PVC Technology: Chapter 12

CHAPTER 12
Miscellaneous Properties ofSpecial Interest

in PVC Materials and Products
W. V. TITOW
12.1 INTRODUCTION
All properties of a PVC material depend, in a more or less complex

way, upon the formulation, and to some extent also on the effects of
compounding and processing (including the 'heat history'). However,
some properties are more directly associated with the nature and
amount of a particular class of formulation component: for example,
softness, extensibility, tensile strength and modulus are particularly
strongly influenced by plasticisation, many mechanical properties are
substantially upgraded by incorporation of fibrous reinforcing fillers,
flame resistance improvement can depend directly on the incorporation
of suitable flame retardants, and so on.
In this book, properties linked in such a manner with individual
formulation components and factors are considered in conjunction with
them in most cases. Some general information and numerical data on
properties are also given in Chapter 1 and Appendix 3. The properties
discussed in this chapter are either those which might be described as
more 'composite' in nature or origin, or which are relevant in some
special context or application.
12.2 LOW-TEMPERATURE PROPERTIES
Many PVC products, both rigid (e.g. pipes, containers) and flexible
(e.g. PVC-coated tarpaulins and clothing, inflatables), are used in
conditions and climates where they may experience low (sub-zero)
439
W. V. Titow, PVC Technology

© Elsevier Applied Science Publishers Ltd 1984
440 w. V. Titow
temperatures. It is necessary, therefore, that their properties should

not be affected by such conditions to the point where serviceability
would be impaired. Securing this objective is essentially a matter of
formulation, supplemented by proper compounding (to ensure good
inter-blending of all formulation components) and care in processing.
With uPVC the most important single consideration in the context of
low-temperature service is to preserve the toughness (avoid embrittle-
ment) of the material. Without appropriate modifiers uPVC can be
brittle even at room temperature: suitable choice of modifier (and its
correct incorporation in the right proportion) can ensure that the
compound is, and remains, tough in sufficient measure. The effects
obtainable are largely a matter of degree, since uPVC compounds
(including the so-called high-impact grades) in most cases exhibit a
definite, often regular, dependence of impact strength (which is related
to toughness) on temperature, with, usually, a fairly well-defined
brittle point, i.e. a temperature at which the mode of failure in an
impact test changes from ductile to brittle (often with a corresponding
drop in strength). Brittle point, coupled with actual impact strength
values at the low temperatures concerned, can be used as a criterion of
low-temperature performance. Other things being equal, the brittle
point of a compound tends to vary inversely with the molecular weight
of the polymer and the amount of impact modifier present (up to a
practical usefulness limit in most cases). Although, in what might be
termed the more academic context, and also in connection with
product design, the fracture toughness approach l - 5 is playing an
increasingly important role in the understanding, determination and
prediction of the toughness of plastics, including PVC, in industrial
practice the results of impact strength tests are still widely used as a
measure of this complex property. This is so, partly because a large
body of relevant test data has been built up over the years, and despite
often comparatively poor correlation between the results of different
tests, and between test results and effects of particular service
conditions.
Standard impact tests of interest in connection with the determina-
tion of brittle point of PVC materials include the following:
ASTM D 759-66 (Re-approved 1976): Conducting physical property

tests on plastics at subnormal and supernormal temperatures.
ASTM D 746-79: Brittleness temperature of plastics and elastomers

by impact:
12 Properties of Special Interest in PVC Materials and Products 441
The method of this standard is technically similar to that of ISO/R

974:1969.
BS 2782:Part 1: Method 150 D:1976: Cold crack temperature of film

and thin sheeting.
The method of this specification is essentially Method 10 of BS
3424:1973, but modified to give more precise determination. Although
intended primarily for flexible film materials it can be used (with
special care) for uPVC film and thin sheet that can be bent into a loop.
Cold crack temperature is defined as the temperature at which cracks
are caused when a loop of film or sheet is flattened by a blow of a test
hammer under standard conditions. This temperature is usually related
to (but not the same as) the low-temperature limit for actual service.
ASTM D 1790-62 (Re-approved 1976): Brittleness temperature of

plastic film by impact.
Both in this method (which is suitable for films up to 0·25 mm thick)
and that of ASTM D 746 (in which thicker, die-cut specimens are
struck by a sharp edge), brittleness temperature is defined as that
temperature at which 50% of the test specimens fail (i.e. break or
shatter) under the conditions of the test. ISO 974-1980 gives a similar
definition in terms of its test. In this, specimens 1·6 mm thick are
struck a sharp blow which bends them round a shaped mandrel.
ASTM D 3029-78: Impact resistance of rigid plastic sheeting or parts

by means of a tup (falling weight).
The main effects of cooling of flexible PVC are stiffening, hardening,

and embrittlement. The temperature of onset, and the extent, of these
changes depend on the formulation. The stiffening and hardening are
much more pronounced than with uPVC; they are also more serious in
practice, since flexibility and softness are among the most important
properties for which flexible PVC is formulated. It is therefore
desirable that these properties should be retained under a wide range
of service conditions, including low temperatures. Correct formulation,
and especially choice of plasticiser(s) is again the key factor in ensuring
good performance in this respect. The best low-temperature properties
are conferred by plasticisers of the aliphatic ester type (see Chapters 6
and 7), whilst aromatic phosphates are among the least suitable
plasticisers (e.g. compounds plasticised with TIP can be quite hard
and stiff at freezing point).
442 W. V. Titow
It is clearly important to have tests available, the results of which can

assist in the evaluation and prediction of the stiffening and hardening
of flexible PVC at low temperatures. The results of relevant standard
tests are particularly useful in monitoring quality in production, or
assessing the effects of formulation modifications in basically the same
type of compound. Correlation between the results of tests by different
methods is not always good, and none of the methods can be said to
provide directly a value for the lowest temperature admissible in actual
service (albeit they do give useful indications in that direction). Useful
standard tests and the properties they determine include the following.
12.2.1 Cold Flex Temperature (Clash and Berg)
This is the lowest temperature at which a standard strip specimen can

be deflected through an angle of 200° under a fixed torque, in
prescribed test conditions. Clash and Berg are the originators of the
apparatus; the method is described in BS 2782: Part 1: Method 150 B:
1976. The cold flex temperature (normally quoted in 0c) is always
higher (Le. 'warmer') than the 'cold bend' temperature (see below).
12.2.2 Cold Bend Temperature
This is determined by the method of BS 2782:Part 1: Method

104A:1970: a strip specimen is cooled at the test temperature for
10 min and wound mechanically round a mandrel of prescribed
diameter, at a prescribed rate. The cold bend temperature is the
temperature at which this treatment causes the specimen to crack or
fracture in the standard test.
12.2.3 Low-Temperature Extensibility of Flexible PVC Sheet

This is the extension produced in a standard specimen at - 5°C under a
prescribed load. It is determined by Method 150 C: 1983 of BS
2782:Part 1.
The effect of temperature upon the stiffness in torsion (apparent
modulus of rigidity) of plastics materials, including PVC, may be
determined by measurement according to the method which forms the
basis of the following standards: ISO/R 458-1965; BS 2782:Part 1:
Method 150 A:1976; ASTM D 1043-72 (Re-approved 1981); DIN
53447:1966. A version of the Clash and Berg apparatus is used in the
determination.
12 Properties of Special1nterest in PVC Materials and Products 443
U.3 HEAT RESISTANCE
This section is concerned with heat resistance of PVC materials and

products in service and service-related tests. Although 'heat resistance'
if often used synonymously with 'resistance to degradation by heat', in
the present context it has a wider meaning embracing the following
effects of heating:
(i) degradation of the PVC material (outwardly manifested in
deterioration of properties and appearance);
(ii) loss of volatile components (especially plasticisers from pPVC,
with consequent hardening and stiffening, leading to deteriora-
tion of many properties);
(iii) temporary, mainly reversible, changes in properties (especially
mechanical properties) at elevated temperatures.
Degradation is the consequence of the breakdown of, and chemical
changes in, the PVC polymer. In practice it is usually detected and/or
monitored by detecting or measuring the evolution of HCI (the
principal breakdown product), colour changes, and changes in
properties. The methods used are discussed in Chapter 9, and some
relevant standards are listed in Section 3.2 of Appendix 1. Thermo-
gravimetric analysis and various analytical methods of identifying
chemical changes in the polymer and its decomposition products are
also employed in more fundamental studies of thermal decomposition
of PVc. 6 Volatile loss is normally determined gravimetrically.
Degradation and loss of volatiles are usually concurrent at least to
some extent, and are often jointly termed 'heat ageing'. The greatest
possible resistance to heat ageing is clearly essential in PVC materials
intended for service above room temperature; it is also desirable in all
PVC products, since loss of volatiles and/or deterioration of properties
on heating in tests are frequently used as indication of likely long-term
performance in these respects in service at room temperature. Such
predictions, as well as those of the maximum acceptable service
temperature, are usually obtained by the following method.
A selected property (e.g. tensile or impact strength, modulus, etc.)
is determined in appropriate tests. Specimens are then heated
at a number of elevated temperatures suitably chosen in the light of
practical experience or other relevant information or requirements.
The property is re-determined at intervals during the heat treatment
(several properties may also be monitored in this way) and the
444 w. V. Titow
100
c
o
~
c
~ 60-------
~ I
~ I
& I
i!- I
I
T(60),
Fig. 12.1 'Percentage retention' of selected property as a function of heating

time at various temperatures (81 ) 8z> 83 > 84 > ( 5), Schematic representa-
tion.
'percentage retention' (i.e. the value after a given heating time as a

percentage of the original value) is plotted against log time, to obtain a
family of curves as shown schematically in Fig. 12.1. The lowest
percentage retention value of the test property acceptable for service
purposes is decided (say, for example, 60%), and the corresponding
times for the test temperatures from Fig. 12.1 (intercepts of the 60%
retention line with the individual temperature curves) are plotted
against the reciprocal of absolute temperature to produce an Arrhenius
plot as shown schematically in Fig. 12.2.
Note: On the assumption that heat degradation is a simple
heat-activated 'reaction' the plot should represent the well-
known Arrhenius relationship, In k = -(E/RT) + constant
(here expressing the effect of temperature on the rate of the
notional 'degradation reaction') and should thus be rectilinear
in the ideal case. In practice curves concave to the
temperature axis may be obtained.
The time for the chosen test property to drop to the pre-selected
percentage retention value at a particular temperature can be read off
the curves of either of the two plots. The expected service time after
which the test property will reach the value at room temperature can be
found by extrapolating the curve of Fig. 12.2.
Reciprocal of absolute temperature, 11K
Fig. 12.2 Time to reduce percentage retention of selected property to 60%,

as a function of the reciprocal of heating temperature «(j expressed in kelvin).
Schematic representation.
Methods of this type are used in deriving the 'temperature index'

values 7-widely used temperature limits for continuous service,
assigned to various polymers and plastics materials by Underwriters
Laboratories Inc. (and published in the Modern Plastics Encyclopedia,
McGraw-Hill Inc., and elsewhere).
The mechanism of heat degradation of PVC is discussed in some
detail in Chapter 9, in connection with heat stabilisation.
Some standard procedures and equipment applicable in the
determination and prediction of heat-ageing effects in plastics,
including PVC, are described in the following specifications:
ISO I137-I975. * Plastics-Methods of test for the determination of

the behaviour of plastics in a ventilated tubular oven.
ISO 2578-1974: Plastics-Determination of time-temperature limits
after exposure to prolonged action of heat.
BS 4618: Section 4.6:1974: The presentation of plastics design data.
The thermal endurance of plastics.
ASTM D 1870-67 (Re-approved 1978):* Elevated temperature
ageing using tubular oven.
* Mutually corresponding in technical content.
446 W. V. Titow
ASTM D 2115-67 (Re-approved 1980): Standard recommended

practice for oven heat stability of poly(vinyl chloride) compositions.
ASTM D 3045-79: Standard recommended practice for heat ageing

of plastics without load.
It may be noted in passing that some mechanical properties of

plasticised PVC (tensile strength, modulus) may appear to improve (in
that their values increase) in the initial stages of accelerated heat
ageing. This is associated with early loss of plasticiser: the tensile
strength and modulus of pPVC normally vary inversely with the
plasticiser content (except for some anomalous 'antiplasticisation'
effects which may occur at very low contents); their values thus
increase at first with the volatalisation of plasticiser, whilst at the same
time this process uses up heat that would otherwise be available for
thermal degradation (which reduces the strength and modulus).
Although loss of plasticiser may thus appear to bring some benefit in
the early stages of ageing of pPVC, it is in fact a contributory factor in
the overall deterioration caused by this process. Plasticiser loss is
accompanied by reduction of extensibility, flexibility and softness;
internal stresses may be set up (especially where the loss is locally
non-uniform) and these-either alone or in conjunction with any
external stress that may be encountered-<:an promote cracking of the
stiffened, hardened material; low-temperature properties (e.g. cold
flex temperature) can also be adversely affected.
Heat-ageing resistance is a significant consideration in connection
with the service performance of such important PVC products as
upholstery fabrics and cable compounds (insulation and sheathing). In
both these applications, and perhaps even more particularly in the
former, resistance to heat ageing of the PVC materials involved is of
interest not only per se, but also because it is normally associated with
good long-term stability in service at room temperature. 'Fogging' of
motor-car windscreens and interiors by plasticiser volatalised from
PVC-coated upholstery is an example of a special practical problem
associated with a formulational factor (nature, volatility and compata-
bility of plasticisers used) instrumental in heat-ageing resistance. Tests
for stability to fogging used by motor-car manufacturers and plasticiser
suppliers to evaluate PVC upholstery coatings in this regard are
essentially heat-ageing tests at moderately elevated temperatures. The
problem of fogging is discussed in Chapter 7.
The performance of pPVC sheets, films and fabric coatings in tests

for loss of volatiles at elevated temperatures is of particular practical
significance, because it is often used as one of the criteria of technical
and commercial acceptability (the implication being that it gives an
indication of likely long-term behaviour in service at ordinary
temperatures). Several standards exist; all give test methods, and some
also lay down permitted loss limits: both the methods and the figures
(where prescribed) are somewhat arbitrary and do not correlate
particularly closely with actual service experience. The following
standards may be mentioned: ISO 176-1976,* BS 2782:1970 Method
107F,* ASTM D 1203-67 (Re-approved 1981),* BS 2601:1973,t BS
3424:1973,t BS 4216:1970,t AS:j: 1441:1973 (Method 8) and AS
1440:1973, Canadian Standard 4-GP-149:1972.
For a given formulation, the volatile loss from a plasticised PVC
sheet, or coating on a fabric, in standard conditions, is a function of
the specific surface (surface per unit volume) and hence the thickness.
Theoretical considerations8 suggest that in the kind of test prescribed
by most standards the total volatile loss in the test period (from 5 to
24 h, depending on the standard used) should conform to the
expression
L = k(~+ ~) (1)
where: L is the volatile loss; n is the thickness of the PVC sheet or

coating on a fabric; P is the perimeter length and A the area of the test
specimen; k is a coefficient dependent on the conditions (including
heating time and temperature) of the test method; and b is a numerical
factor dependent on the proportion of the specimen surface effectively
available for evaporation. For a given set of test conditions the value of
b may vary between 1 (for a coating on an impervious substrate) and 2
(sheet specimen with both sides freely accessible to the atmosphere).
Figure 12.3 shows a plot of loss of volatiles from PVC films of the
same composition but ranging in thickness between 0·1 and 0-4 mm,
determined by Method B of ISO 176-1976(E). The theoretical curve
(plot of eqn (1) with appropriate values) is superimposed (solid line).
The general agreement is good: the moderate departures from
theoretically predicted values at the extremes of the thickness range
* See Appendix 1, Section 4.2.

