Moldova, Chisinau, Republic of Moldova
J. Gröttrup · R. Adelung
Functional Nanomaterials, Institute for Materials Science, Kiel University, Kiel, Germany

446 V. Postica et al.
of gases at room temperature is possible [4]. This is attributed to the higher surface-
to-volume ratio of individual nanostructures, which leads to a higher influence of
surface phenomena (adsorption and desorption of gaseous molecules) on the charge
carrier transport through the conduction channel [5].
This huge advantage opens new possibilities to fabricate miniature gas sensors on
flexible and organic substrates [6]. Other important advantages are the ultra-low
power consumption, which is very important for portable and low-power electronics,
and the possibility to detect sub-ppm concentrations of gases [6, 7].
In this work, we integrated an individual p-type Bi2O3-functionalized ZnO MW
into a sensor device for room temperature detection of H2 gas. The hybrid ZnO MW
was connected to Au/Cr pads thus forming a two-terminal device by a Pt complex
using a FIB/SEM equipment. Experimental results and possible sensing mechanisms
are discussed.
44.2 Experimental Section
Bi2O3-functionalized ZnO tetrapod (ZnO-T-Bi2O3) networks were produced by the

flame transport synthesis (FTS) approach, as was reported previously [8]. The ratio
of ZnO:Bi used in this study is 20:1. Morphological, optical, structural, chemical and
micro-Raman properties of the hybrid networks were reported previously, as well as
DFT calculations [8]. Scanning electron microscopy (SEM) and energy dispersive
X-ray spectroscopy were performed as was described in recent work [8]. In this work
we will mainly focused on room temperature H2 gas sensing properties of an
individual Bi2O3-functionalized ZnO MW, which represents a broken arm of a
tetrapod.
The device was fabricated using the procedure reported by Lupan et al. in a
FIB/SEM system [9]. The release of Bi2O3/ZnO MWs from the ZnO-T-Bi2O3
networks was realized by sonication in ethanol followed by the transfer to a SiO2
coated Si (SiO2/Si) substrate and further dispersion to a lower density [10]. Then, the
individual structure was connected to pre-patterned Au/Cr pads on a SiO2/Si sub-
strate using Pt complex. This procedure allows the connection of nanostructures with
diameters down to 30–40 nm [10, 11]. The electrical and gas sensing measurements
were performed as reported previously at room temperature [4].
44.3 Results and Discussions
44.3.1 Morphology and Chemical Characterization
Figure 44.1 shows SEM images of ZnO-T-Bi2O3 networks, as well as of a single

tetrapod arm. It can be observed that the tetrapods are interconnected. The size of
tetrapods varies in a wide range from 20 to 100 μm [8]. The shape of the tetrapod
44 Hybrid ZnO MW for H2 Detection 447
Fig. 44.1 SEM images of (a) ZnO-T-Bi2O3 networks and (b) of a single tetrapod arm
Fig. 44.2 (a) SEM image and (b–d) elemental mapping of a ZnO-T-Bi2O3 network by EDX at
high magnification: (b) Zn Lα1_2; (b) O Kα1; and (d) Bi Mα1. The scale bar for all images is 10 μm
arms in the case of ZnO-T networks hybridized with Bi microparticles is cylindrical,

compared to the hexagonal shaped arms in pristine ZnO-T networks. A previous study
demonstrated that after annealing at 1150 C for 5 h a crystalline Bi2O3 phase was
deposited on the surface of ZnO tetrapods, forming a ZnO/Bi2O3 core-shell microstruc-
tures [8]. Thus, no other particles were observed in the hybrid networks, as in the case of
ZnO-T networks hybridized with Al, Sn and Fe metallic microparticles [8, 12]. Fig-
ure 44.2 shows the elemental mapping of ZnO-T-Bi2O3 tetrapod networks. It can be
observed that Bi is well dispersed on the surface of the ZnO tetrapod.
Fig. 44.3 (a) SEM image of the fabricated device based on an individual Bi2O3-functionalized
ZnO MW; (b) room temperature current/voltage characteristic of the device; (c) Gas response to
1000 ppm H2 at room temperature
44.3.2 Electrical and H2 Gas Sensing Properties
Figure 44.3a shows the SEM image of the fabricated device based on an individual
Bi2O3-functionalized ZnO MW. The diameter of the MW is ~2.2 μm. The gap
between the electrodes is ~5 μm. A room temperature (RT) current/voltage (I/V)
characteristic is presented in Fig. 44.3b, showing the formation of asymmetrical
double Schottky barriers at the Au/ZnO interface. This can be explained by the
higher work function of Au compared to ZnO [13].
The dynamic gas response to 1000 ppm of H2 gas at room temperature is
presented in Fig. 44.3c. The gas response (S) of ~28% was calculated as:

S ¼ ðRg Ra Þ=Ra 100% ð44:1Þ
where Rg and Ra are the resistances of the device under exposure to gas and in the air,
respectively. The response and recovery time were defined as necessary time to
reach and recover 90% of the signal, respectively. The calculated response time is
~150 s, while the recovery time is >400 s. These values are much higher compared to
sensors based on networks of metal oxide nanostructures due to the operation at
room temperature [3]. However, the obtained values are lower compared to individ-
ual Pt-coated ZnO NW reported by Tien et al. [14].
The gas sensing mechanism can be explained based on an ionosorption model
and surface reactions [2, 3]. Under exposure to ambient air, oxygen molecules will
adsorb on the surface of the hybrid ZnO MW by trapping electrons and forming a
surface depletion layer with a higher resistivity compared to the unaffected conduc-
tive core (conduction channel) [2, 3]. Therefore, these surface reactions will lead to a
resistance increase of the device. Under exposure to H2 gas the hydrogen molecules
will be oxidized to H2O molecules by the adsorbed O2 molecules under the release of
electrons to the surface of the ZnO [2, 3]. This will lead to a narrowing of the electron
depletion region and thus to a decrease in the resistance of the device [2, 3]. More
details on the gas sensing mechanism are presented in previous work [8].
44 Hybrid ZnO MW for H2 Detection 449
44.4 Conclusions
In this work, an individual Bi2O3-functionalized ZnO microwire with a diameter of

~2.2 μm was successfully integrated into a sensing device for room temperature
detection of hydrogen gas. The device showed a response of ~28% to 1000 ppm of
H2 with a relatively fast response of ~150 s and a reversible signal, which is very
important for practical applications. Further investigations are necessary to improve
the room temperature gas sensing performances of an individual ZnO MW which are
in progress in our group.
Acknowledgments This research was sponsored partially by the German Research Foundation
(DFG) under the schemes PAK 902 (AD 183/12-2) and by the STCU within the Grant 6229.
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Electrochem Solid-State Lett 8:G230–G232
Part X
Applications: Water Treatment,
Environment and Health
Chapter 45
Improvement of the Catalytic Activity of Pt
through Synergetic Interaction with Co
Perica Paunović, Orce Popovski, Prashant Khadke, Ulrike Krewer,

Goran Načevski, Anita Grozdanov, and Aleksandar T. Dimitrov
Abstract This study is concerned with the preparation and characterization of

electrocatalysts containing Magneli phases as a support material, and different
metallic systems (Co, Pt, and CoPt, Co:Pt ¼ 1:1 wt.), as catalytic phase. The main
idea was to reduce the amount of Pt with the addition of Co as a non-noble metal.
The studied electrocatalysts were tested for water electrolysis in aqueous electro-
lytes, i.e. for hydrogen evolution reactions (HER) and for oxygen evolution reactions
(OER). They were also tested in PEM fuel cells for oxygen reduction reaction
(ORR). The order of activity for HER and OER was the following: CoPt > Pt >
Co, and for ORR: CoPt Pt > Co. Co has been shown as promoter for reducing Pt
particles (the most active monometallic phase), so the reduction of the Pt quantity in
the metallic phase was compensated by smaller particles. Also, the interaction
between the metallic phases increases the intrinsic catalytic activity for all reactions
(HER, OER and ORR).
Keywords Magneli phases · Hydrogen evolution · Oxygen evolution · Oxygen

reduction · d-band center
P. Paunović (*) · G. Načevski · A. Grozdanov · A. T. Dimitrov

Faculty of Technology and Metallurgy, University “SS Cyril and Methodius”, Skopje, Republic
of Macedonia
O. Popovski
Military Academy “Mihailo Apostolski”, Skopje, Republic of Macedonia
P. Khadke
Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, Germany
U. Krewer
Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, Germany
Institute of Energy and Process Systems Engineering, TU Braunschweig, Braunschweig,
Germany

454 P. Paunović et al.
45.1 Introduction
Considering the exhaustinged and limited reserves of fossil fuels [1], the “hydrogen
economy” is pushed as a potential alternative energy supply system instead of the
current fossil fuel based system [1–4]. Also, the hydrogen economy and hydrogen as
a fuel show several crucial advantages such as: the highest calorific value, high
efficiency (>60%) of energy conversion, the possibility to be stored in all aggregate
states, the renewable nature allowing a clean energy system without pollutant
emission [5]. In all segments of the closed loop of the hydrogen economy, such as
hydrogen production, hydrogen storage and conversion to electricity in fuel cells,
corresponding electrochemical reactions occur. Thus, an essential role for assuring
technical and economic efficiency of a hydrogen economy is taken by the electrode
materials involved in the hydrogen electrolysers and fuel cells. The higher the
electrode activity, the lower is the energy consumption in electrolysers, and the
higher is the conversion efficiency to electricity in fuel cells.
Platinum is the most active electrocatalytic metal and commercially the most used
electrode material for hydrogen electrolysers and fuel cells. But, exploitation of Pt
will be seriously limited in the near future, due to its low abundance and high price.
Worldwide platinum resources are concentrated in only two geological settings –
South Africa and Russia [6, 7]. According to Graedel et al. [6], the current Pt
resources will be sufficient to supply 500 million fuel cell vehicles for only
15 years. Besides the transportation sector, the need for energy in other sectors
such as electricity supply for industry and the domestic sector could not be covered.
Similar predictions were given by Lee et al. [8], who calculated that the present
resources of Pt will be enough to supply only 20% of the automotive industry.
Considering this situation of limited Pt resources and a high percentage of uncovered
energy needs, the price of platinum projected on the supply/demand ratio will be
incredibly high.
One of the main challenges in modern hydrogen economy is thus to reduce the
load of Pt in the electrode materials, or even to completely replace it by other active
non-noble electrode materials. One of the approaches has a physical nature and
means increasing the real surface area of the catalytic material through decreasing
the particle sizes. Result of this approach is the use of nano-scaled catalytic mate-
rials. The other approach has a chemical nature and means increasing the intrinsic
catalytic activity through alloying the catalytic material with other chemical ele-
ments. Strong synergism has been perceived when metals (or their compounds) with
dissimilar electronic character have been mixed [9]. In such systems, titania has
shown the highest interaction with corresponding catalytic metal having more
electrons in the outer shell [10, 11]. Synergism of catalytic activity can also be
achieved when metals with similar electronic character are mixed. This phenomenon
has been studied by Nørskov and his collaborators [12, 13], who established that the
position of the d-band is crucial for determining the affinity of d-metals (Pt, Pd, Ru,
Ir, Ni, Co) to the adsorption of H and O. The higher the d-band center regarding to
the Fermi level, the better is the interaction of metal–adsorbates. Metals with larger
45 Improvement of the Catalytic Activity of Pt through Synergetic Interaction with Co 455
atomic radii and electronegativity up-shift the d-band center of Pt and improve its
adsorptive ability and accelerate the overall electrode reaction. The same effect can
be achieved with reducing the particle size of the catalytic material, which lead to a
d-band center closer to the Fermi level, and consequently better adsorption of H or O
[14, 15].
This research is concerned with reducing the amount of platinum in electrode
materials by addition of cobalt and to explain the changes of electrocatalytic activity
for hydrogen evolution, oxygen evolution and oxygen reduction reactions, as result
of the changes in the structure of the electrocatalytic material.
45.2 Electrocatalysts and Electrodes Preparation
The electrocatalysts studied in this paper are prepared by the sol-gel method using
organometallic precursors such as Co-2,4-pentaedionate and Pt-2,4-pentaedionate
(Alfa Aesar and Johnson Matthey GmbH). As catalyst support commercial Magneli
phases (trade name Ebonex®, Altraverda, UK) were used. Organometallic precursor
and catalyst support were dispersed in ethanol separately; after 1 h they were mixed
and dispersed together and magnetically stirred with 900 rpm. Evaporation of the
solvent (ethanol) lasted until a fine powder of the electrocatalyst was obtained. This
material was further thermally treated at 250 C in a reductive atmosphere to remove
organic residues. The prepared electrocatalysts contain 10% metallic phase; the rest
is the catalyst support.
For HER and OER testing, gas-diffusion electrodes (GDE, Fig. 45.1a) were
prepared from the catalyst powders by hot pressing at 300 C. GDE consists of
two layers: the back layer of carbon black acetylene and PTFE, and the front layer of
the catalyst and PTFE [16]. This structure of the GDE provides several functions:
(i) it serves as a carrier catalyst, (ii) it ensures a highly-developed three phase
Fig. 45.1 (a) Gas-diffusion electrode (GDE) used for HER and OER testing and (b) membrane
electrode assembly (MEA) for ORR testing
boundary where electron exchange reaction takes place, and (iii) it separates the
liquid reactants from the gaseous products (H2 and O2) and provides fast transpor-
tation of liquid reactants/gaseous products to/from the three phase boundary [17].
ORR testing was performed using an alkaline (anion) exchange membrane
(AEM) system. A commercial alkaline membrane from Tokuyama Corp, Japan
was used. Both sides of the membrane were coated with the catalytic layers in the
so-called membrane electrode assembly (MEA, Fig. 45.1b). For better adherence
between the catalytic layers and the membrane, the catalytic layer was coated on
carbon paper using anink consisting of 20% vol. solution of the ionomer (Tokuyama
Corp) in isopropyl alcohol (IPA) and an corresponding amount of the electrocatalyst
to reach 1 mgcm1 of catalytic phase over the electrode surface. The electrodes
were merged with the membrane in the MEA system by hot pressing (1.5 bar) at
100 C for 90 s.
45.3 Electrocatalysts Structure
Structural characterization of the electrocatalysts was performed by means of trans-

