5

Chemical Properties

Not the least remarkable and useful of the properties of polyethylene is its
chemical inertness. PE is unaffected by prolonged contact with those strong acids
(including hydrogen fluoride) which attack many metals, highly caustic alkalis
which rapidly damage glass, as well as most organic substances. Yet the pure
polymer weathers rapidly when exposed outdoors to the atmosphere, burns
easily and may be affected by common detergents. These properties are all
aspects of the chemical behaviour of the material, the subject of this chapter.
The contrast between the inertness of PE and some other polymers towards
many aggressive reagents, including solvents, and its sensitivity to atmospheric
degradation warn us to expect some complexity in the chemical properties of
polymers. We shall discuss a number of agents of chemical change which are of
engineering importance for polymer materials. These are solvents, environmental
agents (producing weathering and ageing), fire, radiation, and biological organisms.

5.1 Solubility and Solution Properties

The action of solvents stands apart somewhat in this list of themes because it
does not produce permanent chemical change in the polymer material. However,
solvents produce profound physical changes in the polymer and these changes
occur as a result of the chemical nature of both the solvent and the polymer.
The technical importance of the solubility properties of polymers is enormous,
and has no real counterpart in the technology of other major classes of
engineering materials. Four examples of technical processes depending on
solvent action illustrate this.
(1) Many polymers can be joined by solvent welding, or by the use of
adhesives consisting of dissolved polymer.

121
122 POLYMER MATERIALS

(2) Synthetic fibres can be produced by continuous evaporation of solvent

from jets of polymer solution.
(3) Polymer films and sheet are produced by solvent casting. Similarly film
formation in paint-drying frequently occurs by solvent evaporation.
(4) In two-phase polymer blends, differences in solubility between the
two phases are used to produce filtration membranes and to modify surface
properties.
Modern approaches to understanding solubility require us to consider the free
energy differences between the two states A and B of figure 5.1. If A has a lower
free energy than B, the solid substance does not pass spontaneously into solution
— it is insoluble. We recall that the free energy is a composite quantity comprising
an enthalpy term (which depends on the strength of the van der Waals' forces
acting between molecules) and an entropy term (depending on the degree of
disorder of the molecules and their constituent parts). If the forces between the
solvent molecules and the polymer molecules are stronger than those between
adjacent polymer molecules in the solid, then solubility is favoured. The inner
cohesion of the polymer solid increases with the degree of crystallinity as the
efficiency of molecular packing assists intermolecular interactions. All other
things being equal, we may expect crystalline polymers to be less easily dissolved
than amorphous. Furthermore the old practical rule like dissolves like carries a
seed of truth, for at least it is the case that polar solvents (water, alcohols,
ketones) are likely to be effective in penetrating and perhaps ultimately
dissolving polar polymers.
Flexible polymer chains are more or less firmly held in the solid state but
acquire considerable configurational freedom on passing into solution. This is
reflected in an increase in entropy on dissolving, a factor which promotes
polymer solubility. However, the gain in entropy is not so great for polymers as
for substances composed of small independent molecules. As a result many
polymers will dissolve in only a few well-matched solvents, and polymers
solutions exhibit an unusual variety of phase separation (demixing), partial
miscibility and fractionation effects.

(A) (B)

Figure 5.1 Polymer solubility. The solid polymer dissolves in the solvent only
if state B has a lower free energy than state A
 CHEMICAL PROPERTIES 123
One approach to predicting polymer solubility has been widely applied for
technological ends. This in essence assumes that the enthalpic term is dominant.
A solubility parameter 8 is defined for both solvent and polymer (table 5.1). 5
is a measure of the strength of intermolecular cohesion in the pure solvent or in
the pure polymer. For the solvent 6 is calculated from the energy of vaporisation.
For the polymer it is obtained indirectly, and may be estimated from the primary
structure of the chain. The significance of the solubility parameter is that
polymers are soluble only in solvents of similar 8. Thus, for example, natural
rubber (5 = 8.3) is dissolved by toluene (6 = 8.9) and carbon tetrachloride
(6 = 8.6) but not by ethanol (8 = 12.7). Unfortunately, this general rule only
holds if strong polymer—solvent interactions are absent. It is unlikely that any
simple predictive method can provide for the whole range of solubility
behaviour.
If a solvent S dissolves a polymer P it is invariably found that the polymer
dissolves the solvent also. Frequently there are limits to the amount of P which S
will dissolve and the amount of S which can be absorbed by P. These limits define
the miscibility range of the two substances. Sometimes the polymer and solvent
are sufficiently well matched that they are miscible in all proportions. The
absorption of small amounts of S by P produces changes in physical, especially
mechanical, properties. Controlled use of such plasticisation is an important
aspect of polymer technology and the matter is taken up in chapter 6. We
note in passing, however, that such external plasticisers are free to migrate
within and permeate through the polymer material. In the following section we
discuss the more important topic of the permeability of polymer materials to
gases and vapours.
Crosslinked polymers cannot dissolve in the sense we have described, for
individual polymer chains cannot be detached from each other. Such materials
show extensive swelling when they come into contact with compatible solvents.
Such effects are often important in the performance of elastomer components
such as seals and hoses.
. An especially interesting property of the polymer solution is its viscosity. In
dilute solution, the individual polymer chains are well separated; the increase in
viscosity (relative to the viscosity of the pure solvent) therefore reflects the
hydrodynamic friction caused by the presence of isolated polymer molecules in
the flowing solution. As might be expected, this is directly related to the size of
the polymer molecule and thus to the molar mass or chain length. The viscosity
of dilute solutions of many linear polymers obeys the Mark-Houwink law

-lWcl =lv]=KMa (5.1)