t See Appendix 1, Section 7.
:t: Australian Standard.
448 w. V. Titow
L =0205 ( %- .0·08)
o 01 02 03 04 05
Nominal film thicknQ:ss (n), mm
Fig. 12.3 Volatile loss from calendered PVC film in test according to Method
B of ISO 176:1976(E), as a function of nominal thickness (~, dotted line).
Solid line: plot of eqn (1) with appropriate constants (PIA = 0·08 mm- 1 for
standard specimens in the method used; b = 2 for a sheet with both sides
exposed). PVC film formulation:
PVC resin (emulsion type) 100
Plasticisers: DIDP 70phr
Polymeric 4·5 phr
Stabiliser 3phr
Lubricant 0·5 phr
covered by the tests must be ascribed to experimental error (or some

other factor, possibly thickness-dependent); otherwise-if the two
extreme results were valid-extrapolation of the experimental curve
would predict that volatile loss should cease altogether at a film
thickness of about 0·5 mm, and that it should be only about 5% for an
infinitesimally thin film, when, in fact, with an almost infinite specific
surface, loss of most of the monomeric plasticiser can be expected,
(i.e. up to about 40% volatile loss from this particular composition-

see caption of Fig. 12.3).
Cable compounds are rated, inter alia, according to the conductor
temperature to be withstood in continuous service, but the effects of
still higher temperatures which may be experienced occasionally (e.g.
heat shock resulting from a short-circuit) are also relevant. The
pertinent standard tests typically involve heating specimens (which may
be under mechanical stress) for relatively short periods at high
temperatures-e.g. 1 h at 150°C (the heat-shock test of BS 6746:1976,
in which no visible cracks must be caused by the treatment), or 40 to
120 min (depending on the type of insulation material) at 200°C (the
thermal stability test of VDE* 0271/3.69, in which the pH indicated by
a standard indicator exposed to the volatile products evolved must not
be less than 3). Heat-ageing tests are also applied in which specimens
are heated for longer periods at somewhat lower temperatures, with
pass requirements in terms of permitted volatile loss and property
change maxima (as in BS 6746:1976) or absence of cracks (as in VDE
0271/3.69 after 7 days at 120°C). Although such requirements may be
coupled with particular service-related temperature rating (e.g. for a
nominal 90°C cable sheath compound, suggested volatile loss limit of
2·5 mg m- 2 on heating for 7 days at 115°C9 ), the test results do not, in
the main, provide a reliable basis for firm predictions of behaviour in
service.
Apart from the question of thermal degradation and ageing
generally, the thermoplastic nature of PVC, coupled with its
comparatively low softening temperature (lowered still further by
plasticisation), is a limiting factor on the maximum service tempera-
ture. The limit for most types of cable compound is 70°C (conductor
temperature). Some special, high-temperature cable compounds are
rated at 85°C (and even up to 105°C for limited periods under certain
conditions) but at high temperatures external damage to, or distortion
under pressure of, the heat-softened material, as well as the possibility
of outward penetration of the hot conductor through it, become
serious considerations. Susceptibility to damage, at room temperature,
by hot objects or materials (e.g. soldering irons, hot oil splashes) may
also have to be considered. The performance of PVC cable compounds
can be substantially improved in these respects by cross-linking the
* Verband Deutscher Elektrotechniker (specification of the German Electrical

Engineers Association).
450 W. V. Titow
cable covering, and this has been receiving attention in recent years,
with special reference to irradiation techniques, including the use of
electron beams. 10,11
Some of the direct (i.e. non-degradative) effects of heat on the
properties of PVC are illustrated by the data of Figs 12.4-12.6. As with
thermoplastics in general, mechanical properties are reduced at
elevated temperatures, as is resistance to creep and fatigue; however
90
80
1... 70
If
~60
Coo
::l
.
1/1
~40
C
~30
:g20
10
o
Fig. 12.4 Effect of temperature on tensile strength and BS softness number of

PVc. 6, uPVC (normal impact strength grade); 0, pPVC (50phr noP).
g·mil
100 in2 ·24h·atm
1·0
Fig. 12.5 Permeability of a uPVC (homopolymer) film to water vapour as a

function of temperature.
12
A
'"'Eu 10
0
-52
..»x
I: 8
". '
3"
"~ 6
....
Q,
.u
.....
1i 4
I:
0
12
2
o 10 20 30 40 50 60 70 80 90
Tllmpcrraturcr. ·c
Fig. 12.6 Effect of fibrous reinforcement on the temperature dependence of

tensile creep of uPVC (ICl's Darvic 110). Curve A, material with 30% glass
fibres oriented parallel to the test direction; Curve B, as A, but fibre
orientation perpendicular to test direction; Curve C, unreinforced material.
452 W. V. Titow
uPVC is more thermally sensitive in this sense than the other common
'engineering' thermoplastics, and its softening temperature is compara-
tively low (see Appendix 3). The reduction of some of the mechanical
properties can be counteracted to some extent by incorporation of
fibrous reinforcement. Whilst improvement in the heat deflection
temperature under load is only moderate with, say, 30% glass-fibre
reinforcement (increase of 5-10°C in some cases) creep at elevated
temperatures can be significantly reduced (see Fig. 12.6).
A non-degradative (though irreversible) effect of heat, which can be
a practical problem in service, is the longitudinal shrinkage of extruded
cladding and beading (finishing strip) sometimes occurring on buildings
and caravans. This is attributable to retraction of stretch imparted
during manufacture (extrusion and take-off).
The principal ways of securing the best practicable resistance of PVC
materials to heat degradation are proper stabilisation (by suitable
stabilisers in appropriate quantities, properly dispersed in the com-
pound by suitable mixing-see also Chapters 4, 9 and 10) and-where
possible-the use of fillers and pigments which can afford additional
protection.
Volatile loss can be counteracted by proper choice of plasticisers
(polymeric plasticisers are particularly useful); use of polymeric
additives with plasticising action (e.g. copolymers of the Elvaloy* type,
highly chlorinated polyethylene, or nitrile rubber); ensuring that
plasticisers and all other constituents of the compound are of good,
consistent quality; and by general attention to the mutual compatabil-
ity of all constituents.
12.4 PERMEABILITY
In the broadest sense permeability may be thought of as the ease (or

otherwise) with which a material will allow the passage of a penetrant.
In plastics this property is of special practical interest in connection
with barrier applications, Le. where these materials are used to exclude
or contain potential penetrants (most often fluids, i.e. gases, vapours
or liquids). For such purposes the lowest possible permeability vis-a-vis
the penetrant(s) concerned is desirable: examples of barrier applica-
* Du Pont trade name for a group of modified ethylene/vinyl acetate

copolymers.
tions of PVC are films (e.g. packaging films, rainwear, inflatables),

containers (e.g. blow-moulded bottles, sachets) and protective coatings
(e.g. on chain-link wire fencing, industrial gloves, tarpaulins). Such
applications may be regarded as particular instances of the general case
of the system penetrant(s)/plastics barrier in which low permeability is
required (for example the 'passage' of water through a good tarpaulin
is virtually nil), although it may be significant (as manifested, for
example, in loss of contents from a shampoo sachet made from badly
formulated PVC).
It can readily be seen, largely as a matter of common sense, that the
permeability of a plastic towards a given penetrant should be a
function of the chemical nature, morphology and composition of the
plastic, and that the barrier thickness and area involved must also be
factors. This is indeed so, and the relevant relationships may be
expressed, in a general way, by the following equation applicable in
steady-state conditions:
J/A = P(F/L) (2)
In this expression J is the flux of the penetrant, i.e. the amount (in
suitable units, e.g. of mass or volume, or in moles) passing through the
barrier in unit time; A is the area through which the passage takes
place; F is the driving force actuating the passage, e.g. the difference
between the concentrations (~c), pressures (~p), temperatures (~e)
or chemical potentials (~Il), of the penetrant at the 'upstream' and
'downstream' boundaries of the barrier; L is the barrier thickness, and
P is the permeability coefficient which embodies (i.e. whose value will
reflect) the effects of chemical and physical interactions in the system
(themselves dependent on the chemical nature and fine structure of the
barrier material).
As can be seen, F/L is the driving force gradient within the barrier.
The various quantities in eqn (2) may be expressed in any convenient
units, so long as those are mutually consistent; their choice will
determine the units (and hence will influence the numerical value)
of P.
In practice the permeability of plastics is commonly determined by
measuring-in standardised, steady-state conditions-the flux of a
penetrant (usually water vapour, oxygen, carbon dioxide or nitrogen)
through a film or sheet. Loss of contents (in terms of weight loss over a
period of time, i.e. average flux) through the walls of a container is
also often measured.
454 w. V. Titow
The results of such determinations can normally be interpreted in

terms of a version of eqn (2), or some analogous expression, but they
may be (and usually are!) stated in various ways and in a variety of
units. This diversity complicates comparison of results from different
sources and can lead to confusion associated with, or compounded by,
the following factors.
(i) Even if the same basic units are used (for flux, driving force,
film thickness, etc.), expression of the result of one and the
same determination (or results of separate determinations for
the same plastic/penetrant system in identical conditions) can
entail different combinations of the units and have different
numerical values, depending on the choice of the 'index' of
permeability (Le. whether permeability coefficient, rate of
transmission, permeance, etc.-see Table 12.1).
(ii) The same 'index' of permeability, expressing the result of the
same determination, will have different numerical values if given
in different units.
(iii) Values are sometimes quoted simply as 'permeability' without a
clear statement which 'index' is being used, so that units have to
be scrutinised to ensure correct interpretation of the figures.
Moreover, the same name is sometimes used for different
permeability indices.
This situation is illustrated by Table 12.1 in which the more common
ways of expressing permeability are listed, with the associated units
and an explanation of their mutual relationship (in terms of eqn (2)).
Since for a given penetrant/barrier system in defined conditions the
permeability coefficient should be a constant, expressing the relevant
intrinsic properties of the barrier material, this coefficient should-in
theory-be the best value to use as an index of permeability, especially
when comparing different plastics materials. It is often used for these
purposes, although here again the variety of units employed can cause
some confusion. The forms of permeability coefficient which are either
fairly widely used, or are of a more standard or fundamental nature,
are given in Table 12.2. A useful discussion of gas permeability
coefficients has been published by Yasuda. 12
However, the permeability coefficient is by no means solely or
universally employed as an index of permeability, because in practice
most plastics are multicomponent (often multiphase) materials; they
may be heterogeneous not only by virtue of these features per se, but
also because the distribution of the various additives in the polymer