mission electron microscopy (TEM) and X-ray diffraction (XRD). A TEM micro-
scope (FEI Tecnai G2 Spirit TWIN) equipped with a LaB6 cathode was used for
microscopic observation, while XRD measurements were performed by a X-ray
powder diffractometer Philips APD 15, with CuKa radiation and a constant rate of
0.02 .
In Fig. 45.2 one can see that metallic particles are evenly dispersed on the support
material. Uniform dispersion makes all active catalytic centers (metallic particles) for
adsorption/desorption processes available, which determines the rate of electro-
chemical reactions. This intensifies the total electrochemical reaction at a constant
intrinsic activity of the metallic phase. The size of the Pt particles in the Pt/Ebonex
catalyst is between 5 and 15 nm, while the Co particles in the Co catalyst are in range
of 2–3 nm, although in the darker parts of the image particles with sizes of 10–15 nm
can be observed. In the bimetallic CoPt/Ebonex catalyst, particles of 2–3 nm can be
seen and fewer amounts with sizes of about 5 nm.
XRD spectra are shown in Fig. 45.3. Below each spectrum, the corresponding
XRD spectrum of the pure Magneli phases is shown, to distinguish characteristic
peaks of the metallic phase and the support material. As can be seen, the Pt/Ebonex
catalyst shows two strong and broad peaks characteristic for metallic Pt. The first one
corresponds to the 111 crystal orientation, the second one to 200. According to the
Scherrer equation [18], the average size of 111 crystallites is 8 nm, that of 200 crys-
tallites 6 nm. The XRD spectrum of monometallic Co/Ebonex electrocatalysts shows
characteristic peaks for cubic and hexagonal crystalline Co with sizes near 13 nm.
The corresponding weakly pronounced and noisy peaks highlight the low amount of
this phase within the catalysts, while the size of the main part of the Co metallic
phase is near 2 nm. In the spectrum of the bimetallic CoPt/Ebonex electrocatalyst,
one can see a weak but broad peak at 2θ ¼ 41.8 , corresponding to the solid state
Fig. 45.2 TEM images of the studied electrocatalysts: (a) Pt/Ebonex, (b) Co/Ebonex, (c) CoPt/
Ebonex
PtCo
CoPt/Ebonex
Ebonex
Intensity, arb. units
Pt
Pt/Ebonex
Ebonex
Co(cub) Co/Ebonex
Co(hex) Ebonex
30 40 50 60 70 80
2q, degrees
Fig. 45.3 XRD spectra of the studied electrocatalysts
solution of the CoPt alloy. The size of these particles was 2 nm. This suggests that in
the presence of cobalt, platinum forms smaller particles. Cobalt is a promoter to
reduce the platinum nanoparticle size, as was also observed elsewhere [19, 20].
The results of XRD analysis are in wellgood accordance with those of the TEM
analysis.
The specific surface area of the catalysts was determined using measurements of
isothermal nitrogen adsorption by a Quantachrome NovaWin (version 11.0). The
determined values from the linearized nitrogen adsorption curves are shown in
Table 45.1. Pure Ebonex has a value of 4.2 m2g1, while addition of metallic
phases increases the surface area related to the catalyst support. In the monometallic
systems, addition of Pt insignificantly increases the BET surface area (4.3 m2g1),
Table 45.1 BET surface area Sample BET surface area, m2g1
of the studied electrocatalysts
Ebonex 4.2
and the catalyst support
Co/Ebonex 6.1
Pt/Ebonex 4.3
CoPt/Ebonex 7.6
while addition of Co increases it to 6.1 m2g1. The most developed surface area was
shown the bimetallic CoPt/Ebonex catalyst (7.6 m2g1). The results of the BET
analysis are in accordance with the particle size analysis by TEM and XRD.
45.4 Electrochemical Characterization
Electrochemical characterization of the studied electrocatalysts was performed by

means of cyclic voltammetry in the potential region between the hydrogen and the
oxygen evolution reactions. The measurements were performed with two types of
electrochemical cells. The first one was an aqueous alkaline three-electrode electro-
chemical cell, aimed for water electrolysis. A gas-diffusion type of working elec-
trode was used (Fig. 45.1), a platinum wire as a counter electrode, a Hg/HgO
reference electrode and 3.5 M solution of KOH (p.a., Merck) as an electrolyte.
The cyclic voltammograms of this type of cell are shown in Fig. 45.4a. The second
electrochemical cell was a real (two-electrode) alkaline hydrogen fuel cell, using an
alkaline membrane (Tokuyama Corp) as a solid electrolyte. The MEA (Fig. 45.1)
consisted of a cathode of the studied electrocatalyst and an anode of a commercial
Pt/Vulcan XC-72 catalytic layer (60 wt% Pt), merged with the alkaline membrane.
The cyclic voltammograms of this type of cell are shown in Fig. 45.4b.
Corresponding cyclic voltammograms (CV) (Fig. 45.4) of the same
electrocatalyst for different types of electrochemical cells have similar shapes, but
those scanned in the alkaline fuel cell show more pronounced and better shaped
peaks for characteristic electrode and surface reactions. The following comments
therefore hold for both types of voltammograms.
In the CVs of the Co based electrocatalyst, several characteristic peaks for Co appear.
Peak I (0.98 V vs. Hg/HgO (a) and near 0.09 V vs. NHE (b)) corresponds to the
transition of Co(0) to the Co(II) oxidation state. This is a potential region where
oxidation of hydrogen surface species still occurs. Peak II corresponds to the Co
(II) ! Co(III) transition. This peak is less shaped and widespread as result of only
few transformations occuring. Also, Co(III) ! Co(IV) occurs, which is in accordance
with literature data [21, 22]. The oxygen evolution reaction is denoted as peak III. In the
reverse polarization, transition of the higher valence states of cobalt to Co (II) occurs,
which is observed in peak II’. In both cases this peak is shifted to negative potentials
related to peak II, which points on the irreversibility of the Co(II) ⇆ Co(III) transition.
Fig. 45.4 Cyclic voltammograms of the studied electrocatalysts in (a) an alkaline hydrogen
electrolyser and (b) a real alkaline hydrogen fuel cell
The very little shaped peak I’ corresponds to the Co(II) ! Co(0) transition and to
adsorption of hydrogen adatoms on the electrode. Peak IV denotes the hydrogen
evolution reaction.
In the CVs of the Pt based electrocatalyst, peak I (0.96 V vs. Hg/HgO (a) and
0.065 V vs. NHE (b)) denotes the beginning of the covering the electrode surface
with OH ions. The adsorption of OH ions plays a significant role in the develop-
ment of surface processes on platinum in an alkaline environment [23]. The covering
of platinum with OH ions (oxygen-forming species in anodic oxygen evolution
reactions denoted with peak II) occurs at a potential close to the hydrogen region.
This is the reason why both the anode and cathode parts of the CVs in the area of
charge and discharge of the double layer are not parallel to the abscissa [24].
The CVs of the bimetallic CoPt electrocatalyst contain all characteristic peaks
observed in the previous spectra of the monometallic Co and Pt electrocatalysts.
Adsorption of OH ions over the electrode surface starts from peak I (0.92 V
vs. Hg/HgO (a) and 0.1 V vs. NHE (b)). Also, Co(0) ! Co(II) transformations occur
in the same potential region. The peaks II and II’ correspond to the Co(II) ⇆ Co(III)
transition. Thhe poorly shaped peak I’ denotes the opposite surface reaction of the
peak I – desorption of OH. The peaks III and IV correspond to oxygen evolution
and hydrogen evolution reaction, respectively.
45.5 Electrocatalytic Activity for HER and OER
The electrocatalytic activity of the studied electrodes for HER and OER was
observed in the aqueous alkaline three-electrode electrochemical cell described
above. Polarization curves for both HER and OER (Fig. 45.5) were obtained by
means of steady-state galvanostatic measurements. Converting this curve into a log
(i)/η plot in the region of low current densities allows the determinationof the
exchange current densities for HER. These values are given in Table 45.2.
Analyzing the electrocatalytic activity for hydrogen evolution in the monometal-
lic systems, one can see that the platinum based catalyst shows a better activity than
the Co based. The difference in the overpotential η80 for HER at the reference current
density of 80 mAcm2 is 50 mV (445 mV for Co/Ebonex vs. –395 mV for
Pt/Ebonex). This order of activity was expected considering the intrinsic activities of
pure platinum and pure cobalt. But the bimetallic electrocatalyst shows a consider-
ably better catalytic activity as compared to the monometallic ones, even a 115 mV
lower overpotential than that of the monometallic Pt catalyst. This catalyst contains
only half of the platinum load as the monometallic Pt based catalyst.
To analyze the reasons for the improvement of the electrocatalytic activity of the
bimetallic electrocatalysts, one should consider that the electrocatalytic activity is the
sum of: (i) the intrinsic activity, which is the ability of a material to exchange
electrons with H+, to adsorb discharged H adatoms at the electrode surface and to
desorb H2 from the surface and (ii) the surface activity meaning a higher developed
surface area of the catalytic material available for the adsorbed species. The smaller
the particles size, the higher developed is the surface area. The intrinsic catalytic
activity of some materials can be evaluated according to the value of the exchange
current density, while the surface activity can be recognized by the specific BET
surface area or the particle size.
Fig. 45.5 Polarization curves for hydrogen and oxygen evolution reactions
Table 45.2 Overpotential for HER at a reference current density of 80 mAcm2 and exchange
current density i0 determined from the log(i)/η plot
Sample η80, mV i0, Acm2
Co/Ebonex 445 1.6104
Pt/Ebonex 395 1.8104
CoPt/Ebonex 280 1.9104
The comparison of the values of the BET surface area of the Pt/Ebonex and CoPt/
Ebonex electrocatalysts (see Table 45.1) show that the bimetallic catalyst has a
higher BET value than the monometallic one (7.6 m2g1 vs. 4.3 m2g1). This
higher value of the specific surface area is a result of the smaller Pt particles sizes in
the bimetallic catalysts, which was shown in the TEM and XRD analysis. In the
presence of Co, the size of Pt particles reduces approximately four times (2–3 nm
vs. 5–15 nm). Therefore, one can say that the higher surface activity (size effect)
contributed to the improvement of the electrocatalytic activity of the bimetallic CoPt
based catalyst. Comparing the exchange current densities (see Table 45.2), one can
say that the CoPt electrocatalyst has a higher value, which points at an improved
intrinsic activity. This improvement of the intrinsic activity can be result of both,
hypo-hyper d-interaction between the metallic phase and the Magneli phases, and
hyper-hyper d-interaction between Co and Pt. The first interaction can be considered
as constant in all catalysts studied, therefore the improvement of the catalytic activity
as result of this interaction is the same in all catalysts and included in the presented
values of exchange current densities. So, the increase of the exchange current density
of the bimetallic CoPt catalyst is result only of the interaction between Co and Pt. As
was mentioned in the introduction, combining Co and Pt shifts the d-band center
closer to the Fermi level and consequently improves the adsorption/desorption
affinity of the catalytic material to hydrogen or oxygen adatoms. This can be
achieved by addition of a metal with a larger atomic radius or by reduction of the
Pt particles [13, 14]. In this case, improvement of catalytic activity was caused by the
second reason. Namely, in the presence of Co a considerable reduction of the Pt
particles was observed.
Finally, the improvement of the overall catalytic activity of the bimetallic CoPt
based catalyst with only half the amount of platinum than in the case of the
monometallic Pt based catalyst is the result of both intrinsic and surface effect.
The electrocatalytic activity for HER of the electrocatalysts studied and deposited
on Ebonex as support material is not so good compared with the same bimetallic
systems deposited on multiwalled carbon nanotubes and nano-scaled TiO2 [20]. For
example, the overpotential at the same reference current density of CoPt/ (MWCNTs
+ TiO2) was 140 mV, while the overpotential of Pt/(MWCNTs + TiO2) was 150 mV.
The reason for the poor catalytic activity for HER of the studied systems is the very
low BET surface area of the catalyst support (Ebonex), only 4.2 m2g1, to be
compared with that of MWCNTs of more than 250 m2g1.
The electrocatalytic activity for OER can be seen from the polarization curves
shown in Fig. 45.5 (upper curves). The trend of the catalytic activity is similar to that
for HER. The monometallic Pt sample shows a slightly better activity than the Co
based sample. This low difference is because Co is an appropriate catalyst for OER,
considering its transition from metallic to Co(II) and further to the Co(III) oxidation
state as was shown in the CVs in Fig. 45.4. In the region of oxygen evolution Co is
present as Co(III)oxide, which facilitates the OER. The bimetallic electrocatalyst
shows also in the case an improved catalytic activity as compare to the the mono-
metallic ones. The overpotential at the reference current density of 80 mAcm2 was
490 mV for the Co, 475 mV for the Pt and 425 for thr CoPt based system. The
explanation for the improvement of the electrocatalytic activity for OER is the same
as in the case of HER, i.e. it is the result of both intrinsic and surface effect.
But, in contrast to the poor catalytic activity for HER, the studied electrocatalysts
show a very good activity for OER [25–27]. This is due to active participation of the
support material (Magneli phases) in the overall catalytic activity of the electrode
material. Namely, Ebonex (Magneli phases) are non-stoichiometric oxides of tita-
nium, and as oxides predestinated for OER. So, in addition to the metallic catalytic
phase, also the rest of the electrode material is catalytically active. The surface of the
oxide electrode possesses a high energy content and a strong hydrophilicity [28]. As
a result, the electrode surface interacts with water molecules and covers itself with
OH ions, which are responsible for the high electrocatalytic activity for oxygen
evolution. They behave as weak acids or bases and exchange protons with the
solution. This is the basis of the mechanism by which the inner sites can be active
in reactions involving water molecules [29].
One of the key advantages of catalysts deposited on Magneli phases aimed at
oxidative electrode reactions is their high chemical stability as compared to similar
catalytic systems deposited on carbon. Namely, carbon can be oxidized easily during
the oxidative electrode reaction, especially at the high potentials present during
electrolysis, causing the so-called carbon monoxide poisoning of PEM fuel cells
or hydrogen electrolysers [30].
45.6 Electrocatalytic Activity for ORR
The testing for ORR was performed in a real (two-electrode) alkaline hydrogen fuel
cell (AHFC), using an alkaline membrane (Tokuyama Corp) as a solid electrolyte.
The polarization curves of the studied electrocatalysts are shown in Fig. 45.6. The
registered potential of the potentiodynamic polarization measurements was the
actual voltage of the fuel cell (cell voltage). More precisely, the polarization curves
reflect the performance of the fuel cell rather than the OER activity. But, taking into
consideration that the other electrode reaction, the hydrogen oxidation reaction
(HOR), has a very low overpotential, one can assume that the cell voltage is close
to the OER overpotential.
Comparing the activity of the monometallic electrocatalysts on Ebonex, the Pt based
sample shows a better activity than the Co based one, which was expected according to
the intrinsic activity of the pure metals. But, comparing the monometallic Pt sample and
the bimetallic CoPt system, one can see that they show very close catalytic activities for
ORR. In some parts of the polarization curves pure platinum shows a better activity, in
other parts CoPt. However, the bimetallic catalysts contains only half of the amount of Pt
than the monometallic, and its activity for ORR can be considered as a good achieve-
ment in comparison to the activity of monometallic Pt catalyst.
Fig. 45.6 Change of cell voltage with change of current in an alkaline membrane fuel cell for
various catalysts at 60 C
Comparing the activity of the commercial Pt catalysts deposited over Vulcan