[(i-)A]
*•
where TJ is the solution viscosity, tj 0 the solvent viscosity, and M the molar mass.
The quantity [TJ] is the limiting viscosity number (or intrinsic viscosity), obtained
as the limiting slope of (TJ/T}0 - l)/c as the polymer concentration c approaches
124 POLYMER MATERIALS
zero. The Mark-Houwink parameters K and a depend on the polymer and the
solvent. This relation is widely used to determine the molar mass of polymer
samples since the viscosity is easily measured, usually in a simple U-tube capillary
viscometer (see, for example, ASTM method D2857). The parameters K and a
provide information on the polymer-solvent interaction and on the mean end-to-
end separation of the polymer chain in solution (represented in figure 1.6 by
the quantity r p ). In a 'good' solvent, the polymer molecule adopts a relatively
open random chain conformation, the distance rp being somewhat greater than
the value r p0 calculated for the freely jointed chain; when the polymer-solvent
interaction is less favourable, the polymer adopts a tighter conformation, reduc-
ing its mean radius. The tightest coiling occurs in a solvent in which the polymer
will only just dissolve. In this case, the polymer chain tends to coil back upon
itself to maximise the number of contacts between different parts of the chain
and to minimise molecular contact with the solvent. Further reduction in the
quality of the solvent produces precipitation of the polymer as separate chain
molecules aggregate together. Solvents in which rp has the unperturbed value
r po are called Flory or theta solvents. In practice, these are poor solvents and the
polymer chain cannot shrink its end-to-end separation much below rpQ without
precipitating from solution. (Since polymers dissolve in most solvents over a very
limited range of temperatures, there is also a theta temperature in any solvent.)
In a theta solvent, the Mark-Houwink parameter a = 0.5; in better solvents, a is
larger, rising to a maximum of about 1.0.
The separation of individual polymer molecules which occurs in dilute solu-
tion in good solvents can be exploited in other ways to determine molar mass (or
chain length) distributions. The angular intensity variation of light scattered
from a dilute polymer solution provides a direct measure of the molar mass
distribution of the polymer. In size exclusion chromatography, the polymer
molecules flowing through a chromatograph column packed with porous solid
are retained to an extent which depends on their ability to enter the pores of the
packing. This subtle effect causes a separation of molecules according to molecular
size (and hence molar mass). An example of a molar mass distribution obtained
by this technique (also known as gel permeation chromatography) was shown in
figure 1.5.
We have emphasised the ability of solvents to separate polymer molecules and
to transform solid materials into a fluid state for various practical purposes. We
end this section with a reference to the ability of some polymers in solution to
achieve precisely the opposite: namely, to convert the solvent into a solid or
semi-solid material. The process of gelation, in which small quantities of dissolved
polymers link together to form a continuous network throughout the solution,
is both useful and scientifically interesting.
An aqueous gel is a random polymer network structure within which sub-
stantial amounts of water are retained. Gels are usually formed from aqueous
solutions of linear polymers which crosslink by chemical reaction or physical
entanglement. As crosslinking develops, the solution viscosity rises rapidly,
 CHEMICAL PROPERTIES 125
becoming infinite at the gel-point (or the sol-gel transition). Several water-
soluble polymers can form hydrogels at concentrations as low as 1 per cent by
weight of polymer. The properties of chemically crosslinked aqueous gels
(particularly of poiyacrylamide and acrylamide-acrylic acid copolymers) have
been investigated by Tanaka whose work has revealed a variety of striking
physicochemical effects. For example, aqueous gel samples exposed to mixed
acetone/water solvents or to salt solutions may collapse dramatically at critical
acetone or salt concentrations, shrinking in volume by a factor of as much as
100 (figure 5.2). The theory developed to explain these transitions is in essence
an extension of the theory of rubber elasticity to take account of the interionic
forces between the aqueous solution and the ionic groups attached to the gel
network. The phase transitions which are observed arise when the gel is unable
to find a stable balance between the osmotic, electrostatic and rubber-elastic
forces acting within it.

8
CD

1
0.05 0.5 5.0 50.0
Swelling ratio (final volume/initial volume)
Figure 5.2 Volume of a crosslinked acrylamide/acrylic acid polymer gel in
acetone/water mixtures, showing the sudden and very large shrinkage transition
at a well-defined acetone concentration (after Tanaka)

5.2 Permeability

Many engineering uses of plastics and rubbers depend on their often excellent
barrier properties. The rate at which gases and vapours permeate polymer films
depends on the partial pressure gradient across the film (figure 5.3). The
following relation generally holds at least approximately (at a given temperature)
Flux/Area =/>(/>, - p2)/l (5.2)
where the permeability coefficient P depends on the polymer material and the
permeating substance, partial pressure p. If the steady-state diffusion of penneant
within the film obeys Fick's law then
Flux/Area = ~D(dc/dx) (5.3)
 TABLE 5.1
Solubility parameter 8 of polymers and solvents 8
Polymers 5 (cal* c m - 3 ' 2 ) Solvents 6(cal cm /2
)

PTFE 6.2 n-Pentane 6.3

Poly(dimethyl siloxane) 7.3 n-Hexane 7.3
PE 8.0 n -Octane 7.6
PP 7.9 Di/sopropylketone 8.0
PIB 8.0 Cyclohexane 8.2
SBR 8.1-8.6 Carbon tetrachloride 8.6 3
Natural rubber 8.1 Toluene 8.9 r
><
BR 8.5 Ethyl acetate 9.1 S
Polysulphide rubber
PS
9.0-9.4
8.5-9.7
Dioxane
Acetone
9.9
10.0
I
CR 9.2 Pyridine 10.9
PVAC 9.4 Ethanol 12.7 >
PMMA 9.2 Methanol 14.5
PVC 9.6 Glycerol 16.5
PVDC 9.8 Water 23.4
PETP 10.7*/
Cellulose acetate 11.4'
EP 11.0V
POM 11.1*
Nylon 66 13.6<
PAN 15.4 r

Note: 1 cal = 4 . l 6 J.
 CHEMICAL PROPERTIES 127

Flux

Figure 5.3 Permeation of gases and vapour through a polymer under the
action of a partial pressure gradient (px - p2)/l

where D is the diffusivity. If D is independent of c then

Flux/Area = -Dicx - c2)/l (5.4)
where cy and c 2 are the concentrations of the diffusing substance at the
surfaces 1 and 2.
If in addition the gas or vapour dissolves in the film according to Henry's
law
c = Sp (5.5)
(S is the solubility). It follows that
P = DS (5.6)
Thus the observed permeabilities depend on the interplay of diffusion and
solubility parameters. Table 5.2 lists permeability coefficients, diffusivities and
solubilities of a number of gases and vapours in common polymers. The
atmospheric gases generally have relatively low solubilities and obey Henry's
law, but diffuse freely through amorphous regions of solid polymer. Vapours of
organic substances with 5 values similar to the polymer have relatively high
solubilities with deviations from Henry's law, but diffuse more slowly. The slower
diffusion is a result of larger molecular sizes and often strong interactions with
polymer chains. Permeability generally increases with increasing temperature;
and for a particular polymer decreases as crystallinity increases (figure 5.4).
Important high barrier polymers with low permeabilities to both gases and
water include PVDC and copolymers, acrylonitrile—styrene copolymers, EP
resins, PVDF, PETP and PVC. PUR, PS and common elastomers have poor barrier
properties. PVAL and regenerated cellulose (cellophane) have very low resistance
to the passage of water but are good gas barriers when dry. Conversely, PE, PP
and PTFE are good water barriers, but have quite high permeabilities to
permanent gases. Table 5.3 shows the importance of primary structure in
controlling permeability.
 TABLE 5.2
Permeability of common polymers to gases and vapours, together with corresponding diffusivity and solubility data at 25 °C

Polymer Permeant 10 IS P 10I2D 10 3 5

(kgm" 1 kPa (m2s-') ( k g m - J k P a-i-,
-')

PA 6
(Nylon 6 ) , / Nitrogen 0.023 0.025 0.94
PETP Nitrogen 0.063 0.13 0.48
PVC Carbon dioxide 0.52 0.21 2.5
PCTFE -PVDF
copolymer Nitrogen 0.85 0.36 2.4
PIB Nitrogen 3.1 4.5 0.69
Carbon dioxide 77 5.8 13
CR Nitrogen 11 25 0.44
Carbon dioxide 300 24 16
NR Nitrogen 76 110 0.69
Carbon dioxide 1900 110 18
n -Propane 2500 21 120
HDPE Helium (30 °C) 1.9 360 0.005 4
Oxygen (30 °C) 5.4 22 0.25
Nitrogen (30 °C) 1.7 12 0.14
" Carbon dioxide (30 °C) 31 16 2.0
LDPE , Isobutene (30 °C) 680 4.7 140
n-Hexane (30 °C) 6200 2.5 2500
Water 540 23 24

Note: 1 kPa = (1/101.3) atm = 0.01 atm.