may not be uniform. Moreover, local differences in density and fine
structure may occur (e.g. due to orientation, or 'skin-and-core' effects
in, say, sheets and mouldings) as well as irregularities in thickness.
Thus the concept of uniform flux per unit thickness of a homogeneous
material, implicit in the definition of the permeability constant, may
not be applicable in practice, and it may be more realistic to quote,
say, transmission rates through a film or container wall of stated
average thickness, in strictly defined conditions.
The permeability considered so far is that of plastics materials in
continuous, i.e. non-porous form: even the cellular plastics mentioned
in Table 12.1 are of the kind in which the cells are separated by walls
of 'solid' material, and thus are not inter-communicating pores. In its
passage through a plastics barrier which is 'solid' (continuous) in the
above sense, the penetrant will normally be in a molecular state of
division:* it may be considered to dissolve in the plastic at the
'upstream' face of the barrier, diffuse through, and come out of
solution at the 'downstream' face. In this diffusional transport mechan-
ism the chemical nature of the penetrant and the barrier material. as
well as the composition and fine structure of the latter, will be cardinal
factors. Moreover, the state of the plastics material (i.e. whether glassy
or rubbery) can affect the rate of diffusion. For a given composition
(e.g. a particular PVC compound) the state will depend on the
temperature and may also be influenced by the sorbed penetrant
concentration: this effect can be especially strong if the penetrant
interacts strongly with (i.e. is a good solvent or plasticiser for) the
polymer. 13
For simple gases, and many other penetrants sorbed from the vapour
phase, the solubility in the plastics barrier material will-under certain
conditions-be proportional to the partial pressure (i.e. Henry's law
will be obeyed), and the rate of diffusion will be directly proportional
to the concentration gradient (i.e. Fick's law will be obeyed). In such
cases permeability may be defined by the expression
P=DS (3)
where P is the permeability coefficient (as in eqn (2)), D the diffusion
* Clustering may occur inside the barrier material in some cases, but this is
exceptional rather than typical.
TABLE 12.1
Some Common Ways of Expressing Permeability .j:>.
'-"
a..
Penetrant Plastics htdex of permeability Data required Relevant determination
barrier in methods,
Description Special unit Constituent conjunction references and
name and/or simple remarks
Name In terms of eqn (2) symbol units
Water Film or thin Transmission J/A - g Barrier thickness (L) ISO/R 1195-1970
vapour sheet rate m2.24h Pressure difference (~p)Q
Temperature
RH
Water Film or thin Transmission J/A - g Barrier thickness (L) BS 2782:Part 8:
vapour sheet rate m2.24h Pressure difference (~p) Methods 820 A to G
Temperature (in preparation)
RH ~
Water Flexible 'Permeability' J/A - g Barrier thickness (L) BS 3177: 1959 :<::
vapour sheet m2.24h Pressure difference (~p) :::l
Temperature 0
~
RH
g
Water Sheet up to 1. Transmission J/A WVT Barrier thickness (L)
about 1/8 in rate m2.24h Pressure differance (~p)
vapour
thick grain Temperature
or
ft2.h RH
1 grain
2. Permeance J/(A.~p) Perm = Barrier thickness (L)
ft2.h.(in Hg) Temperature
~ASTM
RH E 96-66(1972)
19
Metric perm =
m2.24 h.(mm Hg)
1 grain.in
3. 'Permeability' (J.L)/(A.~p) Perm-inch = Temperature
Le. =P ft 2.h.(in Hg) RH
Metric perm-
19.cm
centimetre =
m2.24 h.(mm Hg)
Water Rigid cellular Transmission J/A WVT g As for ISO/R 1195 ISO/R 1663-1970
vapour plastic rate m2 .24h
(block)
Water Expanded 1. Permeance J/(A.t.p) - ng Barrier thickness (L)
(for boards
......
vapour polystyrene N.s Temperature tv
(board) with surface RH BS 3837:1977
skins) (prescribing tests by
the method of BS
I 4370: Part 2: 1973)
1'"?to
2. 'Permeability' (J.L)/(A.t.p) - ng.m Temperature technically similar to ~
(for boards i.e. =p RH ISO/R 1663
N.s ~
without .g>
surface skins) J '"
1 fm b ["
Gas Films and Transmission J/(A.t.p) SI unit = -- Barrier thickness (L) ISO 2556-1974
thin sheet rate Pa.s Temperature (identical with BS S'
~
RH 2782 Part 8: Method ...
also
cm 3 (at STPj" ~
821A 1979)
m2 .24h.atm S·
'"0
Gas Films and Transmission J/(A.t.p) - ml (atSTP) Barrier thickness (L) BS 2782:Part 5: 1970 ~
thin sheet rate (also Temperature Method 514 A (in ()
m 2 .24h.atm
termed 'per- RH 1979 replaced by new ~
I::>
meability') method 821A of BS
2782 Part 8: 1979-see
...5'~
l:;-
also ISO 2556) I::>
1 cm 3 (at STP) ;:<
Gas Film and 1. Transmission J/(A.t.p) GTR unit = Barrier thickness (L) ASTM 01434-75 I::>..
sheeting rate m2 24 h.atm Temperature NB This specification
RH also recognises (and ~
I::>..
$::
1 cm 3 (at STP).cm T gives conversion fac-
2. Permeability (J.L)/(A.t.p) Punit = 2 emperature !:;
"
cm .s.(cm Hg) RH tors for) the following
coefficient i.e. =P units of P: (cm3 .mil)/
barrer = 10- 10 P unit (m 2 .24 h.atm);
(cm 3 .mil)/(lOO in 2 .24 h.atm);
~
(cm 3 .mm)/(m2 .24 h.atm) Vl
-..l
~
00
TABLE 12.1-eontd.
Penetrant Plastics Index of permeability Data required Relevant determination

barrier in methods,
Description Special unit Constituent conjunction references and
name and/or simple remarks
Name In terms of eqn (2) symbol units
Any Walls of Permeability (J.L)/A p1 g.cm Temperature ASTM D 2684-73

(consti. plastics con- factor m 2.day RH
tuents tainer
of con-
~
tents of ~
a plas- :::J
tics con· 0
:;;
tainer)
Any Any plastics Resistance factor (A.t1p)/J - N.s Barrier thickness (L) Ref. 90
(but lamina (in i.e. = lI(P/L)
-- Temperature
mol
mainly practice film RH
fluids) or sheet)
a Fixed in terms of the RH in standard determinations.

b i.e. one femtometre per pascal per second = 8·752 em' (at STP)/(m 2 .24 h.atm).
c STP: 760 mm Hg and 273 K.
d i.e. permeability factor at temperature I.
TABLE 12.2
Some Common Fonns and Units of the Permeability Coefficient
......
Physical Flux Area Driving force Thickness Equation (2) Resulting '"
state of (J) (A) (F) (L) in terms of units of ~
penetrant units units units the units permeability .g
"-
....
in contact Nature Units coefficient ::>.
with (P) ~
barrier ~
~
"-
Any mols- I m2 Concentration molm- 3 m mol mol m 2 s- 1
difference (dC) -= P- - '"~
s.m 2 m3 .m S-
~
Any mols- I cm 2 Concentration mol cm- 3 cm mol mol cm 2 S-I ....
difference (dC) --= P- - ~
s.cm 2 cm 3 cm S·
Gas or mols- I m2 Pressure" Pa(=Nm- 2 ) m mol N molms- I N- 1 "tl
-= P- - -.::::
vapour difference (dp) s.m 2 m2 .m (j
b cm 2 Pressure" cmHg b cm 3 (cm Hg) cm 2 s (cm Hg)-l

Gas or cm3 S-I cm ~
--= p--- ~
vapour difference (dp) s.cm 2 cm :::!.
l::l
;;;-
Gas or b cm 3 (24 h)-l 100in2 Pressure" atm mil b cm 3 atm cm 3 mil (24 h)-I l::l
=P- ;:s
vapour difference (dp) 24 h.l00 in 2 mil (100 in 2 )-1 atm- I ~
Water g (24 h)-I m2 Pressure" mmHg cm g (mm Hg) g cm (24 h)-I ~

--= p m- 2 (mm Hg)-I ~
vapour difference (dp) 24h.m 2 cm i:
I;;;
'"
"Or partial pressure, as applicable.
bAt STP.
.,..
v.
ID
460 w. V. Titow
coefficient (assumed to be constant or dependent only on concentra-

tion) and S is a solubility factor expressing the equilibrium content of
the penetrant in the plastics barrier material at the relevant
temperature.
If S is given in the form of a ratio, viz.
equilibrium concentration of penetrant in barrier material
S = concentration of penetrant 'upstream' of barrier
with both concentrations expressed in the same units, it becomes a
dimensionless partition coefficient, and P will have the same
dimensions and units as the diffusion coefficient (length2 time- 1-ef.
the first two entries in Table 12.2).
Solubility factors and Fickian diffusion coefficients can be deter-
mined fairly readily for plastic/penetrant systems of practical interest.
However, there is still no general, complete explanation of the way in
which the chemical structure and interactions of the components in
such systems influence the mechanisms of solubility and diffusion.
There is also no comprehensive theoretical treatment available for
diffusion of penetrants in polymers below the glass temperature (Tg ),
where complex time-, history- and concentration-dependence may
occur. This is relevant in connection with rigid PVC compounds which
are essentially glassy (non-crystalline) with Tg values well above room
temperature. Flexible PVC of medium and high plasticiser c;ontents is
normally rubbery, as plasticisation reduces the effective Tg •
A more extensive discussion of the mechanisms and theories of
diffusion in polymers would be beyond the scope of a short section in a
technological book on PVC. Informative accounts are available in
publications by Fujita 14 and Meares l 5-17 (theory and various features
of diffusion), Crank and Park 18 (most aspects), Stafford and Braden 19
(diffusion of water in polymers).
The permeability of a porous plastics material (i.e. one containing
inter-communicating voids) is a matter of the rate of passage of the
penetrant concerned through the pores. On the assumption that the
pores are large in comparison with the size and the mean free path of
the penetrant molecules (the situation of practical interest in this
section), two general cases may be distinguished.
(i) The penetrant may be moving through a fluid (in practice most
frequently air or water) which fills the pores but does not itself
flow through them to an appreciable extent. The transport
mechanism will be 'straight' diffusion, or movement under a

directional driving force, e.g. the electrical force actuating the
passage of ions through the water filling the pores of a PVC
battery separator: apart from this example there are not many
instances of this kind of permeability relevant to practical
applications of PVC.
Equation (2) can be applied to describe the general
relationships in this case, but here the permeability coefficient
will represent essentially the effects of interactions between the
components of the system penetrant/pore-filling fluid integrated
with those of any other factors or constraints operative in the
system.
(ii) The penetrant, in this case itself a fluid, may be flowing through
the pores. The transport mechanism will be viscous flow (i.e. the
penetrant will continue to behave as a fluid whilst in the pores):
in practice the driving force will most often be a pressure
difference ('pressure drop') across the porous barrier.
In this case the relevant relationships can still be represented,
in general terms, by an expression closely analogous to eqn (2).
However, the expression must contain a viscosity factor, since
the viscosity of the fluid penetrant is an important parameter.
This is exemplified by the well-known D'Arcy equation which
may be written in the form
J/A = K[~p/(L1])] (4)
where 1] is the viscosity of the penetrant, K is the permeability

coefficient, and the other symbols have the same meanings as in
eqn (2).
For a given penetrant under standard conditions K represents
the combined effects of the internal structural characteristics of
the porous barrier (with the total volume, configuration and size
of the pores as especially important factors).
As can be seen, in neither of the above two cases are the chemical
and other intrinsic properties of the solid material of the barrier
particularly important. Hence, say, porous uPVC may be expected to
behave much like any other solid porous barrier of the same porosity
characteristics. For this reason the permeability of porous PVC will not
be considered further. The books by Carman20 and Scheidegger,21 and
the excellent papers by Rodebush and Langmuir,22 Davies,23 Iberall,24
462 w. V. Titow
and Thomas 25 may be referred to for further information on flow of

fluids through porous media.
Many aspects of the permeability of 'solid' (i.e. non-porous) plastics,
with special reference to films and coatings, are discussed in a
collective publication edited by Hopfenberg. 26
Two useful, earlier publications by Lebovits,27 and Hennessy et al. 28
review the permeability of polymers and plastics to fluids. The latter
work deals in considerable detail with practical methods of determina-
tion.
In virtually all procedures for determining the gas permeability of
polymeric barriers, the amount of gas passing through in measured
time is determined from the volume change at constant pressure, or
the pressure change at constant volume (the manometric method), or
the contents of the penetrant gas in a carrier gas 'upstream' and/or
'downstream' of the barrier. The equipment used is normally an
appropriate 'gas cell' (e.g. a variant of the so-called 'Dow cell' as
employed in the method of ASTM D 1434-see Table 12.1). Various
types of apparatus and their commercially available embodiments are
mentioned in a paper by Pye et al. ,29 which also describes a particularly
versatile gas-permeability apparatus (of the manometric type) de-
veloped by the authors.
Water vapour permeability is most often measured by 'dish' or
'sachet' methods, prescribed by several of the standards listed in Table
12.1. In a 'dish' method the specimen forms the closure (secured with a
vapourtight seal) of a dish or beaker containing a desiccant. The
container is placed in an enclosure at a constant temperature and
controlled (normally high) relative humidity, and the passage of
moisture through the specimen is followed by repeated weighing. In
the sachet method, a sealed sachet containing water is placed in a
constant-temperature enclosure in which the humidity is controlled at a
low value. The sachet is weighed periodically to determine the rate of
loss of water. Other methods are also available. 28
Permeability to other penetrants may be determined by methods
similar to those used for gases and moisture. The container method of
ASTM D 2684 (see Table 12.1) is also used. In some cases the amount
of penetrant passing through a plastics barrier in measured time is
determined by chemical, chromatographic or gravimetric techniques. 28
Considerable success has been claimed for predictions of the
long-term barrier performance of plastics containers in service, based
on permeability coefficients calculated with the aid of the 'permachor'
concept, first developed-largely on an empirical basis-in the 1950s in

connection with the storage properties of blow-moulded polyethylene
bottles. 30 ,31 The method is to calculate a so-called 'permachor value'
for a given potential penetrant by summating appropriate values
allocated to its constituent atoms and/or functional groups: in this
respect the approach is somewhat similar to that involved in calculating
solubility parameters. 32 Certain corrections are applied, and the final
figure is substituted into the equation
log P = K - Rn (5)
where P is the permeability coefficient, K is a temperature correction
factor and R is another correction factor associated with the polymer
(or polymer compound).
R values of 0·22 and 0·26 have been quoted 31 as appropriate for
polyethylene (apparently regardless of density) and polypropylene,
respectively, with values of K varying not only with temperature but
also with polymer density (for polyethylene) and nature (e.g. K = 2·3
for polyethylene of density 0·945, and K = 4·2 for polypropylene, both
at 23o C).31 So far no analogous data appear to have been published for
PVC. Computer prediction of long-term gas transmission characteris-
tics of polymers in service has been discussed by Horsfall and James. 33
Unplasticised PVC is a reasonably good barrier against simple gases
and water vapour. Taking the relevant permeability value of
unstretched uPVC 40,um film as unity in each case, some typical
comparative permeabilities of similar films of other polymers would be
as follows:
Nylons Polyolefins
6 6·6 11 HDPE LDPE PP
O2 0·3 0·6 4 22 57 22
N2 0·7 0·6 2·5 44 146 36
CO 2 0·6 0·4 7·5 36 125 30
H2O 8 2 0·3 0·1 0·4 0·3
Permeability to other penetrants depends strongly on their chemical

nature.
To the extent to which it is valid to generalise over a broad range of
conditions and potential penetrants, the following points may also be
464 W. V. Titow
made. Other things being equal, PVC compositIOns based on

homopolymers are less permeable than those based on copolymers
with vinyl acetate, but more permeable than vinyl chloride/vinylidene
chloride copolymer compositions (ct. Table 12.4). Blending with other
polymers tends to increase permeability, but the opposite effect can
occur: even with the same component in a blend the permeability can
increase or decrease depending on the proportions and processing
conditions. Such effects have been observed, e.g. in the case of
penetration of oxygen and nitrogen through blends of PVC with
ethylene/vinyl acetate copolymer (EVA):34 they can be explained in
terms of the way in which composition and processing influence the
morphology and phase structure of a blend, both factors affecting the
rate of diffusion of penetrants. Stretch-orientation can reduce the
permeability of uPVC film by a factor of 2 (more in some cases).
Plasticisation, and generally incorporation of fully intermiscible
additives (e.g. impact modifiers, processing aids, internal lubricants)
tends to increase the permeability of PVC to most penetrants.
However, transmission of water vapour may be reduced in some
compositions by the inclusion of chlorinated plasticiser extenders.
Addition of fillers, which form a separate phase in the compound,
TABLE 12.3
General Order of Permeability of PVC to Some Common Penetrants at Room
Temperature
a Units: cm 3 (at STP).cm.cm- 2 .s- I.(cm Hg)-I.