XC-72 (60 wt% Pt), one can see that the studied samples have much lower activities.
The reason of this poor activity compare to the commercial Pt catalyst can be
explained as follows: the Pt content in the whole commercial catalyst is 60 wt%,
while the content of the metallic phase in the studied electrocatalyst is only 10 wt%.
So, to achieve a load of 1 mgcm1 of the metallic phase over the electrode surface,
only one layer of the catalyst is needed in the case of the commercial Pt, while in the
case of the studied catalysts this would be too many layers. Therefore, the electrodes
with studied catalytic systems become significant three-dimensional structures as
compared to the usually thin electrodes. In a two-dimensional electrode the whole
amount of the metallic phase is available for electrode reactions, while this is not
case in a three-dimensional electrode. So, less than 10 wt.%, of metallic phase are
available for electrode reactions, in contrast to the whole 60 wt.%. Pt in the case of a
commercial Pt/Vulcan electrode. But with increasing content of the metallic phase,
the catalysts deposited on Magneli phases can be considered as very promising
electrode material for both OER and HOR in AHFC.
45.7 Conclusion
The results of this research have shown that mixing Co with platinum in an
electrocatalytic material for water electrolysis or fuel cells is an appropriate approach
for reducing the content of platinum and to reach the same activity or even exceed
considerably the activity of catalysts with pure platinum as metallic phase.
The improvement is result of: (i) a surface effect, i.e. reducing the Pt particle size
in the presence of Co for four times which increases the real surface area of the
catalyst and (ii) intrinsic effects between Co and Pt, i.e. Co reduces Pt particles,
which causes a shift of the d-band center closer to the Fermi level and consequently
an improvement of the adsorption characteristics toward H, O and other adsorbates.
The studied bimetallic electrocatalytic system deposited on Magneli phases
(non-stoichiometric oxides of titanium) are very promising for electrodes on which
oxidative reactions occur, especially for the oxygen evolution reaction. There are
two main reasons for that: (i) Magneli phases behave not only as catalyst support but
also as active electrocatalyst for oxygen evolution and (ii) the oxide nature of the
support material which is the dominant fraction in the entire catalyst shows a high
chemical stability compared with carbon based support materials which can easily be
oxidized and cause the so-called CO poisoning of hydrogen electrolyser or fuel cell
and lead to electrode dissolution even for electrolysers.
Acknowledgments This paper has been supported by DAAD, Germany, and most of the research
was carried out at the Max Planck Institute for Dynamics of Complex Technical Systems, Magde-
burg. Great thanks to the colleagues Maurizio Avella and Gennaro Gentile from the Institute for
Chemistry and Technology of Polymers, Napoli, Italy, for their collaboration on TEM observation
and analysis. Also thanks to Elefteria Lefterova from the Institute of Electrochemistry and Energy
System within the Bulgarian Academy of Sciences, Sofia, Bulgaria, for useful consultations
connected with XRD analysis.
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Chapter 46
Antibacterial Coatings for Biomedical
Applications
P. Písařík, M. Jelínek, J. Remsa, and J. Mikšovský
Abstract Diamond like carbon (DLC) and Ag-doped DLC (Ag-DLC) films were
prepared by dual pulsed laser deposition using graphite and silver targets and two
KrF excimer lasers. The silver concentration in the films was varied from 1.1 to
9.3 at. %. The surface topography was analysed by atomic force microscopy. The
pure DLC was very smooth, but the roughness increased with rising silver content.
Ethylene glycol, diiodomethane and deionized water were used to measure contact
angles (CA). The measurements for water showed that the CA of Ag-DLC films
(78–98 ) was higher than that of the DLC film (77 ). In order to understand the
influence of incorporated Ag on the wettability, the surface energy and the protein
adsorption as an indirect measure of the hemocompatibility were calculated. The
surface energy of DLC and Ag-DLC films was same. The hemocompatibility was
examined by the adsorption ratio of albumin/fibrinogen as an indirect method and
improved with the increase of the Ag concentration. The antibacterial activity of the
films were evaluated by bacterial eradication tests with Staphylococcus aureus and
Pseudomonas aeruginosa at different incubation times. DLC and Ag-DLC films
demonstrated good results against Staphylococcus aureus and Pseudomonas
aeruginosa, meaning that DLC and Ag-DLC can be useful to produce coatings
with antibacterial properties for biomedical devices such as sensors.
Keywords Silver doping · Diamond like carbon · Thin films · Dual pulsed laser
deposition · Antibacterial properties
P. Písařík (*) · M. Jelínek · J. Remsa · J. Mikšovský

Institute of Physics of the Czech Academy of Sciences, Prague, Czech Republic
Faculty of Biomedical Engineering, Czech Technical University in Prague, Kladno, Czech
Republic

468 P. Písařík et al.
46.1 Introduction
While the antibacterial effects of silver are known for more than a thousand years,
the nanoparticle form is researched for about a hundred years. With the development
of nanotechnologies, the attention is again focused on silver nanoparticles, especially
for their antibacterial properties. These were tested and verified.
Metal nanoparticles, compared to bigger ones, exhibit higher inhibition effects
and potential for a removal of chemical and microbial pollution. The properties of
nanoparticles strongly depend on size and shape, because a small size means a higher
surface area that can interact with microorganisms. The smaller the particles the
higher their catalytic activity [1]. The main trend nowadays is the utilization of
nanolayers applied on a specified material surface. Silver nanoparticles are strongly
fungicidal, algicidal, and bactericidal even at relatively low dosage, which enables
their use in medicine, healthcare, and pharmacology for manufacturing antibacterial
materials and disinfectants.
The exact nature of the toxic effect is still discussed, especially if the cause are
nanoparticles or silver ions that emerge [2]. Toxic effects of silver on microor-
ganisms are observed not only for silver ions, but also for silver compounds
[3]. Some studies show that the decisive factor for silver toxicity is the positive
ion charge. Due to electrostatic attraction between a positively charged silver
surface and a negatively charged membrane surface the nanoparticle bonds to cell
surface [3].
Nanoparticle penetrating cell walls can damage the cell inner structure, but this
effect is strongly dependent on the cell species. The silver toxicity on gram-negative
bacteria depends on nanoparticle concentration and closely correlates with the semi-
permeability of cell membrane [4]. Gram-positive bacteria exhibit higher resistance
for silver nanoparticles than gram-negative bacteria, caused by cell wall composition
and the presence (or lack) of extracellular polymers [5, 6].
The silver antimicrobial activity is manifesting on several levels. The
nanoparticles can damage the cell wall either by itself or by releasing silver ions or
by forming reactive oxygen compounds [7]. Silver nanoparticles generate free
radicals inside microorganisms, which disrupt the cell function [3]. Silver blocks
electron transfer between breathing cycle enzymes and reacts with SH- groups of
oxidation enzymes by stopping cell metabolisms, and the cell dies [6, 8].
Incorporation of selected metallic elements (silver) into diamond-like carbon
(DLC) has emerged as an innovative approach to add unique functional properties
to DLC coatings, thus opening up a range of new potential applications in fields as
diverse as sensors, tribology, and biomaterials.
46 Antibacterial Coatings for Biomedical Applications 469
46.2 Experimental
46.2.1 Layers Preparation
Silicon (100) wafers were used as substrates. DLC and Ag-DLC films were prepared
by dual PLD using graphite and silver targets and two KrF excimer lasers
(λ ¼ 248 nm, τ ¼ 20 ns) [9, 10]. Both systems were running simultaneously, the
fluxes of materials intersected on the substrate. The carbon and silver flows were
regulated by the laser repetition rates (atomic silver contents from 1.1 to 9.3 at. %).
The number of pulses were adjusted to reach approximately the same layers thick-
ness (100 nm). The base vacuum of the coating system was 5 104 Pa. The films
were deposited in argon ambient (0.25 Pa). More information and the deposition
parameters are summarized in Table 46.1 and in [10].
Thickness The films thickness was determined using the Alphastep IQ mechanical
profilometer (KLA Co.). The alphastep profilometer with a diamond tip (radius
5 μm, 60 ) scanned 2 mm film surface [10].
Composition Wavelength dispersive X-ray spectroscopy (WDS). The composition
of Ag-DLC thin layers was determined by an electron microprobe using WDS. The
WDS was performed using a JEOL 840. The energy of the primary electrons was
kept at 5 keV to minimize their penetration depth and the absorption of emitted
X-rays. For this energy, the electron spot diameter was estimated to be in the range of
1–2 μm, which gives information at a depth of about 0.5 μm. The accuracy of the
measurement of Ag and C using the STRATA program was better than 5% [10].
Morphology Atomic force microscope (AFM) measurements were realized in the
dynamic regime with Etalon HA_NC tips (6 nm or higher curvature) on a Solver
Table 46.1 Deposition conditions and silver contents

Laser 1 – carbon Laser 2 – silver
(LED ¼ 8 J∙cm2) (LED ¼ 5 J∙cm2) WDS
RR (Hz) RR (Hz) SC (at. %)
DLC 45 0 0.00
Ag-DLC-1 45 1 1.07
Ag-DLC-2 45 2 2.44
Ag-DLC-3 45 3 3.49
Ag-DLC-4 45 4 4.90
Ag-DLC-5 45 8 9.34
RR repetition rate, SC silver content, LED laser energy density
NEXT (NT-MDT) device. Several AFM scans (10 10 μm2 and 50 50 μm2) with
2048 2048 digital resolution were performed and quantified in terms of roughness
average (Sa) and root mean square (Sq), adapted from ISO 4287/1 (Gwyddion
2.39) [10].
Contact Angle (CA), Surface Free Energy (SFE) The film wettability was mea-
sured using distilled water, diiodomethane and ethylene glycol by a contact angle
measurement system (DSA100, Krüss Company). The droplet volume was
1.5 0.2 μl. The humidity was 25 5%, the temperature 22 1 C. The
Dropshape3 analysis program was used for contact angle and surface energy anal-
ysis, the Laplace method for profile extraction, and the extended Fowkes method for
calculations of the disperse and polar parts of the surface free energy [10, 11].
The fractional polarity (FP) is a sensitive indicator of the surface energy and gives
information about cell adhesion. It is defined as the ratio of the polar component γ P
and the total SFE (polar component γ P, dispersive component γ D) [12]
γP
FP ¼ ð46:1Þ
γP þ γD
The interfacial tension γ SL determines the wetting characteristics and hence, the
shear stress generated when the liquid come into contact with the surface [13]. First
we calculated total surface energy (γ SV) of the DLC and Ag-DLC films using
following expression [14, 15]:
qffiffiffiffiffiffiffiqffiffiffiffiffiffiffi qffiffiffiffiffiffiffiqffiffiffiffiffiffiffi
γ LV ð1 þ cos θÞ ¼ 2 γ LV
P γ SV
P þ 2 γD
LV γ SV
D ð46:2Þ
where is contact angle, γ SV

P
and γ SV
D
are the polar and dispersive components of the
surface energy of DLC and Ag-DLC films, and γ LV P
and γ LV
D
the polar and dispersive
components of the surface energy of the testing liquids, respectively (Table 46.2)
[14, 15]. Because there are two unknowns, γ SV P
and γ SV
D
, in Eq. (46.2), two liquids
with the known dispersive and polar components are needed to solve it. In this work,
distilled water and diiodomethane were used.
The interfacial tension (γ SL) between the solid surface and biological fluids
(blood, fibrinogen, immunoglobulin G and albumin) was calculated using the
equation [14, 15]:
qffiffiffiffiffiffiffi qffiffiffiffiffiffiffi2 qffiffiffiffiffiffiffi qffiffiffiffiffiffiffi2
γ SL ¼ γ LV
P γ SV
P þ γ LV
D γ SV
D ð46:3Þ
The energetic characteristics (polar and dispersive components of the surface

energy) of the biological liquids are shown in Table 46.3 [14, 15].
Antibacterial Properties In the in vitro anti-bacterial tests, the method described in
[10] was employed to determine the antibacterial performance against Pseudomonas
aeruginosa ATCC 27853 (gram-negative) and Staphylococcus aureus ATCC 6538
Table 46.2 Surface energy of the testing liquids [14, 15]

Test liquid γ LV
D
(mJ∙m2) γ LV
P
(mJ∙m2) γ LV (mJ∙m2)
Distilled water 21.8 51.0 72.8
Diiodomethane 50.8 0.0 50.8
Ethylene glycol 30.9 16.8 47.7
Table 46.3 The surface energy of the biological liquids and plasma proteins [14, 15]
Biological liquid γ LV
D
(mJ∙m2) γ LV
P
(mJ∙m2) γ LV (mJ∙m2)
Blood 11.20 36.30 47.50
Fibrinogen 24.70 40.30 65.00
IgG 29.46 35.53 64.99
Albumin 31.38 33.62 65.00
(gram-positive) bacterial strains (Czech Collection of Microorganisms, Brno, Czech

Republic). The tested layers (1 1 cm2) were washed with PBS, sterilized in the
autoclave and placed into 12-well culture plates. 50 μl of bacterial suspension
were placed on the tested layers, covered with glass cover slip and incubated at
35 C. After 3 h, 450 ml of PBS was added and the bacterial suspension was serially
diluted down to 106 to 107 in PBS. 1 ml of each diluted sample was spread onto an
agar plate (Caso-Agar, Mercoplate®, Merck); the plates were incubated overnight
and the number of colony forming units (CFU) was counted using the ImageJ
software (National Institutes of Health, Bethesda, MD, USA). The layers were tested
in triplicate. A clean Si (100) substrate was used as a control sample. The bactericidal
efficacy in % expressing the antibacterial properties of different DLC and Ag-DLC
films was estimated using the following formula (46.4), where Groupref and
Groupexp stand for the number of live bacteria colonies in the reference group and
the experiment group, respectively [10]:
Groupref Groupexp
Bactericidal Efficacy ¼ 100% ð46:4Þ
Groupref
Composition The Ag content varied from 1.1 at.% to ~9.3 at.% (WDS)
(Table 46.1), the thickness was 100 30 nm on Si 100 substrates.
Morphology AFM showed the pure DLC to be very smooth (Sa around 0.137 nm and
Sq around 0.179 nm); the roughness increases with rising silver content (Sa around
3.87 nm and Sq around 4.94 nm for 9.34 at. %) for 10 10 μm2 scans. For 50 50 μm2
scans the values were slightly higher, as expected, but the trend is the same. The layers
with silver contained significantly more droplets than undoped DLC films, with rising
silver content the number of the droplets increased and their size rose only a little
(Fig. 46.1),
Contact Angle, Surface Free Energy The contact angle values for distilled water
are smallest for undoped DLC (76.7 ) and highest (97.9 ) for 9.3 at. % content of
silver (Fig. 46.2). Usually, a hydrophobic surface has a CA higher than 70 , while a
hydrophilic surface has a CA value lower than 70 . These results imply that Ag-DLC
films are more hydrophobic. For ethylene glycol there is lower CA for doped DLC
Fig. 46.1 Typical AFM surface of pure DLC (up) and Ag-DLC (down) films
Fig. 46.2 Change of CA

with the silver
concentrations (Lines are
added as a guide for the eye)
(39.1–42.7 ) than pure DLC (49.3 ). Ag-DLC layers exhibited higher contact angles
for diiodomethane (46.5–49.5 ) than for pure DLC (44.8 ). This is the same trend as
in [16, 17]. Calculated SFEs did not change with the silver content. The disperse part
is the main component of the surface free energy (Fig. 46.3). Hydrophobicity (higher
contact angles and lower SFE) is considered to be one of the properties that could
positively affect the antibacterial properties [18].
Fraction Polarity(FP) The cell adhesion is mostly dependent on the polar compo-
nent and there is practically no change due to dispersive component [19]. Best
cellular adhesion (for fibroblast) should be for a fraction polarity of 0.3 [19]. For
higher Ag concentrations FP does not change. The highest value of FP was reached
by the layer with 1.1 at.% and undoped DLC (Table 46.4).
The calculated total surface energy (γ SV) of the DLC and Ag-DLC films, it’s polar
and dispersive components (γ SVP
and γ SV
D
) determinated from the linear fitting of
Eq. (46.3) are show in Table 46.4. The γ SV of the DLC and Ag-DLC films was
between 39.19 mJ∙m2 (2.4 at.%.) and 43.72 mJ∙m2 (1.1 at.%). We did not observe
Fig. 46.3 Change of the 50