 CHEMICAL PROPERTIES 129

500 -t 1 1—
PTFE

400 r-

Nitrogen

920 930 940 950 960 10 20 30 40 50 60 70 80 90

Density (kg m~3) Amporphous content (%)
(a) (b)
Figure 5.4 (a) Permeability P to nitrogen of PE films of different densities
(and degrees of crystallinity), measured at 25 °C. (b) Permeability P to carbon
dioxide and nitrogen of PTFE of different crystallinities, measured at 30 C

A variety of units has been used in reporting permeabilities; among the

commonest are
cm3 (at STP) m - 2 d a y - ' atm~' (film or sample thickness / stated)
cm3 (at STP) c m - ' (cm Hg)~' s " '
g c m - 2 s - ' (cm Hg) _ ' (/ stated)
In the SI system the quantity V has the units m 2 s~' and the Henry's law
solubility 5 usually has the units kg m - 3 k P a - ' . The units of P then follow

TABLE 5.3
Effect of primary structure on oxygen permeability
P of carbon chain polymers f CH2 - CHX)-
(adapted from Nemphos et al.)

-X 10' 5 P
( k g m - 1 kPa - 1 s - ' )

-OH 0.000 6
-CN 0.002
-CI 0.51
-F 0.96
-CH3 9.6
-C6HS 27
-H 31
130 POLYMER MATERIALS

directly from equation 5.5, that is, kg m kPa s .It follows from the gas
laws that
cm 3 (at STP) c m - 1 (cm Hg)~' s - * =
(3.346 3 x l O " 3 M / k g m o r 1 ) kg m " 1 kPa - 1 s" 1
where M is the molar mass of the permeant.
In British practice the water vapour permeance of membranes (whose
thickness may not be known) is commonly reported in units g MN~' s~' .The
reciprocal of this quantity is the water vapour resistance.

5.3 Environmental Stress Cracking and Crazing

Some polymers when stressed are adversely affected by contact with certain
active chemical substances. Aqueous solutions of surface-active compounds such
as detergents can produce slow largely brittle cracking in stressed PEs. The term
environmental stress cracking (ESC) was introduced to denote this particular type
of failure. ESC is now used more generally to describe the promotion of slow
brittle failure in stressed polymers by organic substances, as for example the
cracking of PVC gas pipes by certain hydrocarbon impurities. Organic liquids
and gases can also promote the formation of fine networks of voids {crazes)
in amorphous polymers, such as PS. Crazed material retains considerable
strength, but it is usually unsightly, and its appearance may precede crack
formation. In both ESC and crazing, damage arises from the conjoint action of a
substance in the environment and stress (either externally imposed or arising
internally from processing). Direct chemical attack on the primary bonds of the
polymer chain is not involved. In both cases it appears that the promoting
substance is adsorbed or locally dissolved at defects so as to assist failure, perhaps
by modification of the surface energy or by plasticisation of highly stressed
material at the crack tip. The susceptibility of a polymer to ESC failure depends
on structural factors. For example, the resistance ofPEto stress cracking varies
considerably with molar mass and melt flow index, crystallinity, and density.

5.4 Chemical Attack

The effects of solvents on polymer molecules are usually physical rather than
chemical. The primary polymer chain remains intact, and the polymer can be
recovered by evaporation of the solvent. Of course the microstructure
(morphology) of the recovered polymer solid may be quite different from that
of the original solid.
In addition, as organic (carbon-based) compounds polymers are attacked by a
number of chemical substances which produce irreversible chemical changes
in the chain. These chemical reactions are determined principally by the chemical
 CHEMICAL PROPERTIES 131

structure of the polymer. For example, sulphuric acid H2SO4 reacts with
phenyl groups. Thus PS may be sulphonated

fCH-CH^ 4CH-CH 2 )-
H2SO<
•loj
Similarly PE may be (partially) chlorinated in the same manner as short-chain
paraffins
CI,
fCH^ fCHCl>
Those common polymers which are paraffinic in structure exhibit the relative
chemical inertness of their class. They are attacked only by strong chemical
reagents. However, other polymers (condensation polymers particularly) are
susceptible to chemical attack under milder conditions. Manufacturers of
commercial polymers provide information on the resistance of their products to
a wide range of chemical substances likely (and often unlikely!) to be
encountered in engineering applications. Chemical reactions between polymers
and other substances may sometimes produce useful modifications of properties,
and in fact both the chlorination of PE (and also of PVC and of natural rubber)
and the sulphonation of PS yield commercial polymer materials.
Polymers (in common with all other organic compounds) are vulnerable to
oxidation. Unstabilised polymers undergo slow ageing in contact with air.
Outdoor conditions in particular are very aggressive, for oxidation reactions are
frequently strongly promoted by the ultraviolet radiation present in sunlight.
Degradation of the primary chain occurs more rapidly the higher the
temperature, and heat is an agent of polymer deterioration both in the presence
and in the absence of oxygen. These various processes are classified in table 5.4.

TABLE 5.4
Major agents and modes of polymer degradation

Oxygen Moderate temperature (Thermal) Oxidation

High temperature Combustion
Oxygen Ultraviolet radiation Photo-oxidation
Water Hydrolysis
Atmospheric oxygen,
water, natural light Moderate temperature Weathering, atmos-
pheric degradation
Heat alone Pyrolysis
Ionising radiation Radiolysis
132 POLYMER MATERIALS

The oxidation of polymer materials involves free radical chain reactions

(see section 1.12). Even substances such as PE which are expected to be inert at
moderate temperatures in the absence of light react quite rapidly with oxygen
unless stabilised. It is not likely that direct attack of oxygen on the strong C—H
or C—C bonds occurs under such mild conditions, and it appears that the reaction
is initiated by hydroperoxide impurities incorporated during synthesis and
processing

R-O-O-H • RO- + -OH (i)

and R-O-O-H » R 0 2 - + -H (ii)
The R0 2 * peroxy radicals formed are sufficiently reactive to attack some primary
CH bonds of the chain
fCH 2 > + R0 2 • > £CH> + ROOH (Hi)

and then very rapidly O—O

4CH)- + 0 2 • fCH)- (iv>
The peroxy radical is thus reformed and can attack another CH bond. The action
of this radical continues (the chain reaction propagates) until a termination
reaction intervenes. Then
2R0 2 -
or 2R- non radical products (v)
or RO,-+R-
Generally the rate of oxidation, after an initial period during which hydro-
peroxides accumulate, is determined by process (iii) above. Consequently the
observed rate of deterioration may be considerably increased by the presence of
a small number of easily removed H atoms at irregularities in the chain. For
example it is known that a hydrogen atom is less easily removed from a location
such as I (secondary H atom) than from II (tertiary H atom).