b Units: g.mil.(lOO in 2 )-1.(24 h)-latm- 1.
C Typical, approximate factors representing order of change in comparison with values
for comparable uPVC compounds.

may have no effect on permeability, or it may reduce or increase it,

depending on the penetrant, and on the frequently complex effects of
the chemical nature, particle size and shape, distribution, orientation,
amount, and surface properties of the filler. The reduction in water
vapour transmission sometimes brought about by the incorporation of
relatively small amounts of certain waxes is probably associated with
the incomplete compatability and hydrophobic nature of this type of
additive.
Some permeability data are given, by way of illustration, in Tables
12.3-12.5.
TABLE 12.4
Permeability of PVC Homopolymer and Copolymer Compounds to Gases
TABLE 12.5
Water Vapour Transmission of Breon Films 0·004 in Thick,
Containing Various Plasticisers
(Room temperature, dish method at 100% RH)
Plasticiser
DOP 1·15
Oetyl deeyl phthalate 1·35
Trioetyl phosphate 1·61
Tritolyl phosphate 1·70
Dioetyl adipate 1·77
Cresyl diphenyl phosphate 1·91
466 W. V. Titow
The rate of transmission of water vapour (in a dish test with desiccant,
at room temperature and 100% RH) through some commercial PVC
sheeting products is illustrated by the following figures (grams per
square metre per 24 h):
Rigid sheet (homopolymer-based) 0·050 in thick: 0·1
Pipe-wrapping PVC tape with polyisobutylene adhesive layer
(PVC thickness 0·013 in, adhesive layer 0·008 in): 0·6
General purpose adhesive tape (PVC layer 0·010 in thick): 2·5
It will be clear from what has been said in this section, that the
results of permeability tests are valid and their numerical expression
meaningful only for strictly standardised test conditions, which should
be specified. Moreover, even when these requirements are met, and
the results are given in appropriate units, comparison between sets of
data from different sources should be made with caution, as materials
of apparently the same kind (say two rigid PVC films of comparable
thickness) may differ in composition or nature of individual consti-
tuents (e.g. different lubricants, processing aids, stabilisers, may be
present), processing history and fine structure. Differences in the
performance of basically the same equipment in two different
laboratories may also be significant.
12.5 ENVIRONMENTAL STRESS CRACKING AND

CRAZING
Plasticised PVC is not normally susceptible to failure of this kind.

uPVC can be, albeit cases are not so common or frequent as to
constitute a serious practical problem: however, since they do occur,
the subject merits a brief discussion.
Crazing is a characteristic, localised deformation of a polymeric
material. A craze may be defined, after Kambour,35 as a thin,
plate-like region containing apparently continuous but in fact micro-
cellular material, usually oriented, interconnected with the surrounding
'normal' material. Craze matter has the general characteristics of
open-cell foam. In most cases it is load-bearing, but-as would be
expected-its mechanical properties are different from (and generally
inferior to) those of the solid 'parent' material. 35,36 Thus crazes
constitute regions of comparative weakness in a polymeric material,
often discernible visually because of their opacity.
Cracking is a type of complete, local brittle failure. The term 'crack'

needs no special definition, but it may be recalled in passing that cracks
typical of environmental stress cracking of plastics are wedge-shaped,
and range in size from hair-cracks to large discontinuities, depending
on the material and conditions.
Environmental stress cracking and crazing may jointly be termed
'environmental stress failure' (ESF). The cardinal features of ESF are
that it occurs in the presence of an 'active environment' (a cracking or
crazing agent, which is normally a fluid, i.e. a gas, vapour or liquid),
and either in the absence of externally imposed stresses or at external
stress levels significantly below the normal short-term yield strength of
the material in air. In practice the stresses responsible (jointly with the
active environment) for ESF can be either internal, or external or (as is
often the case) a combination of both. As has been pointed out by
Ziegler,37 internal stresses may arise from the following causes:
(i) differential cooling of the polymer in the final stages of
moulding (thermally induced moulding stresses);
(ii) molecular orientation, with or without crystallisation, arising as
a result of the flow and the cooling process in the course of
moulding (orientation stresses);
(iii) forced introduction of additional polymer into the mould when
that already present in the mould has begun to cool and
contract (packing stresses);
(iv) thermal shock either to the whole or to parts of the moulding,
caused by treatments such as, for example, machining (thermal
stresses).
The external stresses instrumental in ESF may be those encountered
in any processing or handling after moulding, or in service, or those
deliberately applied in tests.
Some environments (e.g. certain organic liq4ids), strongly active as
cracking agents for certain glassy polymers, can promote ESF under
stress two orders lower than the minimum cracking or crazing stress in
air at the same temperature. 36
Under given conditions the environmental stress failure of a plastic
will occur when local elongation within the material exceeds the
maximum such elongation that the material can accommodate without
failing. This is essentially the concept of critical strain, which has been
defined 38 as that minimum strain at which under a particular set of
conditions stress cracking or crazing is known to start. The main
468 W. V. Titow
factors making up the 'set of conditions' are the nature of the

environment (i.e. the cracking or crazing agent), the stress, the
temperature, and the rate of strain. Most of the methods used to study
ESF are ultimately concerned with the determination of critical strain
and the associated (critical) stress, by various means and in various
kinds of apparatus. 39 Practical tests, applied in production control and
occasionally in 'trouble-shooting' investigations, are mainly qualitative.
They usually involve immersion of a moulding in a liquid (frequently a
mixture of solvents) known to be active as a cracking or crazing agent
for the plastic concerned: development of cracks or crazes within a
prescribed period is taken as evidence of the presence of internal
stresses of unacceptable magnitude, and hence risk of failure in service
under conditions conducive to ESF. 39
Standards of main, general relevance to the understanding and
investigation of ESF phenomena in plastics include the following (some
still in draft form at the time of writing).
ISO 4600:1981: Plastics-determination of environmental-stress-

cracking resistance (ESCR)-ball or pin impression method.
ISO 6525:1981: Plastics-determination of resistance to cracking
under constant tensile force in the presence of chemical agents.
BS 4618: Subsection 1.3.3:1976: The presentation of plastics design
data. Environmental stress cracking.
British Draft Document 79/50196:3/79: Determination of environ-
mental stress cracking resistance.
DIN 53 449:1970: Testing of plastics; evaluation of resistance of
thermoplastics to environmental stress cracking; steel ball impression
method. This specification is technically similar to ISO 4600.
Other standards (largely specific to particular materials and/or

products) as well as many literature sources on ESF are given in Ref.
39.
Two main hypotheses have been advanced to explain the origin and
mechanism of ESF in glassy polymers (of which PVC is one).
According to one, the 'active environment' reduces-by wetting-the
surface energy for crack or craze formation, and thus facilitates and
promotes growth of holes (craze cells and cracks) from minute voids in
the polymer which serve as nuclei. The second explanation is the
so-called 'plasticisation hypothesis'. Currently this appears the more

firmly supported by the available evidence, although it is possible that
surface energy reduction may be a contributory factor. According to
the plasticisation hypothesis, the cracking or crazing agent actually
penetrates and plasticises the polymer. As is well known, plasticisation
reduces the temperature of glass-to-rubber transition (Tg ) as well as
the modulus and viscosity of a polymer. When operating locally at the
tip of a forming crack or craze these effects should make the polymer
yield more easily under the high concentration of stress obtaining at
that point, but because the degree of plasticisation is still relatively low
(in comparison with, say, that of bulk-plasticised flexible PVC
materials) the critical strain is not substantially increased: the net result
is that propagation of a craze or crack is facilitated and promoted.
In flexible (bulk-plasticised) PVC the plasticiser concentration, and
hence the degree of plasticisation, are relatively high. The material is
well above its effective Tg at room temperature (i.e. in the rubbery
state): it is thus able to relax sufficiently readily for internal stresses to
dissipate rapidly, so that this important contributory factor to ESF
(internal stress) does not normally exist in plasticised PVc. Moreover,
pPVC is extensible and its critical strain is consequently relatively high.
These are the main reasons why environmental stress failure is not
normally encountered in plasticised PVc.
Under suitable conditions (including sufficiently high contact
concentration of agent, and magnitude of stress) some aliphatic and
aromatic hydrocarbons (or their mixtures) in liquid or vapour form can
act as cracking or crazing agents for uPVc. This has been
demonstrated in the laboratory, e.g. for n-hexane and toluene. 4o In the
author's own recent experience, local cracking (and a subsequent
burst) in service of a 90-mm high-pressure uPVC water pipe occurred
in a section found to have been in temporary contact with toluene
(through accidental spillage). In an earlier case, investigated in
Holland in 1967 by Wolf,41 the appearance of hair-cracks in a uPVC
pipe conveying natural gas was identified as environmental stress
cracking promoted by naphthalene found to be present in the Dutch
gas in appreciable concentration.
U.6 WEATHERING RESISTANCE

Weathering may be broadly defined as the overall change in a material,
brought about by outdoor exposure. In PVC the change is the
470 w. V. Titow
combined effect of several factors, interacting and affecting the

material in a highly complicated manner: thus from the technical
standpoint the weathering of PVC is a composite phenomenon,
complex in both its mechanism and nature. Some of the principal
factors instrumental in this process are listed in Table 12.6, with
indications of their main effects on PVc. However, it is a cardinal
characteristic of weathering that the factors never operate singly in
actual service conditions, but co-act and interact in many ways:
moreover their individual roles, and their contributions to the overall
result, can vary considerably depending upon the place and conditions
of exposure; seasonal variations at one and the same site also affect the
progress of weathering.
Extensive practical experience and data are available to aid
producers in formulating PVC compounds for good weathering
resistance, particularly important in such uPVC products as house and
caravan cladding, rain gutters and down-pipes, and window frames, as
well as in pPVC garden hoses, reservoir linings, tarpaulins and
outerwear. However, because of the complexity of the weathering
process and wide variability of service conditions, confident prediction
of the performance, and in particular of the likely length of useful
service life, is still very often difficult. Tests to help such predictions,
and to enable different compounds to be compared or effects of
formulation changes to be evaluated, are clearly desirable and
important. Any test method must include two elements:
(i) means of inducing in the material changes identical with, or
equivalent to, those caused by actual weathering in service over
relevant periods; and
(ii) means of assessing or measuring the degree of changes caused
(extent of deterioration).
There are three general ways of inducing weathering (or similar)
effects in a plastics material for test purposes.
1. Exposure of specimens at outdoor sites in locations and
conditions corresponding to (or correlating with) those to be
encountered in actual service, and for periods comparable with
the service life contemplated.
2. Outdoor exposure at selected sites, with the time scale substan-
tially shortened by suitable intensification of at least some of the
main factors instrumental in 'natural' weathering (e.g. amount
and intensity of incident sunlight, amount or frequency of contact

with water), or by increasing the susceptibility of the material
specimens to weathering, or both.
3. Artificial ageing in the laboratory in conditions designed to
produce, in a much shorter time, changes similar to (and/or
sufficiently well correlating with) those caused by natural
weathering.
In all three cases the effect of exposure may be assessed in terms of

changes in optical properties (e.g. colour changes-with PVC often
darkening or yellowing-or changes in surface gloss, or in trans-
parency), or differences between the 'before' and 'after' values of
other properties (with PVC products often tensile and/or impact
strength, modulus, elongation). Some standard methods relevant to
evaluating weathering effects in this way are given in ISO 4582
('Plastics-Determination of changes in colour and variations in
properties after exposure to daylight under glass, natural weathering or
artificial light') and many are listed in the Appendix to ASTM D
1435-79. In more fundamental investigations changes in some of the
properties and characteristics of the PVC polymer (e.g. the molecular
weight and its distribution, presence and nature of functional chemical
groups, IR absorption) .may also be followed, sometimes in conjunc-
tion with microscope or electron-scan examination of material surface,
and DTA or DSC determinations.
Whilst the long-term exposure approach (1 above) is the most
reliable it is in many cases impracticable as the sole means of testing,
because of the time periods involved. However, long-term exposure at
representative sites is often used to provide (eventually) reference data
against which the results of accelerated tests may be evaluated. Site
selection is important: sites in regions which provide severe conditions
are widely favoured (e.g. Arizona, the Australian interior, the
Transvaal in South Africa, for dry heat and maximum sunshine;
Florida, Natal for humid heat). More than one site may advantageous-
ly be used to allow for different types of conditions, although a recent
world-wide study of weathering of PVC42 has been held to suggest that
a reasonable correlation can be established between results from
different geographical locations. The mounting and positioning of
specimens playa part: backing with a good insulator (e.g. plywood)
helps to bring out the effect of temperature stresses; exposure racks
are normally south-facing (north-facing in the southern hemisphere)
TABLE 12.6
Some Factors Instrumental in the Natural Weathering of PVC, and Examples of Their Main Effects ~
Factor Typical action on PVC material Main observable Remarks
(environmental effects a
agent)
Sunlight Degradation of PVC polymer by UV 1, 2, 3, 4, 5, 6, Direct sunlight is also a
component of the radiation 7, 8 source of heat and hence
Fading of colourants can promote temperature
effects (see below)
Temperature Mainly effects of heat and tempera- Temperature effects can
ture fluctuation, including: promote and enhance those
(i) Heat degradation 1, 2, 3, 4, 5 of other agents
(ii) Exudation and volatalisation 6,8 ~
of components (especially :0::::
plasticisers)
(iii) Physical disruption by local ~;0
and general stresses caused by
temperature changes
Water (i) Mechanical erosion of surface 1,3 Effects aggravated by the
(including (especially by wind-borne action of other factors
atmospheric precipitation) (e.g. chemical reactions,
precipitation, (ii) Leaching out of components 1,8,9 UV, heat)
i.e. rain, snow, (especially plasticisers)
hail, vapour (iii) Mechanical disruption (especially 1,5,7,8
and condensate) of surface) by repeated
absorption and desorption
(which may be aggravated by
presence of absorbent fillers
in the material)
(iv) Chemical effects of pollutants 1,2,4,9
(e.g. acids) dissolved in rain
Air Oxidation of reactive sites in PVC 1,2,4,5,6 Effects promoted and
polymer and some other components enhanced by those of UV
radiation (instrumental in
.....
N
creating reactive sites, '1:l
eS{J~cially double bonds) ~
~
Atmospheric (i) Leaching out of components 1,2,3,4, Effects can be accelerated
pollutants (ii) Chemical reactions with the PVC 5,6,8,9,10 by heat and sunlight ~.
(in vapour, polymer and possibly other ~
liquid and solid components of the material ~
particle form) (iii) Surface erosion (by wind-borne
particulate pollutants) ~
S
a 1, dulling, marring and pitting of surface; 6, reduced extensibility; ~
2, cracking (in severe or advanced cases); 7, surface buckling or rippling; ~
3, stiffening; 8, distortion (various degrees and kinds);
s·
'1:l
4, discoloration (e.g. yellowing or darkening); 9, development of microporosity;
5, reduced strength; 10, environmental stress cracking or ~
crazing. ~
~.
0;-
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I'>..
~
f}
a
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474 w. V. Titow
with the specimens vertical, horizontal, or tilted at 45°. In some