SFE (polar and disperse Dispcrsc part Polar part
Surface free energy SFE [mJ.m-2]
component) with the silver

concentration 40
30
20
10
0
0 1 2 3 4 5 6 7 8 9 10
Silvet content [at. %]
Table 46.4 Calculated fraction polarity and energy components for DLC and Ag-DLC films
Surface energy (mJ∙m2) γ SL (mJ∙m2)
Ag FP γ SV
D
γ SV
P
γ SV Water Blood F IgG A Ratio of A/F
0.0 0.11 34.66 5.86 40.52 23.77 19.45 16.27 12.75 11.49 0.71
1.1 0.13 39.71 4.01 43.72 29.08 24.92 20.66 16.43 14.90 0.72
2.4 0.06 38.23 0.97 39.19 40.21 33.46 30.25 25.34 23.52 0.77
3.5 0.07 38.95 1.20 40.15 39.01 32.66 29.19 24.32 22.51 0.77
4.9 0.06 39.15 0.67 39.82 42.49 35.57 32.22 27.12 25.22 0.78
9.3 0.03 40.05 0.07 40.12 50.12 42.14 38.93 33.32 31.21 0.80
Ag silver content (at. %), F fibrinogen, A Albumin
a decrease in the surface energy due to the decrease in SFE as publish in [16]. In our
case, SFE was constant and therefore (γ SV) is a constant too.
The calculated interfacial free energy (interfacial tension γ SL) between DLC
(or Ag-DLC films) and water, blood and plasma proteins (fibrinogen, IgG, albumin)
is summarized in Table 46.4, too. The interfacial tension between water and DLC
(Ag-DLC) films increased with the silver content in the layer. The interfacial tension
increased from 23.8 mJ∙m2(pure DLC) to 50.1 mJ∙m2 (Ag-DLC 9.3 at. %). The
same trend of results are obtained for the interfacial tension for blood, fibrinogen,
IgG and albumin. The results indicate that layers with Ag increased the plasma
protein absorption, which in turn may cause decreased blood coagulation [15]. An
absorption of albumin in high amounts would inactivate the blood-materials inter-
face, while fibrinogen adsorbed in high amounts would favor platelet adherence and
the activation of blood coagulation system. The adsorption ratio of albumin/fibrin-
ogen increased with increasing silver content (Table 46.4).
Antibacterial Properties DLC layers doped with various concentration of silver
were tested for their antimicrobial effects against the bacterial strains Pseudomonas
aeruginosa and Staphylococcus aureus. A comparison of their bactericidal efficacy
after 3 or 24 h cultivation expressed as percentage of killed cells is present in
Fig. 46.4 The antibacterial

efficiency of Ag-DLC layers
after 3 h (A) and 24 h
(B) (Lines are added as a
guide for the eye)
Fig. 46.4. The antibacterial efficiency of the films increased with the Ag concentra-
tion (Fig. 46.4). The layers with the highest silver content (9.3 at. %) exhibited
a antibacterial efficiency of 98.6% for Pseudomonas aeruginosa, and 81.6% for
Staphylococcus aureus after 3 h (Fig. 46.4). For the same samples, the antibacterial
efficiency rose after 24 h to roughly 100% for both gram-negative and gram-positive
bacteria. Our results demonstrate unequivocally the excellent antibacterial properties
of Ag-doped DLC and correspond with [20], but our values of efficiencies are
substantially higher.
46.4 Conclusions
Silver doped DLC layers were grown by the dual pulsed laser deposition technology
using silver and graphite targets and two lasers. The Ag content increased from 1.1 to
9.3 at. % (WDS). AFM showed the pure DLC to be very smooth but an increasing
roughness with rising silver content. The water contact angle rises with increasing
silver content, thus the layers become more hydrophobic. The interfacial tension
increased from 23.8 (pure DLC) to 50.1 mJ∙m2 (Ag-DLC 9.3 at. %). The same
trends apply to the interfacial tension for blood, fibrinogen, IgG and albumin. The
adsorption ratio of albumin/fibrinogen increased with increasing silver content,
which in turn may decrease blood coagulation. The antibacterial effects increased
with the Ag concentration, while the maximum antibacterial efficiency of the 9.3 at.
% Ag-DLC was 100.0% for Staphylococcus aureus and 99.9% for Pseudomonas
aeruginosa after 24 h. Our results demonstrate that Ag doped DLC films are
potentially useful biomaterials, e.g. sensors having both good blood compatibility
and antimicrobial characteristics.
Acknowledgments This work has been supported by the Grant Agency of the Czech Technical
University in Prague (grant No. SGS16/190/OHK4/2T/17), the Grant Agency of the Czech Repub-
lic (grant No. GA15-05864S) and the Ministry of Education, Youth and Sports of the Czech
Republic (grant No. LO1409).
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(2012) In vitro cyto and blood compatibility of titanium containing diamond-like carbon
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films on surface properties and protein adsorption. Diam Relat Mater 17(3):252–257
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Relationship between surface properties (roughness, wettability) of titanium and titanium alloys
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Chapter 47
Identification and Evolution of Biocatalysts
of Interest
Ioannis V. Pavlidis
Abstract Enzymes are potent biocatalysts for the detection and degradation of
chemical warfare agents, due to their activity under mild conditions, the minimiza-
tion of toxic intermediates, and their high specificity. Despite their numerous
advantages in comparison to chemical catalysts, their application is hindered from
the difficulty to identify enzymes which are active against a specific agent, as well as
to optimize their catalytic activity for a desired process. Recent advances in the field
of molecular biology and biotechnology promoted significantly these efforts and
pave the way for a vast spectrum of applications, including the biocatalytic
processing of chemical warfare agents. Herein, current methods for the identification
of enzymes with desired properties are described as well as methods to further
evolve the identified enzymes, in order to meet the needs of the desired process.
As an example, the application of protein engineering on enzymes active on
organohalogen compounds is discussed.
Keywords Protein engineering · Rational design · Directed evolution · De novo

design · Organohalogen compounds
47.1 Introduction
Biocatalysis is an established alternative to chemical catalysis for a wide variety of

applications, such as organic synthesis of products or building blocks for different
industrial branches (such as pharmaceutical, food and cosmetic industry), remedia-
tion and sensing. The use of biocatalysts and whole cells for the bioremediation of
chemical warfare agents and other pollutants possesses a great potential, as several
enzymes have been identified to be able to degrade nerve and blister agents
I. V. Pavlidis (*)
Enzyme Technology Laboratory, Department of Chemistry, University of Crete, Voutes
University Campus, Heraklion 70013, Greece

478 I. V. Pavlidis
[1, 2]. The main advantage of the application of enzymes compared to chemical
decontaminants is that biocatalysis, in most cases, is environmentally friendly, while
chemical decontaminants like bleach and other antioxidants are toxic, they can
generate toxic by-products and they can be aggressive on materials. Moreover,
enzymes, in most of their applications, exhibit high specificity and selectivity thus
enabling for instance the production of optically pure products. However, the major
challenge in biocatalysis is to identify enzymes that fit to the desired processes. For
instance, many of the pollutants and warfare agents are synthetic, as a result of
anthropogenic activity, and thus nature did not evolve so far any efficient biocata-
lytic toolbox to degrade them. The same holds for novel active pharmaceutical
ingredients. Even if some wild-type enzymes can perform the desired reaction, the
efficiency of the process does not grant the application in an economically feasible
large scale. Thus, there is a constant need of engineered tailor-made biocatalysts, in
order to be able to develop efficient biocatalytic applications. Some of the enzyme
features of wild-type enzymes requiring optimization are the substrate scope, the
specificity, the catalytic efficiency, the stability, and the elimination of any potential
substrate or product inhibition [3]. Several techniques of enzyme identification and
protein engineering have been developed the last years to address this demand;
together with the advances in the fields of molecular biology and bioinformatics they
paved the way for the fourth wave of biocatalysis [4].
47.2 Enzyme Identification
Protein engineering efforts require a template, and in most cases one of the most
difficult questions to answer is: “which protein do I use as a scaffold?”. This first
question is, in most cases, the most important, as the success of the engineering
efforts relies on this decision. If there is a known scaffold with minimal activity for
the desired reaction, this should be used as a template [5]. In the case that there is no
biocatalyst with the desired activity known, there are three major methods of enzyme
identification: (i) screening for enzymes in the genome of organisms in contaminated
areas, (ii) screening the sequencing data, and (iii) de novo design of a biocatalyst.
A well-established approach for enzyme identification is to rely on the evolution-
ary mechanism of nature and screen for the desired biocatalyst in the environment. In
this method, which is widely used in bioremediation processes, samples collected
from contaminated areas are screened for microorganisms that can survive in the
presence of the contaminant (the compound is added in a specific concentration in
the cultivation medium), or use it as sole carbon source (use of minimal medium with
the compound of interest being the only one containing carbon). If a microorganism
has a catalytic machinery for the desired process, further investigations follow in
order to identify which enzymes are involved. A recent successful application of this
approach is the identification of a bacterium that degrades poly(ethylene terephthal-
ate) (PET) [6]. As known, the accumulation of PET plastics is a significant challenge
of our age, and—as PET is a synthetic material—at that time there was not any
47 Identification and Evolution of Biocatalysts of Interest 479
known enzymes active on this polymer. Yoshida and coworkers collected samples
from contaminated areas and screened for microorganisms that could grow, using a
PET film as the sole carbon source. Thus, they were able to identify a bacterium of
the genus Ideonella (named Ideonella sakaiensis 201-F6) that can feed on PET. By
monitoring the transcript levels of genes, they were able to identify two enzymes
(hydrolases) that catalyse the release of terephthalic acid from the polymer, which
can be further degraded by known metabolic pathways.
The disadvantage of this approach is that only a limited number of microorgan-
isms can grow under laboratory conditions, and the possibility to overlook a potent
microorganism is quite high. For this reason, metagenomic approaches are more and
more often used, as the recent technological advances on molecular biology facili-
tated the process. In this approach, DNA is isolated from collected samples, which
includes genetic information from the whole population of the microorganisms. This
DNA is fractured in smaller pieces and cloned in expression vectors, thus producing
a metagenomic library. This library can be either expressed and screened for
enzymes that can perform the desired reaction via an activity test, or it can be
sequenced, and the genes of interest can be located later using known motifs. The
current advances of the sequencing technology produce a vast sequence-space,
where the full characterisation of all encoded proteins is not possible. For instance,
just one metagenomic project on the human gut flora resulted in 3.3 million
nonredundant microbial genes [7]. This sequence-space can be the source of novel
enzymatic activities that were not documented so far. Höhne and coworkers used
such an approach to identify the first (R)-selective amine transaminases [8]. Amine
transaminases are a subgroup of pyridoxal phosphate (PLP) dependent enzymes.
Höhne et al. developed an algorithm, with which they could sort the sequences of the
family to specific substrate selectivity groups, based on motifs they identified. Their
suggestion was that the sequences that do not fit to any of the known motifs/groups,
should be the “missing” (R)-selective amine transaminases. Indeed, once they
expressed 17 proteins encoded from the identified sequences, they could observe
that all of them were transaminases with (R)-selectivity.
The most sophisticated method of identifying enzymes for novel reactions is the
de novo design. In this approach, an artificial active site, using amino acids that
participate in the catalytic mechanism, is designed around the substrate of interest by
means of bioinformatics tools, providing the functional groups and the geometry
required for the catalysis. Later, other amino acids are added to this structure to
facilitate the coordination of the substrate. The implementation of this amino acid set
in several protein scaffolds is performed in silico (i.e. using a computer), in order to
identify the one that provides the optimal geometry. Once the optimal structure is
designed, the gene is synthetically generated and is expressed in order to evaluate the
prediction. Two of the most prominent examples of de novo design are the produc-
tion of a Kemp eliminase [9] and a Diels-Alderase [10]. Nevertheless, this is a time-
intensive method that leads to an output of a low number of proposed enzymes,
while the catalytic efficiency of the resulting enzymes is quite low and requires
further improvement by means of protein engineering.
480 I. V. Pavlidis
47.3 Protein Evolution via Directed Evolution
Usually, the enzymes identified with the aforementioned methods do not meet the
criteria for the desired bioprocesses. The most significant challenges to be addressed
are the low catalytic efficiency and/or low selectivity, the low stability under process
conditions (operational stability), and the possibility of inhibition at higher substrate
or product concentrations. Directed evolution approaches are preferred in cases
where there are not enough structural or mechanistic information, or the target is
not correlated to a specific area of the structure that can be modelled. For instance,
the stability of a protein can result from its whole structure and not from specific
hot-spots [11]; thus, directed evolution approaches, such as error prone polymerase
chain reactions (epPCR; a technique that introduces random mutations during
amplification of a given DNA sample), may be more suitable for such a target.
The benefit of these approaches is that the libraries produced are not target-oriented,
meaning that they can be screened for mutants with improved catalytic behavior for
any characteristic of interest. For instance, the same library can be screened for
mutants that are more thermostable, and/or for mutants with desired selectivity
towards a specific substrate. It is thus understandable that the challenge here is the
selection process: a high-throughput assay that allows a fast and accurate selection
for the desired characteristic is required; in many cases, the development of the assay
is as timely as the screening phase. For instance, the evolution of transaminases was
relying for years on chromatographic (HPLC) assays, or even medium-throughput
photometric assays [12]. The need for rapid evolution of this class of enzymes led in
the recent few years to the development of different high-throughput assays that can
assist the selection of the evolved variants even from the expression plate [13, 14].
Nevertheless, random mutagenesis requires a lot of screening effort, without any
guarantee that the screening will reveal an improved variant. In the case that the
targeted feature is the catalytic activity and selectivity (and in some cases, the
inhibition), rational design approaches may be the method of choice, as these
features are derived from residues around the active site [15].
47.4 Protein Evolution via Rational Design