H
T/ H
H
(I) (»)

Thus in PE the solitary hydrogen atom directly bonded to the chain at branch
points is especially vulnerable. It is found that the rate of oxidation is closely
related to the degree of chain branching. The presence of a double bond activates
 CHEMICAL PROPERTIES 133

the adjacent H atom; thus saturation (the absence of double bonds) improves
oxidation resistance. Because of oxygen permeability differences (see section
5.2) crystalline forms of polymers are much more resistant to oxidation than
amorphous forms. The C—F bond is much more resistant to free radical cleavage
than the methylene CH, and PTFE shows exceptional resistance to thermal
oxidation.
It is possible to increase greatly the oxidation resistance of polymers by
incorporating small amounts of additives which interfere with the chain
mechanism outlined above. Such stabilisers are discussed at greater length in
chapter 6.
Both natural rubber and synthetic elastomers such as SBR are attacked by
atmospheric ozone. If the materials are under stress, the degradation leads to a
characteristic form of deterioration known as ozone cracking, in which cracks
appear perpendicular to the stress. The ozone content of the atmosphere is
usually about 0.01 mg k g - ' (one part in 10 8 ), although in polluted air the
concentration may be as much as 100 times greater. Even at such low ozone
levels as these, rubbers require stabilisation against ozone attack if acceptable
service lifetimes are to be achieved. The 0 3 molecule attacks C=C bonds (not a
free radical reaction) and can cause scission of the main chain

Natural rubber NR

5.5 Thermal Stability

The oxidation reactions just described proceed more rapidly at higher

temperatures. However, even if we can stabilise a polymer against thermal
oxidation, the thermal stability of most polymers is limited. By comparison with
ceramics and metals the useful temperature span of polymer materials is restricted.
Table 5.5 indicates the practical maximum service temperature of a number of
engineering materials. Of course the limit is often set by deteriorating physical
performance rather than by thermal instability of the chemical structure.
Nevertheless, heat alone brings about degradation of polymer chains, frequently
by main chain scission with the formation of radicals

In some cases, such as PMMA and PTFE, it is the bond between the terminal
mer and the rest of the chain which breaks. This unzipping reaction releases
134 POLYMER MATERIALS

TABLE 5.5
Upper service temperatures of selected materials

Metals and ceramics (°C)

Plain carbon steels 550

Austenitic stainless steels 800
Nickel chromium alloys 900
Cobalt alloys 950
Molybdenum 1000
Niobium 1150
Silica 1000
Borosilicate glass 450
Asbestos 600
Portland cement concrete 300
Aluminosilicate firebrick 1500
Boron nitride 2000
Graphite 3000

Polymers Intermittent use Continuous use

Polyethersulphone 250 190

Polyurethane elastomer 120 80
PA 66 180 110
PMMA — 80
Acetal copolymer 105 80
PTFE 260 —
EPDM elastomer 180 150
NR 100 80
Fluorocarbon elastomer 260 200
Silicone elastomer 300 —

Nbte: Data for polymers are based on manufacturers' recommendations for particular
materials; precise limits depend on service conditions and performance requirements.

monomer in high yield. (In the hot conditions prevailing in pyrolysis the
monomer is volatile and the material loses weight: see also section 5.9.)
In the case of other polymers, such as the polyolefins, scission occurs at
random locations on the chain and the monomer yield is extremely small. The
degradation reduces the chain length (molar mass) and secondary reactions may
produce more or less complex mixtures of volatile degradation products.
The thermal degradation of PVC occurs by elimination of HO gas without
 CHEMICAL PROPERTIES 1 35
scission of the main chain; at 250 CC and above the reaction occurs rapidly and
almost completely
4CH 2 -CHClf > fCH=CH> + HCl
The reaction is accompanied by embrittlement and by severe discoloration of
the material, arising from light absorption by the alternating C=C and C—C
bonds of the main chain.
At temperatures above about 400 °C, the rate of degradation of the common
polymers is rapid, with pyrolysis largely complete in a few minutes. At such
temperatures, the pyrolysis products may be entirely volatile (as when monomer
yield is high). In other cases (notably crosslinked polymers and some thermo-
plastics such as PVC and PAN) much of the main chain carbon is incorporated in
a non-volatile char. Figure 5.5 shows the weight loss curve of a laboratory
sample of PAN heated at a rate of 5 °C/min. The polymer is stable up to about
250 °C, at which temperature 20 per cent of the material volatilises rapidly with
loss of an organic nitrogen compound. Further degradation occurs steadily up to
about 480 CC. At this temperature, the sample is a black powder in which
nitrogen and carbon atoms have become incorporated in a thermally stable ring
structure (see also section 6.9).
Such carbonaceous residues, which sometimes contain mineral fillers from
the original polymer material, resist much higher temperatures than the parent
substance, especially in a non-oxidising atmosphere. Surface chars have low
thermal conductivities and may protect underlying material from the effects of
heat for a long period. The good performance of timber structures in building
fires is explained in this way. Nylon-phenolic (PA—PF) blends are used as
ablative heat shields on space vehicles during re-entry, when surface temperatures
of several thousand degrees are attained.
Some degree of stabilisation against thermal degradation at modest
temperatures (say below 200 °C) is possible through the use of additives. These
are important in preventing degradation during polymer processing (for example

0.8

0.6
Fractional loss
of weight
0.4

0.2

0
150 250 350 450 550
Temperature (°C)
Figure 5.5 Pyrolysis of PAN: loss of weight at a heating rate of 5°C/min
136 POLYMER MATERIALS
of PVC). The melt temperatures may be sufficiently high for some degradation
to occur in unstabilised materials.
A method devised by Underwriters Laboratories is widely used to assess the
thermal endurance of polymer materials. Put simply, the method determines
the maximum temperature at which a physical property retains 50 per cent of its
initial value for a period of 60 000 hours. This temperature is called — somewhat
curiously - the relative thermal index of the material. The test method is based
on a statistical analysis of how one or more physical properties (such as impact
strength or electrical resistivity) vary with time at different temperatures. It has
proved possible from large amounts of thermal ageing data to establish so-called
generic thermal (or temperature) indices, which provide a comparative indication
of the thermal stability of polymers for the purposes of materials selection (see
table 5.6).

TABLE 5.6
Underwriters Laboratories thermal index (°Cj

ABS 60
PA, PP 65
PC, PETP, PBTP 75
EP 90
UF 100
UP, silicone rubber 105
PCTFE, FEP, PF, MF, PSU 150
PTFE,PES 180
PEEK 240

5.6 High Temperature Polymers

The search for polymers with outstanding thermal stability has been vigorous,
for obvious engineering reasons. Specialised materials have been successfully
developed which owe their heat resistance to features of the primary chain
structure. From the data of table 5.5 it appears that a heat-resistant polymer
should melt above 300 °C and have useful thermal (and preferably oxidation)
resistance in that region. These are severe requirements since some method of
fabrication or processing must also be possible (the polymer must be stable in
the melt or soluble or capable of formation in situ).
Diamond, which may be regarded as a completely crosslinked carbon polymer
based on the C—C single bond, is stable to well over 1000 °C. At higher
temperatures it transforms spontaneously into graphite, a carbon polymer based
on flat sheets built of 6-carbon (aromatic) rings. Graphite is thermally stable at
temperatures well over 2000 °C. These facts suggest that polymeric carbon-based
 CHEMICAL PROPERTIES 137
materials of good thermal stability are possible, although in their physical
properties they may exhibit some of the properties of ceramics.
The examples of diamond and graphite suggest that crosslinking and structural
rigidity bring thermal stability. Strengthening the main chain by incorporation
of aromatic 6-carbon and similar rings, and the synthesis of polymers with
ladder-structure chains have yielded useful heat-resistant materials. Some
structures are given in table 5.7. The aromatic polyimides and polyamides
(aramids) are now important commercial materials.