methods specimens are exposed under glass, so that the effects of
certain weathering factors (wind, rain) are excluded (ct. ISO 877-1976,
identical with BS 2782: Part 5: Method 540A: 1977; also ASTM G 24-73,
and DIN 53388). Outdoor exposure procedures and effects are the
subject of several international and national standards, including:
ISO 4607: 1978: Plastics-methods of exposure to natural weather-

ing.
BS 4618: Section 4.2:1972: Resistance to natural weathering. Section
4.4:1973: The effect of marine exposure.
ASTM D 1435-75: Standard recommended practice for outdoor
weathering of plastics.
ASTM G 7-77: Atmospheric environmental exposure testing of
non-metallic materials.
DIN 53386:1974: Testing of plastics; testing of resistance to
weathering in nature (outdoor weathering).
British Draft Document 76/54334 (eventually to become method
828A of the revised version of BS 2782): Determination of resistance
to natural weathering.
Intensified outdoor exposure (2 above) can be effected in various

ways. A useful practical method developed by Caryl and Helmick43
involves boosting the amount of natural sunlight incident on the
specimen. In their apparatus, commonly known as 'EMMA' (Equato-
rial Mount with Mirrors for Acceleration), 10 mirrors direct extra
sunlight onto specimens, producing up to tenfold intensification. This
was found to be capable of accelerating by a factor of nine the
degradation of some uPVC materials: 44 the specimens are cooled
during exposure to prevent undue temperature rise. A further
development of this concept-involving the application of a water
spray and air stream to broaden and increase the weathering effects-is
embodied in the 'EMMAQUA' apparatus 45 in use in America at the
Desert Sunshine Exposure Test Station in Arizona. The rate of onset
of 'normal' weathering effects in PVC can also be effectively increased
(and hence the time scale of outdoor exposure shortened) if very thin
films are used as specimens: in this form the surface-to-volume ratio

(specific surface) is large, so that most of the material of a specimen is
immediately and directly available to the agents instrumental in
weathering, and is affected by changes as soon as they begin to occur.
A potential disadvantage of this approach is that the exposure period
needed to bring about measurable changes may in some cases actually
be too short to encompass seasonal variations and sporadic effects
characteristic of the 'normal' weathering pattern in the particular
locality.
In accelerated artificial weathering (3 above) the aim is to reproduce
or match in suitable degree the effects of natural weathering by
laboratory treatment of comparatively short duration. As in the other
two approaches, evaluation of the results should, in the ideal outcome,
enable accurate predictions to be made of the useful service life of the
material concerned under given climatic conditions. Failing that it is
also of interest to be able to:
(i) place materials in order of qualitative relative merit with regard

to likely weathering resistance in actual service; and if possible
(ii) quantify the ranking, even if still on a relative basis.
The answers to (i) and (ii) would, of course, follow automatically if the
ideal could be achieved of reliably equating a period of standard
accelerated exposure in the laboratory to one in actual long-term
outdoor exposure (say, for example, 1 h in a Wether-Ometer to 50 h
outdoors in Arizona). Unfortunately this is not possible, especially
where long-term predictions are concerned. This well-known fact is
illustrated, for example, by the data of Kuist and Maxim,46 and
Grossman. 47 The former two investigators quote correlation coeffi-
cients for results of accelerated laboratory weathering tests and those
of outdoor exposure as 0·6--D·9 (i.e. unavoidable variability approx-
imately between 20 and 70%). It is also known, moreover, that
differences occur in the rates of failure between long-term outdoor
exposures at the same site. However, with good equipment the relative
performance of materials in accelerated weathering tests can give a
reliable, at least semi-quantitative indication of the relative perform-
ance to be expected in the field (i.e. (i) and (ii) above are attainable).
Three factors are employed to bring about 'artificial' weathering in
accelerated laboratory tests, viz. radiation, heat, and water (as vapour,
476 w. v. Titow
liquid condensate or spray). * Exposure to radiation (light of wave-

lengths extending from about 280 nm into the visible region) is the
basic feature of all such tests: in most procedures this is combined with
the other two factors.
Radiation sources commonly used are listed in Table 12.7: the
emission characteristics of such equipment are discussed in a paper by
Allen et at. 48
It is generally recognised that, as far as radiation effects in the
normal weathering of plastics are concerned, it is the UV component
of sunlight which is the main operative factor.47-49 This is the basis of
the widely held view that the spectral distribution in the UV region of
the light used in accelerated laboratory weathering tests should be as
similar as possible to that of sunlight, t to reduce the possibility that
radiation-induced chemical (and any other) changes in the test
speCimens may differ in kind from the corresponding effects of natural
weathering. However, a strong case has also been made out for the use
of a source (fluorescent UV lamp) emitting intensely and almost
exclusively in the 290-340 nm region, where the intensity of sunlight's
spectrum is in fact comparatively low. This approach is based on the
view that most of the photochemical changes suffered by plastics in
natural weathering are attributable to the 290-315 nm UV band,47 and
that therefore exposure to a source with strong emission in this region
is both sensible and particularly effective as a means of accelerating
radiation effects in artificial weathering. Test apparatus employing this
type of illumination in conjunction with means of subjecting the
specimens to condensed moisture and elevated temperatures (see entry
No.4 in Table 12.7) has been claimed47 to give particularly rapid
accelerated weathering, and results which correlate well with those of
outdoor exposure (within the general limitations mentioned above).
* Resistance to other agencies, of specific interest in connection with

weathering in particular environments, is also sometimes assessed, in separate,
additional tests. Some examples are: Resistance to salt spray (relevant to
marine environments-see, for example, BS 3900:Part F4:1968); to marine
exposure generally (see, for example, BS 4618: Section 4.4:1973); to
microbiological attack (see Section 12.7 in this chapter); or to exposure to
damp heat, water spray, and salt mist (see ISO 4611-1980).
t For this purpose sometimes defined in standard terms as 'global radiation',
i.e. total radiation--direct, scattered, and reflected, incident upon a horizontal
plane in defined conditions (see, for example, Standard D65 of the
Commission Internationale de l'Eclairage).
The following international and national standards are concerned

with the methods and apparatus of accelerated weathering of plastics:
ISO/R 878-1968: Plastics-Determination of resistance of plastics to

colour change upon exposure to light of an enclosed carbon arc.
ISO/R 879-1968: Plastics-Determination of resistance of plastics to
colour change upon exposure to light of a Xenon lamp.
ISO 4892-1981: Plastics-Methods of exposure to laboratory light
sources.
BS 3900: Methods of test for paints. Part F3:1979: Resistance to
artificial weathering (enclosed carbon arc).
BS 4618:Section 4.3:1974: Resistance to colour change produced by
exposure to light.
ASTM D 1920-69 (Re-approved 1976): Determining light dosage in
carbon-arc light ageing apparatus.
ASTM D 1499-64 (Re-approved 1977): Operating light- and
water-exposure apparatus (carbon-arc type) for exposure of plastics.
ASTM D 1501-71: Exposure of plastics to fluorescent sunlamp.
ASTM D 2565-79: Operating Xenon-arc-type (water-cooled) light-
and water-exposure apparatus for exposure of plastics.
ASTM G 26-77: Operating light-exposure apparatus (Xenon-arc
type) with and without water for exposure of non-metallic materials.
ASTM G 53-77: Operating light- and water-exposure apparatus
(fluorescent-UV/condensation type) for exposure of non-metallic
materials).
DIN 53 387:1982: Testing of plastics; accelerated test of weathering
resistance (simulation of outdoor exposure by filtered Xenon-arc
radiation and artificial rain).
DIN 53389:1974: Testing of plastics; short test of the light stability
(simulation of global radiation behind glass by filtered Xenon-arc
radiation).
The results of accelerated weathering are assessed in the same way

as they are for natural weathering, i.e. in terms of colour changes,
TABLE 12.7
Radiation Sources in Common Use in Laboratory Weathering Equipment ~
00
Radiation sources Examples of weathering equipment in Remarks

which used and
References
Nature Approximation of UV Name or Suppliers
spectral distribution designation
to sunlight
1. Enclosed carbon Poor Fade-Ometera Atlas Electric ASTM G 23;

arc Devices Co .. ASTM G 25.
Chicago, Ill. 60613
USA
2. 'Sunshine' Fairly close Weather-Ometera Atlas Electric ASTM G 23; ~
carbon arc (Sunshine arc) Devices Co., ASTM G 25.
:0::::
(open carbon Chicago, Ill. 60613
:::;j
arc with USA o~
'Corex D'
filters)
3. Xenon arc with Close (i) Weather-Omete~ Atlas Electric ASTM D 2565
borosilicate (xenon arc) Devices Co.,
glass filter Chicago, Ill. 60613
USA
(ii) Xenotesta Carl Zeiss Inc.
New York, USA;
Quartz-Lampen
GmbH, Hanau,
West Germany;
John Goodrich,
Ludlow, Shropshire,
England
4. Fluorescent None, but source o-U-V accelerated The O-Panel Co. ASTM G 53;
UV lamp effective in pro- weathering tester Cleveland, Ohio Ref. 47
(mercury arc ducing relevant 44135, USA
lamp phosphor photochemical
coated) degradation (see ......
tv
text)
5. Mercury/tungsten Close Microscal light- Microscal Ltd, Ref. 48
lamp fastness tester Ealing, London,
1"'
i;.
England ~
6. Fluorescent UV Fair GP-PS/BL b General Products Refs 48 and 50 ~

lamp combined (more intense Manufacturing Co., One hour FSB ex- -t'
~
with UV fluorescent below 320 nm) Morristown, NJ, posure sometimes ~
'black-light' source USA approx. equated to S'
(FSB unit) one day outdoors ~
in the UK c ~
7. High-pressure Fair GP UVA ultra-violet General Products Refs 46 and 48 s·
"tl
mercury/quartz accelerometert Manufacturing Co.,
arc with 'Corex Morristown, NJ, ~
D' filters USA ~
~
a Several models available. 5'

1:;-
bOriginated by American Cynamid Co., USA. s::>
;:0
C Ciba-Geigy Technical Service Bulletin PL 9.1, January, 1977. I:l..
d Originated by National Starch and Chemical Corp., USA.