47.4.1 Rational Design Approaches for Improved Catalytic
Efficiency
The advances in bioinformatics methods have enabled us to predict in silico the

selectivity as well as the catalytic activity of enzymes. There are several successful
examples of rational design. One of the most prominent ones on protein engineering
is the evolution of an (R)-selective transaminase for the production of Sitagliptin
from the companies Merck & Co. and Codexis, despite the facts that a chemical
process was already developed and that the compound was already commercialized.
Savile and coworkers were able to enlarge the binding pocket of the enzyme to
accommodate Prositagliptin and produce optically pure (R)-sitagliptin, in better
yield and optically purity compared to the chemical process [16]. Even then, the
enzyme was not fitted for an industrial process, and several rounds of directed
evolution were performed with further goals (such as stability in the presence of
dimethylsulfoxide, high catalytic efficiency at high substrate concentration). In
one of our recent works, we were not only able to enlarge the binding pocket of
(S)-selective amine transaminases by rational design, but, by deciphering the reasons
behind the substrate selectivity, we were able to suggest a motif responsible for the
acceptance of bulky substrates [17]. Using the motif, we interrogated the sequence-
space and were able to identify six novel amine transaminases with the desired
substrate selectivity. It is thus understandable that the benefit of the rational design
approaches does not only rely on the reduced screening effort needed, but also to the
rationalisation of the results that facilitates the design of tailor-made biocatalysts in
the future.
47.4.2 Rational Design Approaches for Improved Stability
Although stability is recognised as a global attribute of a protein that is not located in

specific areas, there are some rational approaches that can accelerate the evolution of
stable variants. The enzymes are catalytic functional once they are properly folded.
Elevated temperatures as well as polar organic solvents can lead to protein
unfolding. Theory suggests that the unfolding initiates from the most flexible
areas, thus if these areas are stabilised, the stability of the enzyme will be increased.
Two major methods for enzyme stabilisation via rational design exist: (i) the B-FIT
[18] and (ii) the stabilisation by creating new disulfide bonds [19].
The protein databank (PDB, http://www.rcsb.org) provides the static three-
dimensional structures of enzymes. However, enzymes in reaction conditions are
flexible molecules. PDB data from X-ray crystallography provide the B-factor, a
factor that describes the spread of the electron density of an atom. This B-factor is
correlated with the flexibility of the atoms and subsequently their amino acids
[18]. The B-Fitter is a simple program that averages the B-factors of all atoms of
every amino acid of the protein and sorts them in descending order. This allows to
target possible “hot-spots” of unfolding. Subsequently these positions are mutated,
either to the whole set of natural amino acids, or to a restricted set of amino acids that
are expected to provide specific interactions in order to stabilise the amino acid. This
method was successfully applied for the evolution of a thermostable lipase [18], but
since then the method has been applied to many enzyme classes.
Another method for stabilisation on a molecular level is the introduction of
disulfide bonds. The algorithm developed by Dombkowski identifies the pairs of
amino acids that can provide a disulfide bond [19, 20]. This takes into account the
distance of the amino acids, their angle, as well as the potential energy of a disulfide
bond. With these calculations, the platform provides a list with potential disulfide
482 I. V. Pavlidis
bonds. Then, the researcher only needs to perform two point mutations to introduce
cysteines on the proposed positions and express the enzyme in a host able to express
proteins with disulfide bonds. Interestingly, the algorithm predicts not only intra-
molecular bonds, but also intermolecular one between different chains of the protein.
This is important for enzymes that are active as homomultimers, as the
intermolecular disulfide bonds stabilize the multimerization process.
47.5 The Example of Enzymes Active Against Halogenated

Compounds
Several enzymes classes have been described to be active against chemical warfares,
especially against nerve and blister agents [1, 2]. As an example of the evolution of
enzyme identification and engineering, a short overview on the enzymes active on
halogenated substrates and blister agents is given here.
Haloalkane dehalogenases (EC 3.8.1.5) are enzymes that convert halogenated com-
pounds into alcohols and the respective halides. They were originally identified as
crucial enzymes for the bioremediation of environmental pollutants [21, 22], but
nowadays several biotechnological applications have been developed, especially by
exploiting their enantioselectivity to produce optically pure compounds [23]. These
enzymes are used for the decontamination of warfare agents, such as sulfur mustard [1],
and for their biosensing [24]. Nowadays we have a good understanding of the catalytic
mechanism [25]; therefore the engineering efforts are facilitated. There are three main
enzymes mostly used for the degradation of environmental pollutants: DhlA, DhaA and
LinB [25]. DhlA was the first enzyme of the class that was characterized, which
catalyses the degradation of 1,2-dichloroethane [26]. This enzyme has a cap over the
active site that is important for the substrate specificity. Directed evolution experiments
increased the activity towards brominated substrates, such as 1,2-dibromoethane and
1-bromobutane [27]. In another work, a Pseudomonas strain that could use long chain
alcohols as sole carbon source, was genetically modified to be able to grow on
1-chlorohexane [28]. The wild-type DhA variant would not be useful in this case, as it
cannot convert this substrate, but Pries and coworkers developed a variant with muta-
tions at the cap domain that could accept this substrate and provide 1-hexanol as carbon
source [28]. DhaA is mostly used for its activity towards 1,2,3-trichloropropane. The
wild-type enzyme can dehalogenate in position 1, producing 2,3-dichloropropan-1-ol,
but the catalytic efficiency is low [25]. Thus, protein engineering was performed and an
32-fold increase was achieved with only five point-mutations [29]. However, this
product is still toxic, and thus a further degradation is required. Dvorak and coworkers
established an enzymatic cascade of three enzymes, including a variant of DhaA, an
haloalcohol dehalogenase and an epoxide hydrolase, that produces glycerol as final
product [30]. Wild-type DhaA and LinB are able to degrade sulfur mustard to non-toxic
product, while the spontaneous hydrolysis of sulfur mustard leads to a release of toxic
intermediates [1].
Another interesting enzyme class are the haloalcohol dehalogenases (also known
as halohydrin dehalogenases), which belong to the enzyme class of lyases
(EC 4.5.1.-) and catalyze the dehalogenation of halohydrins with a subsequent
epoxide formation. If a negatively charged nucleophile is provided, the enzyme
catalyses also the epoxide ring opening, resulting to non-reversible dehalogenation
[31]. Apart from their application in the degradation of 1,2,3-trichloropropane [30],
halohydrin dehalogenases are also used for the detection of azide or cyanide by
catalysing the epoxide ring opening reaction on 1,2-epoxybutane [32]. Most of the
protein engineering was performed on two well characterized enzymes, HheC and
HheA2. Directed evolution via ProSAR was performed on HheC to shift its selec-
tivity from ethyl (S)-4-chloro-3-hydroxybutyrate to ethyl (R)-4-cyano-3-
hydroxybutyrate; after screening more than half a million clones, several variant
with the desired selectivity were identified with at least 35 mutations [33]. The
variant HheC-2360 carrying 37 mutations not only had a threefold improved turn-
over number, and an inverted selectivity, but also an increased thermal stability [31].
These are only two of the most studied classes of enzymes active on
organohalogen compounds, but there are several other enzyme classes studied that
exhibit other selectivities: 2-haloacid dehalogenases that hydrolyses a 2-haloacid to
2-hydroxyacid, fluoroacetate dehalogenases that are able to cleave the strong carbon-
fluorine bond, one of the strongest single bonds in organic chemistry and
2-haloacrylate dehalogenase that acts on unsaturated organohalogen compounds
[34]. Of course, the in vivo solutions are preferred, as there is no need for purification
of the biocatalyst. Very recently a bacterial consortium was developed that can
dechlorinate trichloroethene to ethene, which uses two vinyl chloride reductive
dehalogenases and a trichloroethene reductive dehalogenase for the catabolic path-
way [35]. As discussed above, there are numerous solutions for the biocatalytic
degradation and sensing of halogenated compounds, and the most suited approach
can be selected, according to the characterized enzymes to the date.
47.6 Conclusion
Biocatalytic processes are established in a wide selection of applications. Enzymes

are environmentally friendly catalysts that are more appealing from their chemical
counterparts, especially due to their selectivity. However, the identification of a
suitable enzyme can be a daunting task, and the identified enzyme needs modifica-
tion to fit to the process conditions. The advances of the last few years in genetics,
molecular biology and bioinformatics enable us to develop tailor-made biocatalysts
and predict their selectivity. The forth wave of biocatalysis will lead to more
sustainable and greener bioprocesses.
484 I. V. Pavlidis
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Chapter 48
Self-Organized Magnetic Nanoparticles
in Plant Systems: ESR Detection
and Perspectives for Biomedical
Applications
T. S. Kavetskyy, R. I. Khalilov, O. O. Voloshanska, L. M. Kropyvnytska,

T. M. Beyba, V. A. Serezhenkov, A. N. Nasibova, A. Akbarzadeh,
and S. Ya. Voloshanska
Abstract An innovative approach based on the effect of bio-mineralization as a

response reaction of cells to decrease their damage upon stress was applied for
Juniperus communis, the common juniper (in the following JC). Electron spin
resonance (ESR) was used as the main experimental tool for detecting paramagnetic
species as a result of existence of an antioxidant activity system, represented by
superoxide dismutase with manganese, catalase etc., and the formation of
superparamagnetic iron oxide nanoparticles (SPIONs). SPIONs are found in the
JC shell, while the antioxidant activity due to Mn-containing enzymes is detected in
T. S. Kavetskyy (*)
Joint Ukraine-Azerbaijan International Research and Education Center of Nanobiotechnology
and Functional Nanosystems, Baku, Azerbaijan
and Functional Nanosystems, Drohobych, Ukraine
R. I. Khalilov
Institute of Radiation Problems of NAS Azerbaijan, Baku, AZ, Azerbaijan
Baku State University, AZ, Baku, Azerbaijan
O. O. Voloshanska
Zaporizhzhya State Medical University, Zaporizhzhya, Ukraine
L. M. Kropyvnytska · T. M. Beyba

the seeds. The influence of temperature on the intensity of the ESR signals was also
examined. The detected bio-functionality of the JC shell and seeds could be
recommended for biomedical applications.
Keywords Electron spin resonance spectroscopy · Juniperus communis ·

Superoxide dismutase · Manganese · Superparamagnetic iron oxide nanoparticles
48.1 Introduction
The influence of physical (stress) factors (e.g. temperature, humidity, strong UV

and/or lower level of illumination, radiation, soil salinity, etc.) on plant such as JC
forms an antioxidant system with a larger activity than for other plants. Due to the
existence of antioxidant enzymes among the many pharmacological effects of JC are
antitumor properties, and antioxidant, antitoxic, and anticarious activities. The
pharmacological activity of JC could be allocated either to the shell or to the
seeds. Also, by adding into compositions of other biologically active dietary sup-
plements (BADS), it is possible to utilize the bio-functionality of the drug for
medical purposes. But, if stress factors are influencing the JC bioactivity (this is
expected to happen in different seasons), the properties of JC based drugs could be
uncontrollable. The present research focuses on resolving this problem by using a
V. A. Serezhenkov
Semenov Institute of Chemical Physics of RAS, Moscow, Russia
A. N. Nasibova
Institute of Radiation Problems of NAS Azerbaijan, Baku, AZ, Azerbaijan
A. Akbarzadeh
Stem Cell Research Center, Tabriz University of Medical Sciences, Tabriz, Iran
Universal Scientific Education and Research Network (USERN), Tabriz, Iran
S. Y. Voloshanska
48 Self-Organized Magnetic Nanoparticles in Plant Systems 489
new approach based on the effect of bio-mineralization as a response reaction of

stress-damaged cells, resulting in self-organized magnetic nanoparticles synthesized
by a plant system upon stress (so-called “green synthesis”) [1–4]. This effect is
coupled with electron-transport chain of photosynthesis that leads to a decrease of
Fenton’s reaction due to the transformation of iron ions (Fe2+, Fe3+) to maghemite
and magnetite superparamagnetic iron oxide nanoparticles (SPIONs). Electron spin
resonance (ESR) spectroscopy is used in this research as the main experimental tool
for detecting the self-organized SPIONs in the JC shell and/or seeds.
48.2 Experimental
The methodology of the present work is based on the application of the above
mentioned effect of bio-mineralization of JC samples from the Carpathian region
of Ukraine. The ESR spectra of the biomaterials studied were recorded with the aid
of an X-range ESR spectrometer ECS-106 (Bruker, Germany) under the following
conditions: magnetic field HF-modulation amplitude 0.5 mT, UHF power 20 mW,
field center 260 mT, field scanning 290 mT, temperatures 293 and 77 K, and gain 104
and 5 105, respectively.
Figure 49.1a shows ESR spectra of the JC shell and seeds and their mixture, together
with a differential spectrum between seeds and shell as a function of the magnetic
field at room temperature. We emphasize two ESR signals registered in the bio-
materials. Namely, the ESR signal at g ¼ 2.01 is attributed to paramagnetic Mn
species [3], characterized by a six-component hyperfine structure, in the
Mn-containing enzymes that is found only in the JC seeds. At the same time, the
broad ESR signal at g ¼ 2.28 is attributed to paramagnetic SPION species [3] only
found in the JC shell.
It must be noted here that the SPIONs detected in the investigated material have
an important role in the development of pathological conditions and are frequently
used for biomedical applications, where their toxic potential is still a major concern
[5–14]. The SPIONs have also promising applications in food science [15–
17]. These magnetic nanoparticles lead to the appearance of magnetic properties in
plant systems and the emergence of ESR signals [3]. Magnetic nanoparticles are
present in various natural systems including living organisms of all levels and types
of organization. The biogenic generation of nanophase magnetic oxides is associated
with physiological processes including a number of pathologies, in particularly,
human neurodegenerative diseases, Type 2 diabetes, premature ovarian insufficiency
(POI), and hemochromatosis. As a result, the investigation of the mechanisms of
formation of iron oxide nanoparticles in living systems is important from a
Fig. 48.1 Electron spin

resonance spectra of the JC
shell, seeds, and a mixture of
shell and seeds as a function
of magnetic field at
temperatures (a) 293 K (1 –
mixture of shell and seeds, 2
– shell, 3 – seeds, and 4 –
differential spectrum (curve
3 curve 2)) and (b) 77 K
(1 – mixture of shell and
seeds, 2 – shell, and 3 –
seeds)
fundamental viewpoint and also necessary for the development of novel efficient
methods in pharmacy. The appearance of an ESR signal characteristic for magnetic
nanoparticles has been found [3, 18] in various plants as a result of effects of external
stress factors.
In the present study, the stress factors affecting the JC shell are also directly
confirmed by ESR detected SPIONs as a result of bio-mineralization effect under
stress. In other words, the JC shell with externally-attained functionalities, resulting
in the formation of SPIONs plays a role as protection for the JC seeds. On the other
hand, Mn-containing enzymes presenting an antioxidant activity, are normally found
in the JC seeds. Therefore, SPIONs in drugs based on the JC shell, and the
antioxidant activity detected by enzymes in the case of the JC seeds could be applied
for pharmaceutical and biomedical purposes.
Figure 48.1b shows ESR spectra of JC shell and seeds and their mixture as a
function of the magnetic field at low temperature. As expected, the measurement
48 Self-Organized Magnetic Nanoparticles in Plant Systems 491
performed at 77 K showed an enhancement of the ESR signal from enzymes