5.7 Photo-oxidation

Early failures in outdoor uses of plastics and rubbers quickly revealed the severe
effect of ultraviolet light on many polymers in the presence of oxygen. Figure
5.6 shows the distribution of energy in the solar spectrum (diffuse daylight).
The molar photon energy is given on the lower abscissa scale. The C—C bond
energy is about 330 kJ/mol corresponding to a photon wavelength of 360 nm.
This means that light of this wavelength or shorter is capable of breaking C—C
bonds in polymer molecules by which it is absorbed. 290 nm may be taken as
the shortest wavelength (highest energy) radiation present in the ultraviolet
spectrum of the sun at ground level. Radiation of shorter wavelength is removed
by molecular oxygen and ozone in the atmosphere.
The mechanisms of oxidative photodegradation are probably diverse, and it is
only possible to indicate the kind of processes involved. In fact the direct

10 3

io 2

Intensity
(mWm-2nm-')

10

400 350 300

Photon energy (kJ mol" )
Figure 5.6 Intensity of solar radiation at the earth's surface: spectral
distribution at blue and near-ultraviolet wavelengths. The lower scale shows the
corresponding molar photon energy
 138 POLYMER MATERIALS
TABLE 5.7
Structures of polymers with exceptional high temperature performance

Upper service
temperature
(°C)

polyimide 300-350

aromatic
polyamide 200-250
(aramid)

polybenzimidazole 250-300

_L/^\_ C 0 V^\ o—ff~ \—O-j- polyetheretherketone-2240-260

L NH—CO
1-fM
CO

CO
polyamide-imide 220-240

polyquinoxaline 400—450

breaking of single C—C and C—H bonds is relatively uncommon. The C=0
bond absorbs more strongly and it appears that the following reaction is
important in initiating photo-oxidation in polymers containing CO groups
O
II
R-C-CH2-CH2-CH2 _R. _^ R 4:-CH +CH =CHR'
3 2

Many engineering polymers including polyesters, polyurethanes and polyamides

contain CO groups. In addition, CO groups are present as impurities in PE and
other hydrocarbon polymers. The observation that radiation of wavelength
longer than 340 nm does not produce photodegradation in PE is one important
piece of evidence for this. Photo-oxidation leads generally to discoloration,
surface cracking and deterioration of mechanical and electrical properties.
 CHEMICAL PROPERTIES 139
Controlled crosslinking by exposure to light is exploited in photoresist printing
processes, used for example in making printed electronic circuits. The exposed
areas of the photoresist polymer film are rendered insoluble and the image is
developed by solvent etching. The use of additives to improve photo-oxidative
durability is discussed in chapter 6.

5.8 Ageing and Weathering

No material is immutably stable. The processes of metallic corrosion have their

counterparts in the science of polymers. Even the mildest of human
environments may be extremely aggressive to a synthetic material. To compensate
for this, the resistance to what are ordinarily regarded as highly corrosive
substances may be excellent. Each application and each material must be
considered carefully and objectively. Almost all polymers age at a significant rate
unless steps are taken to stabilise them. In some cases the rate of deterioration
of commercial formulations may set surprisingly short limits on the expected
lifetime. Loss of appearance frequently occurs long before the component
becomes functionally unserviceable. Quite reasonably the designer and the
consumer seek reliable information on durability from materials suppliers.
Polymer scientists and technologists have studied intensively the problems of
predicting weathering performance.
The natural environment is enormously varied. Weathering is the result of
exposure of polymers to conditions under which thermal oxidation and photo-
oxidation may proceed simultaneously; and in addition the effects of water,
abrasion and atmospheric pollution need to be evaluated. Microclimates may
vary even over small distances, and features of the component such as its surface-
to-volume ratio and the aspect of its surfaces may strongly influence weathering.
It is of course impossible to obtain information on long-term weathering
performance quickly. Many possible methods of accelerated testing have been
advocated, but have met with considerable criticism. Testing machines range
from crude devices (in which, for example, test samples are simply exposed to
high intensity visible/ultraviolet radiation) to elaborate environmental simulators.
Inevitably, however, the processes of degradation are somewhat distorted by the
intensification of the environmental conditions; the greater the acceleration the
less the reliability. Despite this, accelerated test methods are widely employed,
and for limited extrapolations may be useful.

5.9 Ionising radiation

Chemical change in polymeric materials may also be produced by ionising

radiations. These effects are important in determining how polymers perform in
radioactive environments, for example in nuclear reactors, or in space. In
140 POLYMER MATERIALS
addition, the controlled use of radiation to produce beneficial changes in polymer
properties during processing is of increasing importance.
Irradiation may be by gamma- or X-rays (high energy electromagnetic
radiation, of wavelength shorter than ultraviolet), by high energy electrons, or
by neutrons. The radioisotope &0Co is an important gamma-ray source. The
nuclear reactor produces both gamma-rays and neutrons. However, the electron
accelerator is the most widely used source of ionising radiation for industrial
applications in polymer processing. All such radiation interacts with polymer
materials to cause ionisation by ejection of electrons from some molecules of
the solid, directly or indirectly leaving these molecules in a highly energetic or
excited state: R^R*.
The e\cited molecule may spread its energy among its neighbours as thermal
vibration (dissipation as heat) or it may emit a photon. Sometimes the energy
of excitation may become localised in a particular chemical bond, causing it to
break. Radiation-induced scission of a primary chemical bond is called
radiolysis. Such scission frequently causes the loss of side groups, as in the case
of PE when hydrogen gas (H 2 ) is formed

radia 0n
iCH2-CH2> " > (CH 2 -CH 2 )-* • 4CH=CH)- + H2

This reaction produces unsaturation in the polymer chain (—C=C—). The

cleavage of the CH bonds may occur on adjacent molecules with the important
effect of crosslinking the chains

—CH 2 — —CH— +H-

•

—CH2— —CH— +H-

—CH—
+ H2
CH—
Crosslinking increases the molar mass of the polymer producing an increase
in insoluble gel material, and may enhance thermal stability and alter mechanical
properties markedly.
Alternatively radiolysis may involve a bond of the main chain; extensive
chain scission leads to reduction in molar mass

—CH—CH 2 — • —C=CH 2 + —

CH3 CH3
 CHEMICAL PROPERTIES 141
The sensitivity of a polymer to radiation effects is shown in the value of a
parameter G, the chemical yield', the number of radiolytic reactions produced
by the absorption of 100 eV of radiation. We may define G values for each of
the processes shown above: G(cl), G(h), G(cs) for crosslinking, for hydrogen
evolution and for chain scission.
If G(cl) < G(cs), the effect of radiation is to degrade the polymer. PMMA
and PIB are notable cases. In PMMA the low molar mass compounds produced
by breaking CH bonds or C—C bonds to side groups are trapped in the brittle
solid, but are released when the solid is heated above Tg producing a foam.
Irradiation produces extensive crosslinking in PE, POM, PP, natural rubber and
some synthetic elastomers. Radiation crosslinking also occurs in PS, but this is
the most resistant of the commodity polymers to radiation damage, as is
shown by the G values of table 5.8. The main effect of irradiating PVC is to
release HC1 (cf. pyrolysis — see section 5.5) for which process G is about 13.
Ionising radiation is used commercially to produce crosslinked PE. Radiation
penetrates deeply into the maleiial, and the effects are relatively insensitive to
temperature. This permits polymer chains to be crosslinked after the product is
fabricated. Such radiation crosslinking increases thermal stability and reduces
creep. Crosslinking probably occurs only in the amorphous regions of the
polymer and the changes in elastic modulus which are observed depend on the
degree of crystallinity. Crosslinked PE film stable up to 200 °C is manufactured.
Certain additives are capable of inhibiting these radiation effects, just as
polymers may be stabilised against photo-oxidation and thermal oxidation
(see chapter 6).