~
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I ;;
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480 W. V. Titow
deterioration of surface, or changes in other properties. In assessing

colour development (yellowing, darkening), colour changes, or
resistance to colour fading in artificial weathering, use is often made of
standard colour indices or scales, and colour fastness standards. Thus
the degree (and hence the development) of yellowness may be
measured and described by reference to the Yellowness Index (BS
2782:Part 5: Method 530A; ASTM D 1925·70 (Re-approved 1977)),
change in colour by reference to the Grey Scale (ISO 105-A02-
1978(E); BS 2662:1961; BS 4618: Section 4.3:1974; ASTM D
2616-1967 (Re-approved 1979)), and colour fastness in terms of the
Blue Wool Standards originally set up for textiles (ISO 105-B01-
1978(E); ISO/R 878-1968; ISO/R 879-1968; BS 1006:1971; BS 4618:
Section 4.3:1974). Other relevant standards include:
ISO 4582-1980: Plastics-Determination of changes in colour and

variations in properties after exposure to daylight under glass, natural
weathering or artificial light.
BS 2782:Part 5: Method 530B:1976: Determination of the colour of

near-white or near-colourless materials. *
ASTM G 45-75: Standard recommended practice for specifying
limits for fading and discoloration of non-metallic materials.
Thermal and thermomechanical analyses (DTA, DSC, TGA, TMA)

have been used as sensitive means of detecting and evaluating the
effects of artificial weathering of plastics; they have also been
employed as the combined means of both the thermal ageing itself and
the evaluation of its effects, useful results being claimed in the
prediction of service life of plasticised PVC formulations. 51
The weathering resistance of PVC is cardinally dependent on the
formulation, and in particular on the stabiliser system. The individual
roles of the major formulation components are mentioned in the
relevant chapters. Here the following general points may be made.
Much practical experience is now available to provide guidance in
the formulation of weathering-resistant PVC compounds for outdoor
service. However, by the same token, the limitations of even the best
formulations are recognised. Thus, in the extreme conditions encoun-
* This is also the subject of an ISO draft standard, ISO/DIS 3558.

tered in some hot-climate areas (e.g. in parts of Australia and South

Africa) where the intensity of incident sunlight, the proportion of
sunlight time, and the ambient temperature are all high, and where
other factors (e.g. severe hail or rain storms, large temperature
fluctuations) may also operate to aggravate the severity of exposure,
the durability-and hence the use-of even the most resistant PVC
compositions in long-term exposure situations is limited or precluded
altogether. Elsewhere PVC is successfully used in many outdoor
applications: e.g. rigid compositions for external wall cladding,
'ranch'-type fencing, road signs, rainwater goods and window frames;
and pPVC as coatings on chain-link wire fencing and tarpaulins, as well
as (in the form of flexible sheeting) for lining swimming pools and
reservoirs (although in this last application the long-term stability is
generally inferior to that of some alternative materials, e.g. butyl
rubber).
Among the formulational factors affecting the outdoor performance
of PVC materials, the following are particularly noteworthy. The PVC
polymer should have the highest molecular weight consistent with the
processing requirements applicable in the particular case. Homo-
polymers are generally preferable, although in certain compositions
(e.g. some PVC window-frame compounds) certain PVC graft
copolymers are used as impact modifiers (cf. Chapter 19, Section
19.4.3). The stabiliser system should be carefully selected, and should
preferably (with BalCd stabiliser systems invariably) include an epoxy
co-stabiliser (typically 2-8 phr): apart from the long practical experi-
ence of the beneficial effect of this type of additive, there is
investigational evidence for its useful role, inter alia, as an agent
facilitating the neutralisation of nascent HCI-evolved in the course of
degradation of the PVC polymer-by the main stabiIiser(s)
present. 52 ,53 As the main stabilisers, selected tin carboxylates can give
very good results, as can BalCd systems supplemented by epoxy
co-stabilisers and phosphite chelators. The carboxylates, too, benefit
from the presence of epoxy co-stabilisers, although there is some
evidence to show that the effect is less pronounced than with BalCd
stabilisers. 42 Where lead stabilisers are permissible, dibasic lead
phosphite is especially useful because of its UV-screening action and
antioxidant effect: combinations of this stabiliser with tribasic or
tetrabasic lead sulphate have also proved very effective for weathering-
resistant compositions. UV absorbers are commonly included (some-
times in conjunction with antioxidants) in transparent compositions for
482 w. V. Titow
outdoor use, to provide additional protection against photolytic

degradation. Polymeric impact modifiers for weathering-resistant rigid
compositions should be carefully selected from among the chlorinated
polyethylene, acrylic, and EVA types. Rubbery modifiers (ABS, MBS)
are not suitable in this application.
Two common pigments are noted for their beneficial effect on the
weathering resistance of PVC: carbon black and titanium dioxide. The
latter can also apparently enhance the effect of certain colourants
which are known to exert a stabilising action of their own: two
examples of such colourants are indanthrene blue and carbazole
violet. 54
The weathering resistance of plasticised compounds can be im-
proved by keeping the plasticiser content as low as possible, using
selected high-permanence plasticisers (some polymerics can be
particularly useful), and incorporating epoxy plasticisers as already
mentioned.
To obtain the best weathering performance possible with a particular
formulation, attention should be paid to the processing conditions (in
particular excessive heating should be avoided), and preferably no
re-worked material should be included. Presence of solvent residues in
solvent-cast films can have an effect: residual tetrahydrofuran was
found to promote photodegradation of PVC in air. 55
External treatment (surface coating) may sometimes improve
weathering resistance: the lacquers applied as thin top coats to flexible
PVC sheet products (e.g. coatings on fabrics-see Chapter 22) can
have this effect. Such coatings, conventionally applied from solvent
solution, normally contain an acrylic polymer as a main component.
Co-extruded protective acrylic coatings on rigid PVC products have
also made their appearance: for example, improved weatherability is
among the advantages claimed for the German 'Vacuplast' PVC
window frame system56 produced from acrylic-surfaced extruded
profiles (with aluminium reinforcement). Application of UV absorbers
to the surface of transparent PVC sheeting by absorption, as well as in
surface coatings, has been suggested57 as a way of obtaining more
cheaply a degree of weathering protection comparable with that
afforded by the conventional incorporation into the compound. The
effectivity of internally incorporated stabilisers can be significantly
affected by their degree of dispersion, migration through the
compound, volatility and extractability. 58
12.7 RESISTANCE TO BIOLOGICAL ATTACK
12.7.1 Microbiological Attack (Biodegradation)
In the plastics context this normally means attack by fungi (mould,

mildew) or bacteria. Whilst infestation by algae might also be included
in the term in its widest connotation, it is not a major problem even
with such PVC materials as film linings for canals, reservoirs and
swimming pools.
The essential mechanism of microbiological attack is enzymatic
degradation of the substrate on which the micro-organisms groW. Both
bacteria and fungi produce enzymes capable of breaking down many
carbon compounds (those containing oxygen-bearing functional groups
can be particularly susceptible) to simpler substances utilisable as
nutrients. Some of the products of the breakdown process can be
coloured, so that the appearance of colour (in PVC often a
characteristic pink stain 59) or black spots, as well as deterioration of
some properties in consequence of the chemical degradation, are the
main outward manifestations of microbiological attack; others include
the development of offensive odours, surface tackiness (in soft pvq,
or surface cracking. The resistance of PVC materials can vary widely
depending on the formulation: some compositions stand up very well
to long exposure in the most unfavourable conditions, such as warm,
humid environments (indoors or out), soil burial or permanent
immersion in water. However, even a very resistant formulation can be
affected indirectly, through contact with a material that is prone to
attack: thus, for example, mildew may grow on the cotton fabric
backing of a PVC-coated protective glove (especially if kept moist with
perspiration for long periods) or on the moist paste layer of a
PVC-coated wall paper, or micro-organisms may flourish on surface
contaminants (grease, dirt) on PVC cladding.
In broad terms, the relevant characteristics and effects of the main
components of a PVC formulation may be summarised as follows. Like
many other synthetic polymers, the polymers and copolymers of vinyl
chloride are resistant to attack by micro-organisms. However, some
commercial PVC resins may contain residual amounts of emulsifying or
suspending agents used in their production, and these may be
susceptible. 44 ,60,61 Many plasticisers are vulnerable to microbiological
attack, as are some stabilisers and lubricants (especially epoxy
484 W. V. Titow
compounds, some stearates and waxes), and certain antioxidants,

although some organotin stabilisers and phosphite co-stabilisers
actually tend to inhibit microbiological growth. 6o The general ranking
of plasticisers, in order of increasing susceptibility, is:
-aryl phosphates and chlorinated paraffin extenders
-phthalates and trimellitates
-aliphatic esters (with sebacates and ricinoleates tending to be least
resistant in this group)
-polyesters (with some exceptions)
-epoxy esters and epoxidised oils
The resistance of plasticised PVC to microbiological attack is also a
function of plasticiser content in many cases. 62 Some fillers may be
vulnerable, e.g. wood flour in wood-filled PVC compounds used for
extruded profiles and trim. 6
Special protective additives are included in PVC formulations at risk
of microbiological attack. Those with a positive ability to destroy fungi
and bacteria are often referred to as fungicides and bacteriocides,
respectively (or, collectively, biocides): the terms 'biostat', 'fungistat'
and 'bacteriostat' are applied to substances which deter micro-
organism growth by whatever mechanism. Kaplan et at. 63 evaluated the
action of 32 biocidal compounds in PVC film: they concluded that of
those only one, 'copper 8-quinolinolate' (bis(8-quinolinolato)-Cu),
provided fully satisfactory protection. N-(trichloromethylthio)-
phthalimide also gave good results, but was considered less effective
and less widely compatible with PVC formulations. This ranking
appears to reverse the order that might be inferred from industrial
usage: although N-(trichloromethylthio)imides and the copper complex
are both used in commercial biostats, compounds of the former group
would be regarded as more versatile and possibly more effective at
least in some cases. Other compounds of practical interest are phenyl
mercury salicylates,6h and organic compounds of arsenic (e.g. Estabex
ABF-AKZO Chemie UK Ltd). Some commercial products are
claimed to give broad biostatic protection (e.g. TV-2-Sanitized Sales
Co. of America Inc.; Mikro-Chek 12-Ferro Chemical Division,
* The use of organomercury biocides in flexible PVC has been discontinued on

toxicological and environmental grounds despite their usefulness as the only
biocides of proven effectivity against Pseudomonas aeruginosa which can cause
problems in pPVc.
USA). A bacteriostat of lower than average toxicity, highly effective in

plasticised PVC products (baby pants, curtains, flooring, gloves)
against both gram-positive and gram-negative bacteria, is
2,4,4'-trichloro-2'-hydroxydiphenyl ether (Irgasan DP 300--Ciba-
Geigy): it is also active against certain fungi which grow on the skin,
e.g. athlete's foot. Its main function is to reduce growth and spread of
bacteria and to suppress odour, rather than to protect the PVC itself
against bacterial attack.
Amounts of biostats used in PVC formulations vary with the nature
of the reagent and the formulation itself, within the range of about
0·1-2% by weight of the formulation. The protection they afford is of
interest in many applications. In addition to those already referred to
in this section, electrical wire and cable coverings, PVC-coated
tarpaulins and foul-weather clothing, garden hose, and some pipe
formulations may also be mentioned.
Testing the resistance of a plastics material to microbiological attack
in the laboratory typically involves placing specimens in contact with
stock cultures of selected micro-organisms under controlled conditions
for a prescribed time, * and determining changes in a selected property
or group of properties. The appearance of the specimens before and
after the treatment is usually noted, either as part of the evaluation or
additionally. Some relevant standards are listed below. Of these BS
4618 gives a short bibliography, and ASTM G 21 lists in an appendix
several standard (ASTM) methods for determining changes in the
properties which may be monitored in the tests.
ISO 846-1978: Plastics-Determination of behaviour under the

action of fungi and bacteria-Evaluation by visual examination or
measurement of change in mass or physical properties.
BS 4618: Section 4.5:1974: The effect on plastics of soil burial and
biological attack.
ASTM G 21-70 (Re-approved 1980): Standard recommended
practice for determining resistance of synthetic polymeric materials to
fungi.
ASTM G 22-76: Standard recommended practice for determining
resistance of plastics to bacteria.
* Actual soil burial tests are also popular with investigators.

486 W. V. Titow
ASTM G 29-75: Standard recommended practice for determining

algal resistance of plastic films.
u.7.2 Insect and Animal Depredations
In practice the only problems of any significance under this heading

arise in connection with attack on PVC products by termites and
rodents.
(a) Attack by Termites

Although this only occurs in tropical and sub-tropical countries it can
be a problem with PVC products, especially soft PVC (e.g. electrical
wire insulation, cable covering, upholstery fabrics and foam). Experi-
ence appears to indicate that termites have a preference for soft
plastics generally, and hence high loading with hard fillers has been
suggested as a possible way to more resistant formulations (see, for
example, BS 4618). Other suggestions that have been made from time
to time included the use of phosphate plasticisers (regarded as more
resistant than other kinds),64 incorporation of lead naphthenate, and
incorporation of insecticides in, or their application in coatings to,
PVC materials. 65 The effectivity of such measures is by no means
established or universal: susceptibility can differ in different localities
and with different species of termite, and no PVC material can be
guaranteed to be generally immune from attack, even if it has
performed satisfactorily in a particular set of conditions. In some
countries a metal barrier (tape) is prescribed by regulations to prevent
termite and animal attack on the PVC covering of electrical cables, and
this is an effective solution in this particular case.
(b) Attack by Rodents

PVC materials are not, in general, palatable to rodents, and are not a
source of food. They are attacked, however, by mice and rats if they
form an obstacle on the way to food or water. Some apparently less
purposeful gnawing is also experienced from time to time on such PVC
products as electrical insulation and conduit, uPVC water pipes, and
reservoir linings.
Although barriers may be incorporated in some products (e.g. cable
coverings, see above) there is no generally applicable way of
preventing these depredations. However, they are neither sufficiently
frequent nor widespread to constitute a major problem.
12.8 CHEMICAL RESISTANCE
At ordinary temperatures PVC homopolymer is resistant to most of