(g ¼ 2.0) for the JC seeds. At the same time, the intensity of the ESR signal from
SPIONs (g ¼ 2.28) for the JC shell is reduced at 77 K. Also, the intensity of the
broad ESR signal at g ¼ 3.26 for the JC shell is found to decrease at low temperature.
Note, that in all dried soil samples at room temperature a broad ESR signal with a
half-width of 150 mT and a position of the maximum of the low-field component at
g ¼ 3.3 has been observed [3], while upon lowering the temperature from room to
80 K the intensity of this broad signal was reduced. Registration of the broad ESR
signal at g ¼ 3.3 in soil samples has been interpreted in [3] to be due to a high content
of iron aggregates, among which there could be magnetic nanoparticles (SPIONs) in
the soil on which plants grew. As seen in our case for the JC shell, the behavior of the
ESR signals at g ¼ 2.28 and g ¼ 3.26 at 77 K is quite similar, supporting the finding
of [3] that these two signals are connected with SPIONs and iron aggregates
(containing SPIONs). Besides, a weak signal of Fe3+ at g ¼ 4.3 (recorded at 80 K
in [3]) is also detected for the JC samples at 77 K (Fig. 48.1b). A broad ESR signal
with a position of the maximum of the low-field component at g ¼ 2.58 is assigned
to SPIONs too, as this signal is closest to that at g ¼ 2.69 detected for the samples
with magnetic nanoparticles in [3].
48.4 Conclusion
An innovative identification method for bioactivity of natural BADS was proposed

using the example Juniperus communis. The presence of an antioxidant activity
system due to the effect of bio-mineralization under stress, represented by
Mn-containing enzymes and other enzymes, and the formation of SPIONs in the
biomaterials studied has been examined using ESR spectroscopy. The SPIONs are
only detected in the JC shell, while the Mn-containing enzymes are only found in the
JC seeds. The observed bio-functionality of the JC based shell and seeds could be
used for pharmaceutical purposes and biomedical applications.
Acknowledgments T.S. Kavetskyy and S.Ya. Voloshanska acknowledge the Ministry of Educa-
tion and Science of Ukraine (project No. 0114U002617).
References
1. Khalilov RI, Nasibova AN (2010) The endogenous EPR-detectable iron nanoparticles in plants
News Baku Univ 3:35
2. Khalilov RI, Nasibova AN, Gasimov RJ (2011) Magnetic nanoparticles in plants: EPR
researches News Baku Univ 4:56
3. Khalilov RI, Nasibova AN, Serezhenkov VA, Ramazanov MA, Kerimov MK, Garibov AA,
Vanin AF (2011) Accumulation of magnetic nanoparticles in plants grown on soils of Apsheron
peninsula Biophysics 56:316
4. Khalilov RI, Nasibova AN, Youssef N (2015) The use of EPR signals of plants as bioindicative
parameters in the study of environmental pollution Int J Pharm Pharm Sci 7:172
5. Ito A, Shinkai M, Honda H, Kobayashi T (2005) Medical application of functionalized
magnetic nanoparticles J Biosci Bioeng 100:1
6. Huber DL (2005) Synthesis, properties, and applications of iron nanoparticles Small 1:482
7. Gupta AK, Gupta M (2005) Synthesis and surface engineering of iron oxide nanoparticles for
biomedical applications Biomaterials 26:3995
8. Roca AG, Costo R, Rebolledo AF, Veintemillas-Verdaguer S, Tartaj P, Gonzalez-Carreno T,
Morales MP, Serna CJ (2009) Progress in the preparation of magnetic nanoparticles for
applications in biomedicine J Phys D Appl Phys 42:224002
9. Berry CC (2009) Progress in functionalization of magnetic nanoparticles for applications in
biomedicine J Phys D Appl Phys 42:224003
10. Singh N, Jenkins GJS, Asadi R, Doak SH (2010) Potential toxicity of superparamagnetic iron
oxide nanoparticles (SPION) Nano Rev 1:5358
11. Soenen SJH, De Cuyper M (2010) Assessing iron oxide nanoparticle toxicity in vitro: current
status and future prospects Nanomedicine 5:1261
12. Ankamwar B, Lai TC, Huang JH, Liu RS, Hsiao M, Chen CH, Hwu YK (2010) Biocompat-
ibility of Fe3O4 nanoparticles evaluated by in vitro cytotoxicity assays using normal, glia and
breast cancer cells Nanotechnology 21:075102
13. Mahmoudi M, Sant S, Wang B, Laurent S, Sen T (2011) Superparamagnetic iron oxide
nanoparticles (SPIONs): development, surface modification and applications in chemotherapy
Adv Drug Deliv Rev 63:24
14. Kandasamy G, Maity D (2015) Recent advances in superparamagnetic iron oxide nanoparticles
(SPIONs) for in vitro and in vivo cancer nanotheranostics Int J Pharm 496:191
15. Miller DD (2010) Food nanotechnology: new leverage against iron deficiency Nat Nanotechnol
5:318
16. Hilty FM, Arnold M, Hilbe M, Teleki A, Knijnenburg JTN, Ehrensperger F, Hurrell RF,
Pratsinis SE, Langhans W, Zimmermann MB (2010) Iron from nanocompounds containing
iron and zinc is highly bioavailable in rats without tissue accumulation Nat Nanotechnol 5:374
17. Zimmermann MB, Hilty FM (2011) Nanocompounds of iron and zinc: their potential in
nutrition Nanoscale 3:2390
18. Nasibova AN, Khalilov RI (2016) Preliminary studies on generating metal nanoparticles in
pomegranates (Punica Granatum) under stress Int J Dev Res 6:7071
Chapter 49
Nanoparticle Based Decontamination
of Bacteria/Pathogens
N. Enaki, T. Paslari, E. Starodub, S. Bizgan, C. Ristoscu, I. N. Mihailescu,

and A. Vaseashta
Abstract The decontamination of pathogens (bacteria and yeast fungi) from

non-transparent fluids (liquids or gases) using periodical structures like small
quartz or glass spheres irradiated by ultraviolet (UV)-C light is proposed. Studies
were devoted to the topological effect of individual metamaterial elements which
modify UV-C evanescent waves in a contact zone of contaminated fluids and
metamaterials, as a function of granule geometry. The efficiency of utilization of
metamaterials in decontamination of non-transparent liquids is demonstrated.
The decontamination efficiency is assessed both in the dynamic and static
regime. Control experiments were performed in the absence of metamaterials
and/or UV-C irradiation.
Keywords Pathogen decontamination · Evanescent field · Pulsed light technique ·

Photonic crystal · Optical fiber · Microsphere · Metamaterial
N. Enaki · E. Starodub · S. Bizgan

Quantum Optics and Kinetic Processes Lab, Institute of Applied Physics of Academy of
Sciences of Moldova, Chişinau, Moldova
T. Paslari (*)
Quantum Optics and Kinetic Processes Lab, Institute of Applied Physics of Academy of
Sciences of Moldova, Chişinau, Moldova
Department of Physics and Engineering, Moldova State University, Chisinau, Moldova
C. Ristoscu · I. N. Mihailescu
National Institute for Lasers, Plasma and Radiation Physics, Bucharest, Romania
A. Vaseashta
USA

494 N. Enaki et al.
49.1 Introduction
We propose new decontamination methods of dispersive (non-transparent) infected

liquids and gases, based on the potentials offered by periodical optical structures.
Classical methods of decontamination using ultraviolet (UV) radiation proposed in
the literature are practically impossible to apply in the case of non-transparent fluids.
Nanoparticles or ensemble of nanoparticles exhibit a high surface/volume ratio. The
collective action property gives us the possibility to use these metamaterials as
antibacterial media against pathogens from contaminated gases and liquids [1, 2],
and solid media. Nanoparticle application in decontamination of non-transparent
fluids using the contact surface of metamaterial is not completely studied and fully
understood yet [1]. An important point to note is the evanescent zone with dimension
ranging from 100 to 200 nm, which appears around the elements of metamaterials
during the propagation of UV-C radiation through periodical optical structures from
packed micro- or nanoparticles. The active decontamination zone is built by the
UV-C evanescent field in which the contaminated fluids flow. The pathogens which
arrive at the surface of microparticles (or nanoparticles) or pass through the evanes-
cent zone are inactivated by UV-C radiation. Using metamaterials, we improved the
active decontamination zone of UV radiation. Such a methodology may be used in
fiber optic systems in which the contaminated fluids are propagated along with the
free space between the fibers [1]. Keeping in mind that using metamaterials formed
from nanoparticles, we have a substantial gain in the decontamination contact
surface during the propagation of contaminated liquids through the free space
between the nanoparticle of meta-materials (or optical fibers), we therefore propose
a new decontamination equipment based on these optical metamaterials [3]. The
increase of the active decontamination zone of non-transparent fluid strongly
depends on the size, shape and structure of each element of the metamaterial. The
relative value of the refractive indexes of metamaterial and contaminated liquids
becomes a main factor in increasing the penetration depth of UV radiation into the
volume of the contaminated fluid flowing between the metamaterial particles
(or along the space between the fibers). Another aspect of decontamination using
metamaterials is related to the ability to capture the pathogens along the surface of
the metamaterial [4, 5] and thereafter their inactivation by evanescent UV radiation.
We propose herein a model of metamaterials (periodical optical structures) to
inactivate microorganisms present in contaminated gases or liquids.
49.2 Experiment Results and Discussions
The possibility to decontaminate non-transparent liquids using a UV filter based on

improving the contact surface with radiation is estimated. The metamaterials with an
accessible price on the market consist of SiO2 spheres with diameters of about
49 Nanoparticle Based Decontamination of Bacteria/Pathogens 495
Fig. 49.1 Left: SiO2 spherical bubbles used in the decontamination core of the reactor, which is
focusing the radiation of six UV-C low-pressure mercury lamps. Right: The crushed quartz glass
granules
Fig. 49.2 (a) Decontamination equipment using metamaterials for inactivation of pathogens in
non-transparent fluids. (b) The core tube filled with SiO2 granules
1–3 mm (Fig. 49.1). Elements of the optical metamaterial can disperse the UV-C
light and improve the contact zone between radiation and contaminated liquids.
The proposed decontamination equipment using metamaterials is presented in
Fig. 49.2a. The radiation of six UV-C (254 nm) lamps is concentrated by the
reflective cylinder in the core of the reactor, formed from one quartz tube with a
diameter about 3 cm. The light radiation of these lamps is effectively focused and
homogeneously distributed along the cylinder axis, with a Gaussian distribution of
the intensity of the reflected radiation from a large aluminum surface of the cylinder
with a radius of about 15 cm which covers the lamps. The power of each lamp it is
about 30 W. The core quartz tube is filled up by the SiO2 granules. The contaminated
fluids can freely flow through the free space between spheres, randomly changing
the optical frontiers between these elements and the liquid (or gas) as a function of
the concentration of the pathogens in it. The decontamination efficiency is
496 N. Enaki et al.
determined by the contact surface zone between the fluid and the periodical spherical
metamaterial, which is proportional to the number of spheres in the core. This UV
decontamination reactor may be utilized directly in installations for water, the
distribution of central water circuits or in each apartment, in order to avoid biological
attacks against our vital necessity in water and air. This equipment may effectively
decontaminate the water and air in each apartment in a city.
We present here results of two decontamination experiments. The first of them is
connected with the decontamination of B. coliform, Intestinal Enterococci,
Escherichia coli (E. coli) bacteria. For this, we took the contaminated water from
the nearest reservoir of the “Valea Morilor” lake from Chisinau. The contaminated
water was divided into two parts. The first part was treated by our equipment
represented in the Fig. 49.2. The pump rotates the contaminated water in intervals
from 5 to 10 min. After 24 h, the bacteria from treated and non-treated liquid probes
were stimulated for reproductions with a special gel. The multiplication results of
bacteria in natural water (a) and treated one in our laboratory (b) are represented in
the Fig. 49.3. As follows from experimental results the E. coli bacteria practically
totally were inactivated from the volume about 1 L of water after 5 min of treatment
in the core tube of our reactor. After 10 min of treatment in the decontamination core
tube, a total inactivation of bacteria was observed. After flowing along the decon-
tamination cylinder filled up with spherical bubbles of SiO2 SiO2(or another
metamaterial) the bacteria periodically collapse on the evanescent zone of UV-C
radiation of the metamaterial.
Other experiments are linked up with yeast fermentation. By fermentation, the
yeast converts carbohydrates to carbon dioxide and alcohols. The fermentation
indicators may be used for estimation of the decontamination rate and efficiency
of our equipment (Fig. 49.2) in two regimes, dynamic and static. The solution of
Fig. 49.3 The dynamical regime of decontamination of water. (a) probe of natural water: (b) The
treated probe for 5 min by the proposed decontamination equipment
49 Nanoparticle Based Decontamination of Bacteria/Pathogens 497
yeast is non-transparent to UV-C radiation. We used metamaterials consisting of

quartz glass granules. After 10 min of treatment in the dynamic regime, when the
core tube was filled up with unordered quartz granules (Fig. 49.1b), the fermentation
was stopped (Fig. 49.4). Thus, in the experiments yeast treated in our decontamina-
tor in the dynamic regime was efficiently inactivated during the process flowing of
liquid through the free space intervals between metamaterial elements (quartz
granules), penetrated by the evanescent radiation.
After 1 h of observation the fermentation is active in the untreated solution
(Fig. 49.4b), while in the treated yeast solution (1 L) during 10 min of circulating
through the core tube filled up by unordered granulated quartz, the fermentation is
stopped (Fig. 49.4a). After 5 min of irradiation of yeast solution using unordered
granulated quartz a partial inactivation of yeast fungus in the treated solution was
observed relative to the control samples.
To demonstrate the efficiency, the same solution of yeast was treated in the core
tube without metamaterials, for 10 and 20 min (Fig. 49.5). In both cases the
unstopped process of fermentation was observed. The inefficient inactivation of
the fungus is related to the non-transparency of the yeast solution for UV radiation.
Fig. 49.4 Yeast at 1-h observations. The first portion (a) was dynamically treated by our equipment
for 10 min while the second (b) remained untreated
Fig. 49.5 Yeast solution after 1 h’s observation. The first portion (a) was dynamically treated by
our equipment for 10 min and the second (b) for 20 min, in both cases without quartz granules in the
core tube. As a result of the test, fermentation started in both cases (a) and (b)
498 N. Enaki et al.
49.3 Conclusions
We demonstrated that using metamaterials, such as photonic crystals, in micro-

spheres or fibers there is a substantial gain in the decontamination of liquids from
viruses and bacteria.The increasing of the surface contact of UV radiation with
contaminated liquid strongly depends on the refractive index of metamaterial, the
liquid volume and the optical properties of viruses and bacteria. The possibility to
effectively inactivate with UV-C radiation pathogens from non-transparent fluids
(liquids or gases) was further presented.
Acknowledgments This paper was supported by the projects: STCU6140&NATO SPS G4890.
References
1. Enaki NA, Bazgan S, Ciobanu N, Turcan M, Paslari T, Ristoscu C, Vaseashta A, Mihailescu IN