5.10 Combustion: Fire Properties of Polymeric Materials

All polymer materials are regarded as combustible, because at sufficiently high

temperatures they undergo more or less complex reactions with oxygen, evolving

TABLE 5.8
Chemical yields for radiolytic reactions in common polymers

G(cl) C(cs) G00

PE 2 0 4
PP 0.26 0.29 2.6
PS 0.04 0.01 0.02
PMMA 0 1.2 —
PIB 0 2.8 1.5
Nylon 66 0.7 2.4 0.5
POM 6.5 11.0 1.7
Natural rubber 3.5 0.5 0.6
142 POLYMER MATERIALS
heat and sometimes producing flame. The range of behaviour observed in,
polymers is once again very wide, and the assessment of fire properties extremely
complicated. There is space here only to outline the main aspects of this subject.

Ignition and Combustion of Solid Materials

In contrast to the slow processes of thermal oxidation involved in ageing,

combustion is understood to be a rapid process of oxidation which takes place
above a critical temperature at which ignition occurs. In the case of most solid
combustible substances, it is clear that the external heat source which brings
about ignition serves to decompose the surface layers of the solid, producing
combustible vapours (figure 5.7). In the case of polymers this process of
decomposition is essentially the pyrolysis (perhaps assisted by oxygen)
described in section 5.5. When the volatile pyrolysis products come into contact
with air, an oxidation reaction occurs, with the liberation of heat. At a

* 1 Pilot ignition
2 Self-ignition

o io External
hot spot
h

Surface Volatile
d)f©°"-
Combustion
fr decomposition products reaction rate
External Surface
r
^ vaporisation mix with oexp(D;
source of temperature °1P air liberates heat
heat/V of P rise Positive feedback
raises temperature \ t

Heat losses
by conduction
convection,
radiation

Forward
velocity

\ / ^ Radiation
v from flame
• J / Evolution of combustible gases

LM£
Conduction
Temperature
r
Temperature of surface

Figure 5.7 Mechanisms of ignition and flame spread in polymer materials

 CHEMICAL PROPERTIES 143
particular temperature (the ignition temperature) the rate at which heat is
released is sufficient to balance heat losses to the surroundings, and a stable
combustion process is established in the region where pyrolysis products and
atmospheric oxygen can interdiffuse. Usually this reaction zone is somewhat
luminous and we speak of it as a flame. Frequently, as in the case of PMMA or
PE rods burning in air, pyrolysis completely volatilises the material, and no
residue is left. In other cases, such as PVC, many crosslinked resins and wood, a
carbonaceous residue (char) remains. Such materials burn in two well-defined
stages. The initial diffusion flame near the surface is succeeded by a slower
combustion reaction within the porous char itself which occurs truly at the
interior surface, and the rate of which is controlled by oxygen diffusion into the
material.
It is clear even from this simple description that the combustion behaviour of
a polymer material results from the interplay of pyrolysis, gas phase oxidation
and flame gas dynamics, all acting in a strongly non-isothermal setting. It is not
surprising that test methods designed to assess fire properties are both numerous
and ad hoc. Such tests have the virtue of simplicity, but their value is frequently
limited by their arbitrariness. It is helpful for the technologist to understand the
test procedures fully to avoid reading too much meaning into test results.
In recent years the concept of the limiting oxygen index (as measured by the
Fenimore-Martin test) has been widely used in comparing the fire properties
of polymers. The apparatus is shown in figure 5.8(a). The specimen (in the form
of a vertical rod or panel) is ignited in an upward-flowing oxygen—nitrogen
mixture, and a stable candle-like flame is established, burning downwards. The
0 2 /N 2 ratio of the gas mixture in the chimney is slowly reduced until the
candle-like flame becomes unstable and is extinguished. The minimum oxygen
fraction which can support steady combustion is termed the 'limiting oxygen
index' of the material. The parameter can be reproducibly measured and the
test procedure is simple. It must nevertheless be emphasised that the LOI
(unlike, for example, density or heat capacity) is not an inherent material
property but describes only the comparative behaviour of materials in a particular
test.
LOI values of a number of polymers are given in table 5.9. Since air contains
21 per cent oxygen, polymers having LOIs greater than 0.21 are self-extinguishing
in air under conditions similar to those of the test. Under fire conditions, where
some convective and radiative heat transfer usually assists burning, a figure of
0.27 or higher may perhaps indicate a useful degree of flame retardancy (see also
chapter 6).
In severe fires, all polymeric materials oxidise and make a contribution to
the heat liberated. The total contribution is determined by the heat of
combustion A//^ (calorific value) which is a thermodynamic property of the
material. AH^ is the quantity of heat liberated in the complete combustion of
unit amount of material. AHC gives no information about the rate at which
heat is released, although this is often critical in assessing fire hazard. Thus, for
144 POLYMER MATERIALS

(at
Figure 5.8 (a) Test apparatus for the measurement of the limiting oxygen index
of polymers (Fenimore-Martin test), (b) Test configuration for the measurement
of the surface rate of spread of flame of building materials

example, PE film and rod have the same AIIC , although film is more easily
ignited and burns faster. Table 5.10 lists heats of combustion of a number of
common polymers. AHf is controlled by molecular structure. Hydrocarbon
polymers have the largest heats of combustion. Oxygen-containing polymers
(wood, cellulosics and oxygen heterochains) release less heat on burning.
In many applications of polymer materials, notably in construction and
textile uses, the rate at which flame spreads across a burning combustible surface
is especially significant for safety. Surface spread of flame rate, although partially
determined by inherent combustion properties of the material, is once again
strongly dependent on circumstantial factors. Figure 5.7 shows that flame spreads
by a succession of ignition processes, the flame zone invading non-burning areas
as these reach sufficiently high temperatures. The rate at which heat is transferred
to cooler parts of the material from burning parts depends on the efficiency of
heat transfer processes. Generally, radiation from the flame, conduction
through the solid and convection adjacent to the surface all make contributions
to this heat transfer. Thus, flame luminosity, thermal diffusivity of the solid,
and orientation of the surface (figure 5.7) are major factors controlling the
surface spread of flame rate. The British Standard test for building materials
classifies materials according to horizontal flame spread rate in the presence of
 CHEMICAL PROPERTIES
TABLE 5.9
Limiting oxygen indices of common polymer materials

POM 0.16
PMMA 0.17
PP 0.17
PE 0.17
PAN 0.18
PE + 50 wt% aluminium oxide 0.20
PE + 60 wt% aluminium oxide 0.30
PS 0.18
Cellulose 0.19
EP 0.20
EP + 50 wt% aluminium oxide 0.25
EP + 60 wt% aluminium oxide 0.41
PVF 0.23
PA-66 0.24
PC 0.27
Silicone rubber 0.30
PEEK 0.35
Polyimide 0.37
PPS 0.44
PVC 0.47
PVDC 0.60
PTFE 0.95

radiation from an external source - figure 5.8(b). A commercial 1.6 mm thick

PVC sheet obtained a class 1 rating when bonded to 6 mm asbestos sheet, but
the poorer class 2 rating both when bonded to 13 mm plywood sheet and when
unsupported. Thinner PVC films on both steel and plasterboard can achieve the
best rating, class 0. The fact that the assessment is based on horizontal not vertical
spread emphasises the probably unavoidable arbitrariness of test procedures.