the common inorganic reagents (including aqueous salt solutions),
oxidising agents (with the partial exception of concentrated nitric acid)
reducing agents, aqueous solutions of detergents, oils (mineral, animal
and vegetable), fats, aliphatic hydrocarbons and alcohols. Its solvent
resistance is, however, limited in certain respects: it can be dissolved
by some ketones (tetrahydrofuran, cyclohexanone, isophorone) and
swollen to varying degrees by others; some nitroparaffins can swell or
even dissolve it; and chlorinated hydrocarbons, aromatic hydro-
carbons, aromatic amino compounds, as well as some other reagents
(e.g. acetic anhydride) are also swelling agents.
Copolymers are somewhat less resistant, especially to organic
solvents (cf. vinyl solutions-Chapter 24), save in the exceptional case
of copolymers of vinyl chloride with maleic acid imide derivatives (cf.
Chapter 1). However, their general resistance characteristics are
broadly comparable with those of the homopolymer.
As is usual with thermoplastic polymers, the susceptibility of PVC
homo and copolymers to chemical attack increases with increasing
temperature: the same behaviour is exhibited by uPVC and pPVC
compounds. The resistance of compounds can also be lower (in some
cases considerably so) than that of the PVC polymer alone, because of
the presence of the various additives. However, uPVC compositions
are not normally significantly inferior in this respect, although the
presence of some impact modifiers may increase solvent susceptibility
somewhat, whilst resistance to acids and alkalis may be affected by
heavy loading with certain fillers (e.g. whiting and wood flour,
respectively). Flexible (pPVC) compositions may be more readily
attacked by solvents; the increased susceptibility depends mainly on
the nature and amount of plasticiser(s) present. The general chemical
resistance characteristics of PVC compositions are summarised in
Table 12.8. Additional data for uPVC are given in Tables 12.9 and
12.10. ISO/DATA 7:1979 gives data on the resistance of uPVC pipes
to many fluids at up to 60°C.
Apart from any direct chemical action, some reagents can affect the
properties of PVC materials by leaching or dissolving out important
components of the formulation (e.g. plasticisers, stabilisers) even if
only from the surface layer. Plasticisers may also be lost by migration
into materials in close contact with pPVC (e.g. adhesives, lacquers)
whose properties may be affected as a result.
.j>-
TABLE 12.8 oe
oe
General Chemical Resistance Characteristics of PVC at Room Temperature
Reagents Rigid PVC Plasticised PVC
General Remarks General Remarks
resistance resistance
Q Q
rating rating
Inorganic acids:
Dilute No attack up to 60°C, but S No significant attack up
max. allowable design to 20°C; plasticisers and
stress should be lowered some fillers may be affected
at higher temperatures
Concentrated M Plasticiser and some ~
fillers may be affected
~
Oxidising
(concentrated)
:1
M Attacked above 20°C;
max. allowable design
U Short-term contact may be
acceptable in some cases :::l
0
stress should be reduced ~
substantially
Organic acids M M
Alkalis:
Dilute No attack up to 60°C; Some plasticisers and
allowable design stress fillers may be affected
Concentrated should be substantially
reduced
Oxidising agents
:}
S Allowable design stresses
:}
S Some fillers may be
should be substantially affected
reduced
Reducing agents S No attack up to 60°C S No attack up to 60°C
Detergent solutions S S
Inorganic salt solutions S S
Halogens:
Chlorine M Little attack in the U
absence of moisture
Bromine U U
Fluorine U U ......
N
Iodine U U
Aliphatic alcohols S Allowable design stresses M ~
should be substantially .g
reduced '"~.
Water S Some softening possible at S Softening, and some
elevated temperatures effects on certain fillers ~
at elevated temperatures ~
Aliphatic hydrocarbons S M Extraction of plasticisers
and some effects on other
'"~'"
components possible ;:-
~
Aromatic hydrocarbons U U
Chlorinated U U
~
s·
hydrocarbons "l:I
Esters U U -.::::
()
Ethers U U
Ketones U U ~
~
Aldehydes M M ::I.
$::>
Amines M M 0;-
$::>
Liquid fuels S-M See also Table 12.10 M-U ;:::
~
Turpentine U U
~
Oils: 0
~
Mineral S M-U l::
1:;'
'"
Vegetable and animal S M-U
Fats S M-U
a Rating key: S = Satisfactory. .j>.
M = Moderate (dependent on formulation and conditions). 00
-a
U = Unsatisfactory.
TABLE 12.9
Effects of Chemical Immersion on a High-impact uPVC Compound
Chemical 30-day immersion 30-day immersion
at room temperature at 60"C
Tensile Weight Tensile Weight
strength change strength change
(lbfin- z) (%) (lbfin- Z) (%)
Acetic acid 20% 5200 0·81 5000 3·29

80% 4500 1·99 2450 8·25
(glacial) 3600 4·48 1450 15·39
Chromic acid 10% 5800 0·50 5800 1·64
30% 5900 0·43 5700 2·26
40% 5800 4900
Hydrochloric acid 30% 5300 0·22 4700 1·48
Nitric acid 30% 4900 0·32 5450 0·98
60% 5700 0·40 4200 6·59
Oxalic acid (sat. soln) 5550 0·48 4950 1·72
Phosphoric acid 75% 5450 0·04 5250 -0·19
Stearic acid 100% 4800 3·54
Sulphuric acid 20% 5500 0·14 5900 0·04
50% 5600 -0·07 5800 0·58
80% 5400 -0·01 5700 12·78
Butyl alcohol 4600 1·20 2150 5·14
Ethyl alcohol 4100 1·21 2400 3·17
Sodium hydroxide 10% 5400 0·14 5400 0·22
30% 5200 0·02 5900 -0·05
50% 5600 -0·02 5400 -0·11
Carbon tetrachloride 1850 59·14 Excessive swelling
Trichloroethylene 1550 103·21 Excessive swelling
Benzene 5000 73-11 Excessive swelling
Castor oil 5300 0·44 5000 0·07
Cotton seed oil 5150 0·18 5400 0·26
Glycerine 5450 0·07 5900 0·18
Hexane 3000 4·24
Linseed oil 5150 0·07 4800 0·44
Salt solutions (sat.)
Barium sulphide 5000 0·61 5450 3·11
Ferric chloride 5100 0·25 4750 0·32
Potassium chloride 5000 0·22 4800 0·20
Sodium dichromate 5400 0·23 5150 0·18
Trisodium phosphate 5050 0·46 4800 0·78
Formaldehyde 5000 0·80 4200 3·57
Hydrogen peroxide 4700 1·53 4800 1·67
Phenol Excessive swelling
Turpentine 2850 3·87 1850 35·49
Distilled water 5200 0·61 5100 0·94
TABLE 12.10
Further Data on Chemical Resistance of Rigid PVCa
Chemical Temperature Chemical Temperature
(0C) (0C)
20 60 20 60 ......
N
Acetaldehyde: 100% U U Chloric acid, 1-20% soln S S ~

40% S M Chlorine: gas S S .g
Acetone U U moist gas S - '"....
:::-.
Aluminium fluoride S S liquid U U ~
Ammonia liquid, 100% M M Chlorobenzene U U ~
Ammonium hydroxide, S S Chloroform U U ~
0·88 Chlorosulphuric acid S U '"
Ammonium fluoride, 20% S S Chromic acid S S
'"
§:
Ammonium sulphide S S Citric acid, sat. S S ~
;;;
Amyl acetate, 100% U U Copper fluoride, 2% S S ....
~
Aniline, 100% U U Copper cyanide S S -s·
Barium chloride S S Cresol M U "'tl
Benzaldehyde M U Cresylic acid S S '<::
(')
Benzine S S Cupric fluoride S S
Bleach lye, 10% S S Cyclohexanol U U
a::
;;;
'"
Bromine gas, weak S - Cyciohexanone U U ....
1:;'
Bromine liquid U U Dibutyl phthalate S S /;;'"
Bromic acid, 10% S - Diethylene glycol S S ;:,

Diglycolic acid S S
'"
l:>..
Butyl acetate U U "'tl
Butyric acid: 20% S M Dioctyl phthalate U U Cl
l:>..
cone. U U Ethyl acetate, 100% U U l'::
Butanol: primary Ethyl alcohol S S I;;

'"
S S
secondary S U Ethyl butyrate M U
Calcium chlorate S S Ethyl chloride S S
Calcium hypochlorite, soln S S Ethyl ether U U .;..
\0
Carbon disulphide M U Ethylene chloride U U
Chloracetic acid, 100% S S Ethylene dichloride U U -
~
TABLE 12.1().......£ontd. \D
tv
Chemical Temperature Chemical Temperature

(0C) eC)
20 60 20 60
Ethylene glycol S U Kerosene S S

Ethylene oxide U U Ketones U U
Fatty acids S S Lactic acid: 10% S M
Ferric sulphate S S 90% U U
Ferrous chloride S S Lead tetraethyl, 100% S S
Ferrous sulphate S S Magnesium chloride S S
Fluosilicic acid S S Magnesium hydroxide S S
Formaldehyde, 40% S S Maleic acid, sat. S M
Formic acid: 50% S M Mercuric chloride S S ~
conc. S U Mercuric cyanide S S :0::::
Fruit juices S S Mercurous nitrate S S ~
Fuel oils S S Methyl alcohol, 10% S S <:;
~
Furfural U U Methyl bromide M U
Glucose S S Methyl chloride, 100% M
Glycerine S S Methyl ethyl ketone U U
Glycol S S Methyl isobutyl ketone U U
Heptane S S Methylene chloride, 100% U
Hydrobromic acid, 50% S S Milk S S
Hydrochloric acid, 30% + S S Mineral oils S S
Hydrocyanic acid S S Molasses, commercial S S
Hydrofluoric acid: 40% S S Naphtha S S
conc. M M Naphthalene U U
Hydrogen bromide, 10% S - Nickel chloride S S
Hydrogen peroxide S M Nitric acid: 1-30% S M
Hydrogen sulphide S S 70% S M
Hypochlorous acid S S 98% U
Nitrobenzene U U Sodium cyanide S S
Octyl cresol M M Sodium ferrocyanide S S
Oleic acid S S Sodium fluoride S S
Oxalic acid, sat. S M Sodium hypochlorite S S
Perchloric acid, up to 70% S S Sodium sulphide, sat. S S ......
tv
Petrol, aliphatic S S Stannic chloride S S
Petrollbenzene, 80/20 U U Stannous chloride S S ~
Phenol, 90% S M Sulphur dioxide: dry S S ~
Phenylhydrazine, 100% U - wet S S '"~.
~
Phosgene, liquid U U liquid M U
Phosphoric acid S S Sulphuric acid, 90% S S ~
Phosphorus pentoxide S - Fuming sulphuric acid U - .g>
Phosphorus trichloride U - Tanning extracts S - "~'"
Picric acid, 1% S - Tartaric acid, sat. S S S'
Potassium bichromate S S Tetraethyl lead S -
Potassium chromate, 40% S U Tetrahydrofuran U U
Potassium cyanide, sat. S S Thionyl chloride U U
"s·~
Potassium hydroxide, cone. S S Toluene U U "1:1
Propyl alcohol S S Transformer oil S S ~
Propylene dichloride U U Trichlorethylene U U ~
Silver cyanide S S Triethanolamine S S
::1.
Soap solution S S Turpentine U U I:;"
"'"
Sodium acetate S S Urea, up to 30% S S
;:s
Sodium bisulphite S S Vinegar S M '"
l:>..
Sodium bromide S S Xylene U - "1:1
<3
Sodium chlorate, sat. S S Zinc chloride, sat. S S l:>..
l=:
Sodium chromate S S Zinc sulphate S S 0;
"
a Key: S = Satisfactory.
M = Moderate (dependent on formulation and conditions).
U = Unsatisfactory. .j>.
'D
W
494 W. V. Titow
The good resistance of PVC to many chemicals is utilised in such

practical applications as, for example, uPVC wall cladding in chemical
plants, or the ducting and fans of fume-extraction systems, and
protective pPVC gloves and clothing for workers in the chemical
industry, laboratories and stores. The susceptibility of PVC composi-
tions to attack by some solvents is also used to advantage in some
processes as well as for certain test purposes: apart from the various
applications of PVC polymer and copolymer solutions (see Chapter
24), such uses include, for example, the incorporation of isophorone as
a keying agent in printing inks for PVC sheeting and coatings, the
use of solvents in tests for the completeness of gelation of PVC paste
coatings on fabrics (see Chapter 22), and solvent-swelling tests (in
acetone or dichloromethane) for homogeneity and structural integrity
of uPVC pipe and other extruded products and mouldings (d., for
example, ISO 3472-1975; BS 3506:1969; ASTM D 2152-80; SABS
791-1975; SABS 966-1976).
The chemical resistance of plastics materials, including PVC, is
normally tested by determining changes in appearance, dimensions,
mass, and/or other properties of specimens after a period of contact
(usually by immersion) with the chemical(s) concerned. Some of the
relevant standards give a list of chemicals for determining the general
resistance and specify the properties to be used as assessment criteria
(see, for example, ISO 175 and 462; BS 4618: Section 4.1; ASTM D
543). Some basic requirements in respect of the general chemical
resistance of uPVC compound are laid down in Table 2 of ASTM D
1784-1981.
The international and national specifications of interest in connec-
tion with various aspects of chemical resistance of PVC include the
following:
ISO 175*-1981: Plastics-Determination of the effects of liquid

chemicals, including water.
IS0/R 462*-1965: (Later incorporated in ISO 175). Recommended
practice for the determination of change of mechanical properties after
contact with chemical substances.
ISO 3473-1977: Unplasticised polyvinyl chloride (PVC) pipes-
Effect of sulphuric acid-Requirement and test method.
* Essentially equivalent to parts of ASTM D 543.

BS 2782:1970: Method 505A: Resistance to concentrated sulphuric

acid of rigid polyvinyl chloride compounds.
BS 4618: Section 4.1:1972: Chemical resistance to liquids.
ASTM D 543-67. (Re-approved 1978): Resistance of plastics to
chemical reagents.
ASTM D 1239-55. (Re-approved 1982): Resistance of plastic films to
extraction by chemicals.
ASTM D 1784-81: Rigid poly(vinyl chloride) (PVC) compounds and
chlorinated poly(vinyl chloride) (CPVC) compounds.
DIN 53476:1979: Testing of plastics; Determination of the be-
haviour against liquids.
DIN 53756:1974: Testing of plastics; Storage in contact with
chemicals.
DIN 53 428:1967: Testing of cellular materials; Determination of the
resistance to liquids, vapours, gases and solid materials.
U.9 HEALTH HAZARDS
Health hazards arise in the production, processing, use, and disposal of

most plastic materials, and PVC is no exception. Some of the hazards
are of a general nature, not directly dependent on the composition of
the plastic: e.g. risks of injury in operating plastics processing
machinery, or the well-publicised danger of suffocation to children
using plastics bags as substitute space helmets in play. This section is
concerned primarily with those health hazards which are specifically
associated with the chemical nature of PVC materials, although some
associated 'peripheral' hazards are also briefly mentioned. The main
hazard areas may be collectively identified as the risk of harmful effects
on contact with the PVC materials themselves, or their individual
constituents, or decomposition products, during any of the above-
mentioned phases of the materials' life history. The principal possible
harmful effects are poisoning (in the widest sense of the term),
carcinogenic action, irritation and tissue damage, and dermatitis. The
forms of contact through which they can arise are ingestion, inhalation,
absorption (e.g. through the skin or mucous membranes), or simple
496 w. V. Titow
'external' contact (which may also lead to some absorption) especially

if prolonged or repeated.
12.9.1 Vinyl Chloride Monomer
In the case of PVC an important potential health hazard is