(2017) Improvement in ultraviolet based decontamination rate using meta-materials. Appl Surf
Sci 417:40–47
2. El-Mashad HM, Pan Z (2015) Food decontamination using nanomaterials. MOJ Food Process
Technol 1(2):00011
3. Bazgan S, Ristoscu C, Negut I, Hapenciuc C, Turcan M, Ciobanu N, Mihailescu IN, Enaki N
(2015) Propagation of UV radiation through meta-materials and its application in
bio-decontamination. Rom Rep Phys 67:1602–1607
4. Ashkin A, Dziedzic JM (1987) Optical trapping and manipulation of viruses and bacteria.
Science 235:1517–1520
5. Daly M, Sergides M, Nic Chormaic S (2015) Optical trapping and manipulation of micrometer
and sub micrometer particles. Laser Photon Rev 9:309
Chapter 50
Development of Nanostructured Materials
with CBRN Agents Sensing Properties
A. Stoilova, A. Georgiev, D. Nazarova, L. Nedelchev, D. Dimov,

and P. Petkov
Abstract Azobenzene containing polymers are a class of optical materials exten-

sively investigated in the past decade. Due to their possibility to undergo reversible
trans-cis-trans photoisomerization cycles and through their attractive photophysical
properties, the azopolymers could be used as storage medium in optical devices, as
optical switches and sensors, as responsive surfaces for biomedical applications, in
polarization holography, and in photonics. The aim of this paper is to summarize the
information available in the scientific literature about the possibility to use these
materials not only for optical application but also as sensing platforms for the
detection of biological agents listed as category A biological weapons. Furthermore,
this review attempts to give the readers insights into the difficulties concerning the
detection of biological agents within environmental samples as well as to outline the
progress and the weaknesses in the development of sensors based on nanostructured
materials to help to combat terrorisms.
Keywords Nanocomposites · Azo polymers · Sensors · CBRN agents diagnostic
50.1 Introduction
The deliberate release of biological agents such as viruses, bacteria or toxins to cause
illness or death is defined by the U. S. Center for Disease Control and Prevention
(CDC, www.cdc.govas) as bioterrorism. The biological agents are classified into
three groups A, B and C based on their infectivity, the mortality they cause, the ease
of spread and the likeliness of use. To category A belong the bacteria Francisella
tularensis, Clostridium botulinum, Yersinia pestis, Bacillus anthracis and also the
Variola virus and some RNK viruses causing hemorrhagic fevers. Historically, the
A. Stoilova (*) · A. Georgiev · P. Petkov

D. Nazarova · L. Nedelchev · D. Dimov
Institute of Optical Materials and Technologies, Bulgarian Academy of Science, Sofia, Bulgaria

500 A. Stoilova et al.
pathogenic microorganisms classified as a category A potential bioterrorism agents

have killed far more people than the First World War itself. For example, 25 million
Europeans died from the bubonic plague alone in the fourteenth century. The
pathogenic species from category A could be find actually all around us. They
spread through the air, the water and the soil. They are also relatively easy to
produce using the common technology available for the production of some antibi-
otics, for example. As a result they are cheaper than the conventional weapon of
mass destruction and also invisible, silent, odourless and stable in environmental
samples. All these characteristics make them very attractive to terrorists but not so
much to the scientific community from which is expected to develop highly sensi-
tive, rapid, portable and if possible inexpensive sensors for their detection.
This review was generated using references published over the last 20 years. The
literature search has been conducted using the database “ScienceDirect” and through
the free search engines “PubMed” and “NCBI” by keywords relevant to the topic.
The purpose of this article is to survey the open literature to determine the current
state of development of biosensors based on azobenzene containing nanomaterials
for the detection of biological agents from category A. The research interest in
nanostructured materials as biodefence detection platforms is due to their dimen-
sions comparable to those of the biological molecules [1]. For example quantum dots
were used for the detection of Botulinum neurotoxin by means of an optical
biosensor, Ln-doped nanoparticles were used for detection of Bacillus anthracis
spores using a photoluminescence based sensor, the Variola virus was detected
using heterogeneous nanowires [2] (Table 50.1).
50.2 Detection of Biological Agents at the Point

of Dissemination
Detection of biological agents or their toxins within soil or water samples is difficult
because they usually contain substances that inhibit the detection technique. The
target micro-organisms must be isolated, concentrated and/or purified [7]. Typically,
after sampling and solubilizing or suspending with phosphate buffered saline, the
sample is being transferred to the testing assay. Many of the commercial detection
systems use test strips based on the affine chromatography principle. The detection
of pathogens within urban aerosols is more difficult. Sampling bioaerosols include
impaction, filtration or impingement [8]. In real situations portable cyclones are used
for collection of bioaerosols from air into the liquid phase; thereafter the samples
obtained are further analysed. Testing for potential biothreat agents in the air is
possible at facilities containing approved air or aerosol chambers and wind tunnels.
The most important physical characteristic by which airborne pathogens could be
classified is their size. Particles with a diameter in the range 1–5 μm behave in
aerosols like gases. Particles larger than 5 μm in diameter settle from the atmosphere
and bind to surfaces; particles with a diameter smaller than 1 μm, such as most of the
50 Development of Nanostructured Materials with CBRN Agents Sensing Properties 501
Table 50.1 A brief summary of the information concerning size range, shape and human’s
infectious dose of the pathogen species listed to category A [3–6]
Infectious dose for
Category A biological agents Size range humans
Francisella tularensis-aerobe bacterium, 0,2–0,7 μm 10–50 organisms
pleomorphic, non-motile, non-spore forming, (aerosol
gram-negative, rod-shaped, responsible for inoculation)
epizootics of tularemia, highly stable in an
environmental matrix
Clostridium botulinum-anaerobic bacterium, 0,1–0,3 μm (aerosolized 0,001 μg/kg body
rod-shaped, gram-positive, spore-forming, particles of the botulinum weight by oral
motile, Botulism causing agent. There are toxins) exposure
seven types of C. botulinum toxins (A–F). 0,07 μg/kg body
Types A, B, E, and rarely F can cause human weight by
botulism inhalation
Bacillus anthracis-aerobic bacterium, gram- 0,95–3,5 μm 8.103 to 50.103
positive, rod-shaped, non-motile, resistant to spores (inhalation)
adverse environmental conditions, spore
forming, anthrax causing agent
Yersinia pestis-gram-negative bacterium, 0,5–0,8 μm (width) 100–500 particles
rod-shaped, facultative anaerobic organism, 1–3 μm (length)
non-motile bacillus, causes Bubonic plague
Variola virus 360–270–250 nm 10–100 particles
RNK viruses cause viral hemorrhagic fevers:
Marburg virus 80 nm (d) 1–10 (ae. o)
Ebola virus 80 nm (d) 1–10 (ae. o)
Lassa virus 80–150 nm (d) 1–10 (ae. o)
Machupo virus 50–300 nm (d) 1–10 (ae. o)
ae.o stands for aerosolized organisms and d for diameter
pathogens belonging to category A, can be collected by processing large volumes of

air and passing the air through a filter or impinging the particles from the collected
air into a liquid or semisolid sample [9]. The traditional methods of detecting
biological agents show high sensitivity and specificity, but these techniques are
often slow, expensive and require sample pre-treatment and laboratory conditions
for their execution.
50.3 Biosensors for Environmental Monitoring

of Biological Agents
To overcome the above mentioned difficulties concerning the biological agent’s

detection within environmental samples the efforts of the scientific community are
focussed on the development of portable and multiplexed nanomaterial-based
sensors. Due to the nanoscale interactions providing unique physico-chemical
properties and the large surface/volume ratios these materials are well-suited for
application in sensing devices [2]. The fastest growing technology for detection of
pathogens in recent years is the biosensor [10]. Several studies report the perfor-
mance of biosensors for detection of category A bacterial agents. For example
Skládal et al. [11] reported an electrochemical immunosensor for rapid and highly
sensitive detection of Francisella tularensis. A detection limit of 1000 CFU/mL
(colony-forming units per millilitre) was achieved. The required detection time
was about 25 min. O’Brien et al. [12] demonstrated an optical bidiffractive grating
immunosensing device for direct detection of Francisella tularensis. A detection
limit of 3104 CFU/ml was obtained. The required measuring time was 50 min. A
novel piezoelectric sensor for direct detection of Francisella tularensis was devel-
oped by Pohanka and Skládal. The device exhibited a detection limit of 105 CFU/ml.
The required measuring time was 5 min after a short pre-cultivation enrichment
[11]. For comparison commercial test strips designed for detection of multiple
biological warfare agents show a detection limit in the range of 105 to 106 CFU/ml
towards Francisella tularensis. Joint Biological Agent Identification and Diagnostic
System is a military, portable, real-time PCR instrument technology (Polymerase
chain reaction, or PCR, is a technique used to make many copies of a specific DNA
region in vitro) detecting simultaneously up to 32 samples. The assay time takes
30 min, not including sample preparation. The limit of detection reported by the
manufacturer is 1000 CFU/ml towards Francisella tularensis [13]. It must be noted
that most of the biosensors reported in the scientific literature for detection of
Francisella tularensis are research-based prototypes not yet ready for integration
into commercial devices.
The biosensor is a small, portable, analytical device made up of a biological
recognition element (also called bioreceptor) consisting of biocomponents (nucleic
acids, enzymes, anti-bodies, cells etc.) able to detect specific target analytes. Attach-
ment of target molecules on the sensor surface brings about physicochemical
changes such as release of heat, flow of electrons, changes in the mass, changes in
the absorption spectra which are converted into a measurable signal by a transducer
component (converter) and passed to a microprocessor where it is amplified and
displayed [14]. In general there are three strategies for immobilization of the
biological molecules onto the sensor’s surface: binding to a support (physical
adsorption or chemical binding), encapsulation or entrapment and cross-linking.
The physical adsorption represents a method for reversible immobilization of bio-
molecules onto support materials which occurs through weak non-specific forces
such as van der Waals or Coulomb’s forces, hydrophobic interactions and hydrogen
bonds. It is a simple method allowing regeneration and reloading of the support
material with a high commercial potential due to its low cost. The limitations of this
method are related to the too weak bonds between the biomolecules and the substrate
leading to leakages [15, 16]. An attractive technique for increasing the immobiliza-
tion efficiency represents the creation of surface relief gratings into thin films of
azobenzene containing polymers. The fabrication of nanostructured materials by
photo inscription of surface relief gratings represents a simple, controllable, eco-
nomical and reproducible method.
50.4 Azo Materials as Sensing Platforms for Detection

of CBRN Agents
The azobenzenes are organic compounds which contain azo (-N¼N-) chromophore
group linked to two aromatic rings. They have two geometrical isomers (trans
(E) and cis (Z)) with strong electronic absorption of the -N¼N- conjugated π system.
The main characteristic UV-VIS absorption bands are at λmax ~440 nm related to the
n!π* transition or S1 excited state and at λmax ~340 nm related to the π!π*
transition or S2 excited state [17–19]. The E!Z isomerization can be driven by
ultraviolet (UV) light irradiation usually at λ ~365 nm, the reverse Z!E isomeriza-
tion occurs spontaneously in the dark, under thermal treatment or by exposure to
visible (VIS) light (Fig. 50.1).
According to the spectral properties, the nature and the position of the substitu-
ents in the aromatic rings azobenzene derivatives can be classified (according to
Rau) [20, 21] as: (i) azobenzene derivatives (ABn); (ii) aminoazobenzene derivatives
(aAB); (iii) pseudostilbenes (pSB) (Fig. 50.2).
The substitution pattern of the AB molecules determines their photochemical
behaviour. The presence of electron withdrawing (EW) groups like -CHO, -CN, -NO2
and electron donating (ED) like N(R)2, -OH, -OR, cause asymmetrical electron (“push-
pull”) distribution on the molecular backbone and a decrease of the energy of the
electron transitions, where the π!π* and n!π* bands are well separated [22].
The azobenzene molecule is of interest because of its colouring properties. The
azo dyes represent approximately 60–70% of all dyes used in the food and textile
manufacture (Tartrazine, Azorubine, Amaranth, Brilliant Black BN, etc.). Another
interesting feature of the azobenzene molecule is the ability to change its spatial
arrangement under light irradiation [23]. It is mainly studied for optical application
but this characteristic of the azobenzene molecule make it well-suited also for
application in bioengineering devices [24–29]. Over the last few years surface relief
gratings (SRGs) created on thin films of azobenzene containing polymers are widely
investigated as nanostructure for biosensing applications. They offer key advantages
for biosensing applications requiring in-situ or portable detection due to their
Fig. 50.1 Photoisomerization of azobenzene chromophores

Fig. 50.2 General types of substituted ABs
inherent compact footprint, compatibility with collinear optical formats and easiness
of integration with other micro-technological platforms, such as microfluidic [28].
A method of detecting G-type nerve agents based on the colouring properties of
azomolecules has been patented by Thoraval and Bovenkamp. The detector material
consists of a paper base in which dyes have been incorporated; each dye is sensitive
to a particular family of liquid chemical warfare agent droplets. In the presence of
specific chemical agent the detector material assumes a characteristic colour [30].
Nair, Escobedo and Sabat have demonstrated a biosensor platform based on
inscription of crossed surface relief gratings (CSRGs) with a depth of 75 nm and
grating pitch of 550 nm on azopolymer thin films with a thickness of ca. 190 nm by
using a solid-state diode-pumped laser (COHERENT, USA, Verdi V5, λ ¼ 532 nm)
with an irradiance of 382 mW/cm2. The prepared CSRGs were coated with gold,
modified with biotin and incubated in a streptavidin solution with different concen-
trations. The CSRG shows ability to detect local refractive index changes due to the
biotin-streptavidin binding events [31].
By photoirradiation the azomolecules deform due to the trans-cis isomerisation. If
there are biomolecules on the surface of the thin azopolymer film during the
illumination, it deforms along their shapes [32]. This strategy has been successfully
used for immobilization of desoxyribonucleic acids, proteins and viruses.
Ikawa et al. [33] reported photoimprint-based immobilization of the Tobacco
mosaic virus (TMV) with cylindrical shape and sizes of 18 nm in diameter and
ca. 300 nm in length onto azopolymer surface. A droplet of an aqueous solution
containing TMV was placed on the surface of a poly{40-[[[2-(methacyloyloxy)
ethyl]-ethyl]amino]-4-cyanoazobenzene-co-methy methacrylate} thin film prepared
via the spin-coating technique. After drying the droplet, the polymer surface was
irradiated with light at a wavelength of 470 nm from blue-light-emitting diodes.
Then the surface was washed by an aqueous solution with detergents. The polymer
surface was observed at each step by AFM. TMV was shown to embed itself
gradually on the polymer surface during photoirradiation in a time scale of tens of

minutes because of the formation of surface grooves complementary to the shape of
TMV. The immobilization process is believed to be a noncovalent physical process,
because the TMV is completely removed from the azopolymer surface only by
washing with surfactants even after 30 min photoirradiation, and because the
absorption spectra of the azopolymer were confirmed to be unchanged under these
experimental conditions.
50.5 Conclusions
For detection of biothreats at the point of dissemination, expensive equipment with