Flame Reactions

The chemistry of polymer flame reactions is not yet known in detail, although
the reactions occurring in the flames of hydrocarbon fuels such as methane have
been much studied. There is evidence that hydrocarbon polymers burn in much
the same way as these fuels. The chemical changes occurring during combustion
comprise complex sequences of gas-phase radical reactions, and undoubtedly all
volatilising polymers burn by such reactions. (The burning of polymer chars,
146 POLYMER MATERIALS
TABLE 5.10
Heat (enthalpy) of combustion AHf of selected
polymers

AHfikJg'1)
POM 16.9
Cellulose: cotton linters 17.4
Cellulose: wood pulp 17.5
PVC 19.9
PETP 21.6
Polyurethane 23.9
PMMA 26.2
PA 66, PA 6 31.9
PC 30.8
PS 42.2
NR: pure gum vulcanisate 45.2
PP 46.0
PE 46.5

however, is a gas—solid surface reaction between oxygen and carbon.) Most

flame-retardant additives act by interfering chemically with these flame reactions.
These additives are discussed in chapter 6.
All radical reactions involve initiation, propagation and termination processes,
and because of the large number of species present in polymer flames several
parallel processes may occur. Somewhat schematically then we may describe the
process of polymer combustion in the following way

polymer • decomposition products RH 2 , R'H 2 , etc.

where RH 2 , R'H2 denote various volatile fragments of the polymer chain.
These fragments invariably contain H atoms which play an important part in
the flame chemistry. For example, the flame reaction is initiated by the
generation of a radical
RH 2 + 0 2 > RH- + -H0 2
Once formed the radical can propagate the chain reaction; for example

RH-+02 • RH0 2 -
RH0 2 - • RO + -OH
•OH + RH2 • H 2 0 + RH-

RH2+02 • RO + H 2 0
 CHEMICAL PROPERTIES 147
The last line of this scheme shows the net chemical change which occurs as a
result of the three preceding reactions (obtained simply by adding these reactions
together). RO represents partially oxidised substances, which are further
oxidised in combustion. An important intermediate of this kind is formaldehyde
HCHO
HCHO + -OH > CHO- + H 2 0
•CHO + 0 2 • CO + -H0 2
Termination occurs by destruction of radicals such as 'HOj in the outer regions
of the flame; for example
•H0 2 + -H0 2 • H202 + 0 2
In fires, combustion is frequently incomplete, and volatile compounds and
smoke are generated in greater or less amounts. The solid particles and liquid
droplets present in smokes are produced by the condensation of organic
substances (particularly acetylenes) in the cooler zones of the flame. Materials
with high smoke yields are clearly hazardous in fires. In addition there is
evidence that volatile toxic substances are produced when certain polymer
materials burn. Carbon monoxide is always produced when carbon-based
materials (including such natural substances as wood and wool as well as
synthetic polymers) burn with a limited supply of air. Nitrogen-containing
polymers (PUR, PA, PAN) may produce hydrogen cyanide under these conditions
and chloropolymers may produce phosgene. However, the quantities evolved
depend on the circumstances of the fire, and the hazards from toxic fire gases
are extremely variable.

5.11 Biological Attack

Synthetic polymer materials generally show a remarkable resistance to attack by

microbial organisms. Because of their comparative softness they are liable to
attack by boring animals. Of common synthetic polymers only plasticised PVC
is subject to microbial attack, and it is now clear that this results from the
presence of the plasticiser rather than the polymeric PVC itself. Certain materials
of animal and vegetable origin such as casein, cellulose and surface coating aikyds
containing natural oils are attacked by bacteria or fungi.

5.12 Biocompatibility: Polymers in Medical Engineering

Polymers for use in surgery and biomedical engineering must be capable of

performing, often for long periods of time, in contact with living tissue and body
fluids. This is a highly specialised environment of great chemical and biochemical
complexity, and is an interesting case study in polymer engineering. The principal
148 POLYMER MATERIALS
medical uses of polymers are
(1) Structural materials in hip, knee, elbow and other reconstructions and
replacements; lenses.
(2) Dental materials.
(3) Devices (including tubing) for transport of blood and other fluids, both
inside and outside the body; and separation membranes (for example, for dialysis).
(4) Tissue adhesives.
(5) Sutures.
In all these applications, materials must of course be demonstrably non-toxic.
Clearly, not only the polymer but also its possible degradation products, any
residual monomer and all additives should be free of harmful effects. This
requirement has not always been met. For example, it is known that methyl 2-
cyanoacrylate (see section 6.7), an adhesive capable of bonding to wet tissue
surfaces, produces a toxic reaction by yielding formaldehyde as it degrades. Other
acrylates have proved satisfactory.
Polymer materials for artificial hip joints and similar uses must be not only
biochemically compatible but also mechanically satisfactory. Friction and wear
are the most critical aspects of mechanical performance and the most difficult
properties to-satisfy. The tribological operation of a natural human joint is highly
evolved and efficient.
Even granted chemical inertness, it is well established that simple surface
roughness can promote blood clotting. There is some evidence that other physical
characteristics of the surface, such as ionic charge and wettability, also affect the
thrombogenicity of polymer materials. The most successful methods of
overcoming undesirable blood clotting involve binding a thin layer of the anti-
coagulant mucopolysaccharide heparin to the polymer surface.
Figure 5.9 shows, as an example of precision medical engineering, a heart-
assist device which makes use of a variety of polymer materials.

Suggestions for Reading

Solubility, Solution Properties and Permeability

ASTM D2857, Standard Test Method for Dilute Solution Viscosity of Polymers
(American Society for Testing and Materials, Philadelphia, Pa, 1977).
Bixler, H. J. and Sweeting, 0. J., 'Barrier properties of polymer films', in
O. J. Sweeting (Ed.), The Science and Technology of Polymer Films, vol. 2,
ch. 1 (Interscience, New York, 1971).
Burrell, H. and Immergut, B., 'Solubility parameter values', in J. Brandrup and
E. H. Immergut (Eds), Polymer Handbook, ch. IV-15,2nd edn (Wiley, New
York, 1975).
 CHEMICAL PROPERTIES 149
Pneumatic drive tube

tube xenograft valve

Figure 5.9 Polymeric materials in medical engineering: a left ventricle heart-

assist device incorporating several polymers (by permission of Thermo Electron
Corporation). The xenografts are pig aortic valves, processed with glutaraldehyde
to crosslink the tissues. Teflon (PTFE) and Dacron (PETP fibre) are trade names
of E.I. DuPont de Nemours Co. Inc.; Silastic (silicone rubber) is a trade name of
Dow Corning Co. Inc.