integrated systems for sample collection, preparation and analyzing is needed, now
available only to the military of a limited number of countries. The biosensor
represents a portable, easy to use, all in one piece of equipment with which sample
collection and analysis can speedily be done. One of the scientific factors which
currently mitigate the use of biosensors for environmental monitoring of biological
agents is the unstable immobilization of the biomolecules. Photoresponsive surfaces
such as azobenzene functionalized thin films whose chemical and physical proper-
ties can be changed or tuned in an accurate and predictable manner are a promising
alternative for switched immobilization/mobilization of biomolecules, such as pro-
tein adsorption, cell adhesion, DNA or RNA attachment and so on [32, 34]. However
there are limited literature sources reporting the development of biosensors for the
detection of category A biological agents using azo polymers as sensing elements.
While the success of the nanomaterials as biothreat detection platforms has been
demonstrated in the laboratory, factors such as scale-up, device fabrication, systems
integration, and interfacing, have yet to be managed.
Acknowledgments This work is financially supported by the National Science Fund of Bulgaria, №
DN 08/10, 13.12.2016.
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Index
A Carbon nanotubes
Absorption, 36–39, 41, 44–46, 56–58, 88, 90, composites, 178, 182–184, 243, 246, 256,
97, 99, 180, 230–232, 234, 255, 274, 262–264, 266–271
275, 277, 294, 295, 302, 376, 377, electrical conductivity, 183, 185, 262, 269,
379–381, 428, 430–432, 469, 474, 502, 270
503, 505 electronic properties, 179, 185, 229, 230
AC conductivity, 134, 155, 160, 162, 269 multiwalled, 262, 462
Activation energy, 96, 117, 125, 126, 133–135, purification, 181, 186, 231
160–162, 262, 267, 269, 271, 289, 291, separation, 179, 230–232, 234, 236, 237
330 CBRN agents diagnostic, v–vii, 499–505
Al-substitution, 33, 35, 36 Chalcogenide films, 50, 51, 318–322,
Amperometric Biosensor, 310, 311, 314, 315, 324–331
334, 337 Chalcogenide glasses (ChGs), 50, 51,
Anodization, 435–437, 439–441 95–98, 310, 311, 313–315, 334,
Anodized aluminium oxide (AAO), 435–441 337, 340
Antibacterial properties, 468, 470, 473–475 Chemical agents, 18, 257, 504
Avrami parameter, 364–366 Chemical agents, 18, 257, 504
Azo polymers, 505 Colorimetric sensor, 428, 429
Composite materials, 70, 95, 185, 256, 257,
262, 269, 271, 282, 334, 402
B Convergence, 4–11, 242
Barium-strontium titanate, 353, 355 Crystallinity, 140, 194, 302
Barium titanate (BaTiO3), 17–19, 21, 22, 24, Crystallization, 72, 128, 129, 350, 352–356,
27, 350, 352, 355, 368, 369, 371 358, 367–372, 418, 420, 424
Bi2O3, 140, 146, 368–370, 372
Biocomposites, 285–289, 291
Biological agents, 247, 248, 254, 255, 257, D
499–502, 505 Data analytics, 4, 7, 8, 11
Bismuth niobate (BiNbO4), 140–148, 150 D-band center, 454, 455, 462, 464
De novo design, 478, 479
Defense, 4–11
C Diamond-like carbon (DLC), 468–475
Carbon clusters, 55, 56, 58 Diamond nanopillars, 201–203

Biophysics, https://doi.org/10.1007/978-94-024-1298-7
510 Index
Dielectric constant, 108, 128, 129, 140, 143, Humidity sensor, 408, 410, 419, 420,
145, 150, 154–156, 169, 170, 172, 263, 439, 440
266, 274, 275, 277, 350, 351 Hybrid film, 38, 40, 41
Dielectric properties, 140–150, 166, 270, 286, Hybrid materials, 37, 345, 346, 408–416
350, 368 Hybrid nanocomposite, 38, 310
Dielectric relaxation, 107, 157, 158, 160, 162, Hydrogen evolution, 455, 459, 460
172, 262, 265, 266, 285–291 Hydrogen gas sensor, 445–449
Directed evolution, 480–483
Dual pulsed laser deposition, 475
I
Impedance measurements, 319, 321
E Impedance spectroscopy (IS), 155,
Electrical characterization, 136 167, 168
Electronic properties, 179, 185, 229, 230 Infrared absorption spectroscopy, 87
Electron spin resonance spectroscopy, 488 Integrated microelectronics, 436
Electrospinning, 242, 243, 246–249, 254–257, Ion implantation, 44–46, 50–51, 55–58, 198,
418 334
Energy, v, 13, 18, 40, 44, 50, 51, 56–58, 63, 96,
98, 117, 122, 125, 126, 129, 133–135,
160, 162, 166, 178, 182, 183, 185, 194, J
197, 222, 231, 232, 234, 250, 258, 262, Juniperus communis, 491
267, 269, 271, 273, 275, 276, 289, 291,
330, 335, 376, 377, 418, 419, 438, 439,
445, 446, 454, 462, 469–474, 481, 503 L
Enzyme, 247, 311, 314, 315, 346, 468, Lab-on-chip, 13
478–483, 488–491, 502 Lawn grass, 294
Etching, 50, 64, 65, 98, 201, 203, 206, 207, LiNbO3, 122, 128–130, 135
209, 211 Lithium sodium sulphate (LNS), 87–92
Evanescent field, 494 Low-power alternating magnetic field, 300,
301, 303
Luminescence, 38, 41, 67, 70, 216, 376, 382,
F 383, 386
Filtration, 13, 230, 241–251
Frequency domain, 106
M
Magneli phases, 455, 456, 461, 462, 464
G Magnetic properties, 98, 99, 166–173, 274,
Gas sensor, 185, 318, 389–395, 418, 446 300, 302, 489
Gel chromatography, 230, 232 Magnetite, 276–278, 281, 300–304, 489
Glass, 38, 50, 69, 95, 107, 122, 153, 186, 287, Magnetoelectrics, 32, 33
310, 318, 334, 340, 361–366, 368, Manganese, 96, 97, 310
375–386, 418, 471, 495 Mechanical ball milling, 88
Glass-ceramics, 122, 128–131, 133–136, Mechanical strength, 242, 246
153–162, 334, 350, 368 Melt quenching, 88–90, 154, 334, 418
Glass crystalline materials, 418–424 Mercury ions, 428
Glass crystallization, 418, 424 Metal nanoparticles, 44, 46, 50, 51, 64, 184,
Graphene, v, 178, 179, 181–186, 221–226, 398 293, 295, 334, 431, 468
Green synthesis, 293–297, 427–432, 489 Metamaterial, 494–498
Microhardness, 342
Microsphere, 498
H Microwaves, 106, 140–150, 216, 277, 294, 301,
Havriliak-Negami function, 286 350, 367
Havriliak-Negami model, 267, 271 Multilayer nanostructures, 98, 99
Index 511
N R
Nanocomposite Raman spectroscopy, 63, 96, 218, 219,
films, 38–41, 51, 56–58, 390 230–232
Nanodiamond, 179, 184, 197, 218 Rare earth (RE), 69–78
Nanofibers, 11, 12, 184, 241–251, 254–258 Rational design, 480–482
Nanoporous materials, 408 Reduced graphene oxide (RGO), 397–402
Nanosized ferrites, 273–282 Relative humidity (RH), 400, 402, 404, 408,
Nanotube, v, 177, 179–182, 222, 229, 243, 246, 410, 414, 416, 418, 420, 422–424, 439,
256, 262–271, 390, 392, 462 440
NiCo2O4, 80–85 Rhodamine 6G, 38
Nucleation, 128, 129, 194, 216, 361–366, 399 Roadmap, 4–11
NV centers, 196, 198, 199, 203
S
O Screen-printing, 410, 419, 420
Optical band gap, 55–58 Security, v, vi, 4–11, 246, 247
Optical fiber, 129, 375–377, 383, 386, 494 Sensor, v, 21, 38, 166, 178, 215, 222, 230, 256,
Optical spectroscopy, 43 310, 318, 325–327, 330, 334, 340, 375,
Organic-inorganic hybrid, 310, 334, 340 389, 400, 408, 418, 428, 436, 446, 468,
Organohalogen compounds, 483 500, 501
Oxyfluoride glasses, 375–386 Shielding, 32, 262, 273, 274
Oxygen evolution, 455, 458, 460–462, 464 Silane, 198, 299–304
Oxygen reduction, 184, 455 Silver doping, 318, 475
Silver nanoparticles, 44, 257, 293–297, 398,
427–432
P SiV centers, 195, 197–199, 204, 205,
Parsley, 294–297 215–220
Pathogen decontamination, 493 Sm oxide, 377
pH, 33, 80, 222, 223, 226 Sol-gel auto-combustion, 32
Phase separation, 344, 352 Sol-gel technique, 398–400, 402
Phosphorescence, 72, 75–77 Solid state, 142, 147–150, 166, 178, 311, 341,
Photolitography, 63 456
Photoluminescence (PL), 38, 67, 70–76, 98, Specific loss power (SLP), 301, 304
196, 197, 216, 379, 382, 383, 500 Spectral parameters of ZPL, 216–218, 220
Photonic crystal, 51, 200, 206, 210, 211, 498 Spinels, 35, 79–86, 302
Platinum-ZrO2, 362 Strontium aluminates, 69, 70, 77, 78
Polyaniline (PANI), 222–225, 389–395 Superoxide dismutase, 488
Polymethylmethacrylate (PMMA), 44, 50, 51, Superparamagnetic iron oxide nanoparticles
55–58, 376 (SPIONs), 299, 300, 489–491
Polymers, 44, 70, 95, 122, 167, 222, 230, 254, Surface enhanced Raman scattering (SERS),
262, 277, 278, 280–282, 286, 287, 294, 50, 63–67
301, 302, 310–315, 334–337, 342, 344, Surface modification, 51, 300
371, 372, 389–392, 394, 395, 408, 464, Surface planarization, 206, 207, 209–211
468, 479, 480, 502–505 Surface plasmon resonance, 44–46
Porosity, 128, 168, 170, 172, 183, 184, 246, Swelling, 334
254, 439
Protective clothing, 246, 248, 250, 254–256,
258 T
Protein engineering, 478–480, 482, 483 Thermal characterization, 87
Pulsed laser deposition (PLD), 17–27, 475 Thermally stimulated depolarization currents
Pulsed light technique, 493 (TSDC), 121–124, 126, 127, 131, 133,
Pyrochlore oxides, 367 135, 136
512 Index
Thermally stimulated polarization currents X

(TSPC), 121, 122, 126, 127 X-ray sensors, 381
Thin films, 18, 38–40, 50, 51, 77, 122, 185,
194, 296, 297, 318–322, 324–327, 346,
502–505 Y
Time domain, 105–118, 376 Yttrium ferrites, 166
Transition elements, 438 Y-type hexaferrites, 31–36
U Z
Ultrasonic co-precipitation, 32 ZnO, 140, 256, 362, 378, 418–424, 445
Ureasil, 310, 334, 340
Ureasilicate materials, 340

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NATO Science for Peace and Security Series - B:

Physics and Biophysics

A. Chemistry and Biology Springer

Series B: Physics and Biophysics

Published in Cooperation with NATO Emerging Security Challenges Division

Library of Congress Control Number: 2018941543

ISBN 978-94-024-1516-2 (PB)

Printed on acid-free paper

All Rights Reserved

The ever-increasing requirements towards different aspects of security, for example,

Soﬁa, Bulgaria Plamen Petkov

Part I General Topics

Part II Material Preparation and Processing

6 Formation of a Periodic Structure in a Chalcogenide Film

Part III Structural and Optical Characterization

Part IV Electrical Characterization

16 Dielectric Analysis of Phosphate-Borate Glass-Ceramics

Part V Materials: Graphene, Nanotubes and Nanodiamonds

Part VI Materials: Nanowires and Fibers

Part VII Materials: Nanocomposites

Part VIII Materials: Glasses and Polymers

34 Sr-Substituted Barium Titanate Glass Ceramics from Oxide

Part IX Applications: Sensors and Detectors

44 Individual Bi2O3-Functionalized ZnO Microwire for

Part X Applications: Water Treatment, Environment and Health

Abstract Setting priorities in a complex defence environment requires technology

Keywords Data analytics · Convergence · Roadmap · Defence · Security

© Springer Science+Business Media B.V., part of Springer Nature 2018 3

In a conventional defence scenario, the outcome can be predicted by estimating the

precise and customized data management and analysis practical. Multidisciplinary

1.2 Advanced Sciences Convergence and Foresight

1.3 Foresight Innovation Pathways Methodology: Data

Table 1.1 Data analytic tools developed and scope [3]

impact in speciﬁc ﬁelds of research. Bibliometrics (aka scientometrics) applies

Table 1.2 Speciﬁc methods used for roadmapping using ASC

1.4 Monitoring, Surveillance, Roadmapping: Metrics

A scientiﬁc landscape in conjunction with future studies methodologies would

Table 1.3 Data analytic tools developed and scope [8]

Within the framework of the recommendations of data analytics and anticipated

1.5 Discussion and Path Forward

Table 1.4 Trends in nanotechnology

Table 1.5 Trends in biotechnology

Table 1.6 Trends in information technology and ambient intelligence

1. Vaseashta A, Dimova-Malinovska D, Marshall JM (eds) (2005) Nanostructured & advanced

Tomáš Kocourek, Miroslav Jelínek, Václav Studnička, and Jan Drahokoupil

Keywords BaTiO3 · Thin layer · PLD · Crystallinity

Barium titanate (BaTiO3 or BTO) is a ferroelectric ceramic material, showing a

T. Kocourek (*) · M. Jelínek

© Springer Science+Business Media B.V., part of Springer Nature 2018 17

2.3 Results and Discussion

The inﬂuence of the following deposition parameters on BaTiO3 growth was

Fig. 2.13 (continued)

1. Chernova E, Pacherova O, Chvostova D, Dejneka A, Kocourek T, Jelinek M, Tyunina M

Borislava Georgieva, Svetoslav Kolev, Chavdar Ghelev,

Keywords Magnetoelectrics · Y-type hexaferrites · Al-substitution · Sol-gel auto-

The continuously increasing use of devices operating at microwave

B. Georgieva (*) · S. Kolev · C. Ghelev · T. Koutzarova

© Springer Science+Business Media B.V., part of Springer Nature 2018 31

aluminum ones in Ba0.5Sr1.5Zn2Fe12O22 results in the appearance of a magnetic

The Ba0.5Sr1.5Zn2Fe12O22 and Ba0.5Sr1.5Zn2Al0.08Fe11.92O22 powders were synthe-

3.2.1 Sol-Gel Auto-combustion

3.2.2 Ultrasonic Co-precipitation

This technique consists in dissolving the corresponding metal nitrates in deionized