Combellick, W. A., 'Barrier polymers', in Encyclopaedia of Polymer Science and

Engineering, vol. 2, pp. 176-192 (Wiley, New York, 1985).
Comyn, J. (Ed.), Polymer Permeability (Elsevier, London, 1985).
Hennessy, B. J., Mead, J. A. and Stening, T. C, The Permeability of Plastics
Films (Plastics Institute, London, 1966).
van Krevelen, D. W., Properties of Polymers: Correlations with Chemical
Structure (Elsevier, Amsterdam, 1972).
Nemphos, S. P., Salame, M. and Steingiser, S., 'Barrier polymers', in Encyclo-
paedia of Polymer Science and Technology, suppl. vol. 1, pp. 65-95
(Wiley, New York, 1976).
Ninnemann, K. W., 'Measurement of physical properties of flexible films', in
O. J. Sweeting (Ed.), The Science and Technology of Polymer Films, vol. 1,
ch. 13 (Interscience, New York, 1968).
Stannett, V. and Yasuda, H., 'Permeability', in R. A. V. Raff and K. W. Doak
(Eds), Crystalline Olefin Polymers, pt II, ch. 4 (Interscience, New York,
1964).
Tanaka,T., 'Gels', Scientific American, 244(1981) 124-138.
Yasuda, H., Clark, H. G. and Stannett, V., 'Permeability', in Encyclopaedia of
Polymer Science and Technology, vol. 9, pp. 794-807 (Wiley, New York,
1968).
150 POLYMER MATERIALS
Degradation

Allen, N. S., (Ed.) Degradation and Stabilisation of Polyolefins (Applied Science,

London, 1983).
ASTM D1435-85, Outdoor weathering of plastics (American Society for Testing
and Materials, Philadelphia, Pa.).
ASTM D1693-70, Environmental stress-cracking of ethylene plastics (American
Society for Testing and Materials, Philadelphia, Pa.).
Bohm, G. G. A. and Tveekrem, J. 0., 'The radiation chemistry of elastomers and
its industrial applications', Rubber Chem TechnoL, 55 (1982) 575-668.
BS 4618 : Part 4 : 1972, Environmental and chemical effects.
Charlesby, A., Atomic Radiation and Polymers (Pergamon, Oxford, 1960).
Davis, A. and Sims, D., Weathering of Polymers (Elsevier Applied Science, 1983).
Dole, M„ (Ed.), The Radiation Chemistry ofMacromolecules, 2 vols (Academic
Press, New York, 1972,1973).
Friedman, H., Thermal aging and oxidation with emphasis on polymers', in
I. M. Kolthoff, P. J. Elving and F. H. Stross (Eds), Treatise on Analytical
Chemistry: Part III, Analytical Chemistry in Industry (Wiley, New York,
1976).
Grassie,N. and Scott, G., Polymer Degradation and Stabilisation (Cambridge
University Press, 1985).
Hawkins, W. L., (Ed.),Polymer Stabilization (Wiley, New York, 1972).
Howard, J. B., 'Fracture: long-term phenomena', in Encyclopaedia of Polymer
Scienceand Technology, vol. 7,pp. 261-291 (Wiley.New York, 1967)
(environmental stress cracking).
Institute of Metals, 'Environmental cracking of polymers', in Mechanics of
Environment Sensitive Cracking of Materials, pp. 213-259 (London, 1977).
Jellinek, H. H. G. (Ed.), Aspects of Degradation and Stabilization of Polymers
(Elsevier, Amsterdam, 1978).
Kelen, T., Polymer Degradation (van Nostrand Reinhold, New York, 1982).
Keller, R. W., 'Oxidation and ozonation of rubber', Rubber Chem. Tech., 58,"
(1985)637-652.
Kiister, E., 'Biological degradation of synthetic polymers',/. Appl. Polymer Sci.:
Appl. Polymer Symp., 35 (1979) 395-404.
Lanza, V. L., 'Irradiation - properties changes', in R. A. V. Raff and K. W.
Doak (Eds), Crystalline Olefin Polymers pt II, ch. 7 (Interscience, New
York, 1964).
Owen, E. D. (Ed.), Degradation and Stabilisation ofPVC (Applied Science,
London, 1984).
Rlnby, B. and Rabek, J. F.,Photodegradation, Photo-oxidation and Photo-
stabilization of Polymers (Wiley, London, 1975).
Reich, L. and Stivala, S. S., Elements of Polymer Degradation (McGraw-Hill,
New York, 1971).
 CHEMICAL PROPERTIES 151
Rosato, D. V. and Schwartz, R. T., Environmental Effects on Polymeric
Materials, 2 vols (Interscience, New York, 1968).
Schnabel, W., Polymer Degradation: Principles and Practical Applications
(Hanser, Munich, 1981).
Winslow, F. H., 'Environmental degradation', in J. M. Schultz (Ed.), Treatise
on Materials Science and Technology, vol. 10, pt B, ch. 6 (Academic Press,
New York, 1977).

Thermal Stability

Cassidy, P. E., Thermally Stable Polymers (Dekker, New York, 1980).

Critchley, J. P., Knight.G. J. and Wright, J. J., Heat-Resistant Polymers (Plenum,
New York, 1983).
UL 746B, Standard for polymeric materials - long term property evaluation,
2nd edn (Underwriters Laboratories, Melville, NY, 1979).

Fire Properties

Aseeva, R. M. and Zaikov, G. E., 'The flammability of polymeric materials' in

Advances in Polymer Science, vol. 70, Key Polymers - Properties and
Performance, pp. 171-229 (Springer-Verlag, Berlin, 1985).
ASTM D2863-7 7 ,Minimun oxygen concentration to support candle-like com-
bustion of plastics (oxygen index) (American Society for Testing and
Materials, Philadelphia, Pa.)
Cullis, C. F. and Hirschler, M. M., The Combustion of Organic Polymers
(Clarendon, Oxford, 1981).
Fabris, H. J. and Sommer, J. G., 'Flammability of elastomeric materials', Rubber
Chem. Tech., 50(1977) 523-569.
Fenimore, C. P. and Martin, F. J., 'Burning of polymers', in The Mechanisms of
Pyrolysis, Oxidation and Burning of Organic Materials, National Bureau of
Standards Special Publication no. 357, pp. 159-170 (Washington DC, 1972).
Gann, R. G., Dipert, R. A. and Drews, M. J., 'Flammability' in Encyclopaedia
of Polymer Science and Engineering, vol. 7,2nd edn, pp. 154-210 (Wiley,
New York, 1987).
Hilado, C. J., Flammability Handbook for Plastics, 3rd edn, (Technomic Pub-
lishing Co., Westport, Conn., 1982).
Kuryla, W. C. and Papa, A. J., (Eds), Flame Retardancy of Polymeric Materials,
5 vols. (Dekker, New York, 1973-79).
Lewin, M., Atlas, S. M. and Pearce, E. M. (Eds) Flame-RetardantPolymeric
Materials, vol. 1 (Plenum, New York, 1975); vol. 2 (Plenum, New York,
1978); vol. 3 (Plenum, New York, 1982).
Stuetz, D. E., Diedwardo, A. H., Zitomer, F. and Barnes, B. P., 'Polymer
combustion',/. PolymerSci., pt A, 13 (1975) 585-621.
• 3^ POLYMER MATERIALS
Troitzsch, J., International Plastics Flammability Handbook (Hanser, Munich,
1983).

Medical Engineering

Chiellini, E., Giusti, P., Migliaresi, C. and Nicolais, L., Polymers in Medicine II:
Biomedical and Pharmaceutical Applications (Plenum, New York, 1986).
Frazza, D. J., 'Sutures', in Encyclopaedia of Polymer Science and Technology,
suppl. 1, pp. 587-597 (Wiley, New York, 1976).
Gebelein, C. G. (Ed.) Advances in Biomedical Polymers (Plenum, New York,
1987).
Halpern, B. D. and Karo, W., 'Medical Applications', in Encyclopaedia of
Polymer Science and Technology, suppl. 2, pp. 368-402 (Wiley, New York,
1977).
Kronenthal, R. L., Oser, Z. and Martin, E., (Eds), 'Polymers in Medicine and
Surgery', in Polymer Science and Technology, vol. 8 (Plenum, London, 1975).
Williams, D., (Ed.), Biocompatibility of Implant Materials (Sector Publishing,
London, 1976).