encountered at the earliest stage of the material's life cycle, in that the
vinyl chloride monomer (VCM) is a recognised carcinogen. The hazard
continues wherever residual amounts of the monomer are present in
PVC resins and compounds, before, during and after their conversion
into end products. This situation necessitates precautions against
exposure to free VCM in the production of PVC polymers and
copolymers, and measures to minimise residual VCM contents of such
polymers and the compounds and products based thereon. The general
objective is to reduce to an acceptable level the amount of the
carcinogen which can be transferred by direct contact, inhaled (or
absorbed) as vapour previously volatilised into the atmosphere, or
consumed in foods and beverages which can extract it from PVC
packaging films or containers. Among the most important problems
arising in this connection is the need to know what should be regarded
as the maximum permissible concentrations of VCM in PVC materials
and the atmosphere, and the associated requirement for suitable
methods of determination. Although the carcinogenic activity of VCM
(in animals) was first made known only in 1970,66 and links with a form
of liver cancer (angiosarcoma) and a rare cancer of the mouth in
humans first recognised in the mid-1970s,66,67 much effort has already
been devoted to meeting both these needs. Several analytical methods
for determining small amounts of VCM in PVC and in air are now
available, with sensitivity in many cases better than 1 ppm, and in some
down to a few parts per (American) billion. 68 Several commercial
detectors and monitors are on the market.69 Gas-chromatography
procedures, involving either direct or head-space sampling, can be
particularly useful,70-72 although IR spectroscopy and photodetection
are also utilised in monitors for VCM in air. 69 Clip-on badges have
been developed for the latter purpose.73 Interest continues in possible
ways of determining the actual extent of damage caused by VCM in
the body: inter alia, a very sensitive method has been reported based
on the alkylating action of VCM (as well as of certain other carci-
nogens) on amino acid constituents of haemoglobin. 74
Ideas on maximum concentrations representing 'acceptable risk'
12 Properties of Specia/1nterest in PVC Materials and Products 497
levels have undergone a considerable change in the past few years with
increasing volume and availability of relevant data.
The first limits recommended in the UK (in the mid-1970s) for
maximum VCM concentration in factory atmospheres started with a
time-weighted average figure of 25 ppm (by volume), soon to be
brought down to 10 ppm with the further proviso that wherever
possible zero concentration should be aimed at. 75 At the same time in
West Germany (North Rhine-Westphalia) the maximum concentration
limits for factories were being lowered from an initial 50 ppm to
5 ppm,76 whilst in the USA a limit of 1 ppm was being demanded, with
the US Food and Drug Administration (FDA) concurrently framing
regulations to prohibit the use of rigid and semi-rigid PVC for
food-packaging applications (bottles, films) unless it could be shown
that no migration of VCM into the contents would occur. Attention
was focused on unplasticised PVC, because available evidence
indicated that plasticisation reduces residual VCM contents to
undetectably low levels. A temporary standard was put out in the USA
by the Occupational Safety and Health Administration (OHSA) in
1974, followed by a finalised version in 1978: in the same year relevant
rules, limiting VCM emission in industrial plant, were formulated by
the US Environmental Protection Agency (EPA), and EEC directives
issued in Europe on VCM content in food-packaging materials.
These moves made themselves felt in the industry in several ways.
PVC resin production, as well as that of packaging films and bottles,
was curtailed by some manufacturers unwilling to face the difficulties
and expense of reducing VCM concentrations in their plants and
products in the face of uncertainty as to what limits might finally be
laid down. Prices of some PVC resins and products were affected as
production became more expensive where removal of VCM and tighter
control over its concentration were being instituted. Some resins, in
which the VCM content was reduced by heat treatment ('stripping'),
became more glassy and harder to process as a result of this addition to
their 'heat history'. On the positive side, R&D work was stimulated
towards methods of reducing VCM concentrations in PVC materials
and factory atmospheres, methods of determining such concentrations,
and the ways in which they were affected by production conditions.
Towards the end of the 1970s the practical improvements achieved in
production and processing, coupled with the results of the R&D
effort, led to a brighter outlook on the VCM risk. Further confirmation
has been forthcoming for the relative safety of plasticised PVC
498 W. V. Titow
materials, as has evidence of a substantial drop in residual VCM levels

in both PVC materials for food packaging and the foods packaged
therein. 67 ,77 It is now practicable to reduce the VCM content of
commercial PVC resins to a few parts per 109 (i.e. by a factor of nearly
106 since the early 1970s), and there is strong evidence (from the Ethyl
Corporation in the USA) that at, or below, 2 parts per 109 VCM will
not migrate into food from PVC materials at a significant rate. 78 ,79 The
latest FDA estimates based on this evidence indicate potential
maximum VCM levels of less than 5 parts per 1012 in PVC-packaged
food. 79 Thus, whilst the fact remains that only complete avoidance of
exposure to VCM can entirely eliminate all risk, a high degree of
confidence in properly processed PVC as food-packaging material may
soon be restored. An excellent review of the VCM problem in all its
aspects was published recently by Clayton. 8o
It may be noted in passing that exposure to VCM (admittedly in
minute quantities) from sources unconnected with PVC may be a real
possibility for large numbers of people both in the industry and
outside: vinyl chloride has been reportedly found in tobacco smoke
(albeit in very small concentrations-up to 0·03 ppm), and the
possibility has been mentioned that it may also be formed as a
combustion product of other plant materials, including vegetable
refuse. 8 !
U.9.2 PVC Compounds and their Regular Constituents
Aside from the effects of VCM, the main health hazard is possible
toxicity in food-contact applications involving such PVC products as
films and containers: this hazard is usually considered from the point of
view of the properties of the individual components of a formulation.
It is normal to 'clear' these, before the formulation is finalised and
made up, on the basis of experience, and/or information from the
manufacturers, and/or the relevant recommendations or rules of the
appropriate national authorities and organisations. In the USA the
organisations most directly concerned are the ones referred to in the
previous section (FDA, OHSA, EPA): the US Department of Health,
Education and Welfare (HEW) may also be mentioned in this
connection. In the UK and Europe the bodies with related interests
and functions (albeit largely different constitutions, and scope and
nature of operations) include the UK Health and Safety Executive,
British Plastics Federation (BPF) , the UK Chemical Industries
Association, the West German Federal Health Office, and correspond-

ing organisations in many other countries. Some of these organisations
(e.g. FDA, BPF) issue lists of materials (e.g. plasticisers, stabilisers,
colourants) approved (or forbidden) for food-contact applications:
such applications constitute the area of primary concern in the context
of this section.
Some aspects of the subject of toxicity of PVC materials are
discussed in a brief paper by Estevez. 82 An earlier review, by Phillips
and Marks,83 is also still of some interest. In the UK the BPF publishes
a code of practice for safety in use of plastics for food-contact
applications, based in part on extensive evaluation tests carried out by
the British Industrial Biological Research Association (BIBRA).
It is normally assumed that PVC homopolymers, vinyl chloride/
acetate and vinyl chloride/vinylidene chloride copolymers are non-toxic
in compounds. Several lubricants (in particular stearic acid) are
regarded as safe, as are some of the other two principal formulation
components, plasticisers and stabilisers, when used in prescribed
concentrations: acceptability, especially the concentration limits, may,
however, vary according to the conditions. For example, more
stringent requirements arise for food-packaging films to be used with
fatty foods (e.g. bacon, butter, etc.) capable of leaching out
plasticisers, than for non-fatty foods with a high water content (e.g.
fruits, vegetables). The packaging of children's toys is also an area of
special concern. Detailed, up-to-date information and guidance can be
obtained from the organisations mentioned in this section. Some
further general information is also given in the chapters on stabilisers
and plasticisers.
U.9.3 PVC Decomposition Products
If thermal decomposition of PVC is permitted to occur in processing,

and when PVC is burned (e.g. in an accidental fire, or as a means of
disposal), toxic and irritant fumes are produced. These contain a
considerable proportion of hydrogen chloride (usually appearing as an
acrid, highly irritant white fume), which is the principal product of
thermal breakdown of vinyl chloride homopolymers and copolymers: 84
a sooty, black smoke usually arises from the combustion of plasticisers
in flexible PVC compositions. Other pyrolysis products of PVC
materials include benzene, toluene, xylene, naphthalene, and certain
derivatives of these compounds: 6,84--86 with an adequate supply of
SOO w. V. Titow
oxygen, water vapour, CO and CO2 are also formed, as combustion

products. 84
U.9.4 Peripheral Hazards
The kinds of hazard that may be mentioned under this heading are
relevant to PVC, although not exclusive to it, * as they can arise in the
production and processing of other plastics. They are:
(i) fire and explosion hazards;

(ii) respiratory hazards;
(iii) toxic hazards;
These occur in the storage and handling of additives and other
formulation components (especially in powder form), and in processing
operations involving the use of solvents (e.g. making up PVC
solutions, printing on PVC materials, preparation and application of
solvent-based lacquers for PVC sheet materials).
The appropriate precautions are nowadays generally reasonably well
known in the industry, but it should also be remembered that many are
prescribed by law, and that the statutory requirements vary in different
countries. Advice and guidance is available from the organisations
mentioned in Section 12.9.2. Relevant information may also be found
in the current editions of the following publications:
Industrial Hygiene and Toxicology. F. A. Patty (Ed.), Interscience

Publishers.
Encyclopaedia of Occupational Health and Safety. International
Labour Office, Geneva.
Health Hazards of the Human Environment. World Health Orga-
nisation.
Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley &
Sons (under 'Industrial Toxicology' and other relevant headings).
* However, two specific points may be made regarding PVC: under certain
conditions the presence of fine PVC resin dust can lower the explosive limit of
VCM/air mixtures; potentially ignitable levels of VCM may arise in high-speed
mixing equipment. Guidance on safety in the operation of high-speed mixers is
provided in a booklet published jointly by the British Plastics Federation and
Chemical Industries Association Ltd, 'Vinyl CWoride Monomer. Guide to the
High Speed Mixing of PVC Resins and Compounds'.
Dangerous Properties of Industrial Materials. N. I. Sax, Van

Nostrand Reinhold.
Fire Protection Handbook. G. H. Tryon (Ed.), National Fire
Protection Association, Boston, Mass., USA.
Publications of the American Conference of Governmental Industrial
Hygienists, Cincinnati, Ohio, USA, including (i) Documentation
for Threshold Limit Values for Substances in Workroom Air; (ii)
Industrial Ventilation: A Manual of Recommended Practice.
Relevant HMSO Publications, (UK).
12.10 BURNING BERAVIOUR
Virtually all plastics are combustible: that is they will-under suitable

conditions (e.g. in a sufficiently intense fire)-undergo exothermic
oxidative decomposition, accompanied by flame and/or glowing and/or
smoke evolution as its main visible manifestations. However, the
nature and severity of the conditions required for ignition and
sustained combustion are different for different plastics and, converse-
ly, the ignition and combustion behaviour will differ under identical
conditions: in both cases the differences are governed by differences in
chemical composition and physical state-e.g. a polystyrene film will
burn readily in circumstances in which a uPVC one will not; a uPVC
bar may have an oxygen index of 40 or only 25 depending on whether
it is solid or cellular, and so on. Thus meaningful comparisons can only
be made on the basis of tests relevant to the purpose of the comparison
and carried out under closely standardised conditions. Moreover,
because they are cardinally dependent upon the conditions, the results
of laboratory tests are strictly relative (as are any comparisons based
upon them) and should not be used as criteria for the prediction of the
degree of hazard in actual fire situations. Similarly, such apparently
definitive terms as 'self-extinguishing', 'non-flammable', 'flame-
resistant', 'slow-burning' can only have meaning in relation to a
specified set of conditions (e.g. a particular standard test). Even when
these principles are observed confusion can still occasionally arise
because the terminology of the burning behaviour of plastics is not
fully uniform: standardisation, and increasing awareness of the factors
and concepts involved, have done much to improve matters, but even
standard definitions of the same important term can still differ
considerably. For example, two sources of relevant standard defini-
502 W. V. Titow
tions, ISO 3261-1975 * and ASTM E 176-82, t define 'flammable',

respectively, as 'capable of undergoing combustion in the gaseous
phase with emission of light during or after application of an igniting
source' and 'subject to easy ignition and rapid flaming combustion'.
Note: Other publications containing relevant terminology are:
Addendum 2 (1983) to ISO 472, comprising definitions of
terms relating to burning behaviour of plastics; and Compila-
tion of ASTM Standard Definitions published by the American
Society for Testing and Materials. Certain terms are also
defined in some of the standard specifications listed in Table
12.12.
The burning behaviour of plastics is of great importance in many
applications, and hence of interest to the user and technologist alike.
The key aspects with which the practically oriented tests are concerned
are ignitability, spread of flame, rate of heat release, and amount of
smoke generated. The chemical composition of the smoke, whilst not
investigated in standard tests, is also important and has been receiving
increasing attention as a toxic hazard in fires. In addition, the
Fennimore-Martin 'Oxygen Index,88,89 (based on the minimum
concentration of oxygen required to support candle-like burning of a
standard size specimen in specified conditions) provides a useful means
of rating the flammability (in the sense of ease of ignition and burning)
of plastics and other materials. Some typical oxygen index values for
plastics, including PVC, are shown in Table 12.11. Standard burning
tests relevant to (including some specifically devised for) PVC
materials and products are listed in Table 12.12. A British standard
covering the development, presentation and use of fire tests is now
available. 91
The' flammability of PVC (resins and solid uPVC compositions) as
determined in standard tests is one of the lowest among those of the
common plastics. However, the smoke emission is relatively high, and
the smoke is irritant and toxic (see Section 12.9.3). The low
flammability is due to the large chlorine content: like the other
halogens (cf., for example, PTFE in Table 12.11) chlorine acts as a
retardant in the process of combustion (see Chapter 11, Section 11.5).
* 'Fire tests-Vocabulary'.
t 'Standard definitions of terms relating to fire tests of building construction
and materials'.
TABLE 12.11
Oxygen Index Values of Some Plastics Materialsa
Material Oxygen indexb

(typical or
representative value)
PVC resin (homopolymer) 45
uPVC compound (medium impact strength) 40
uPVC compound containing 15% glass fibre 40
PVC floor tile (asbestos-filled) 30
pPVC compounds 21-26
PVDC 60
PTFE 95
Polyamide (nylon 6.6) 23
Polycarbonate 23-27
Polymethyl methacrylate 17-18
Polyethylene 17-18
Polypropylene 17-18
Polypropylene with flame retardant 22
Polypropylene asbestos-filled 21
Polystyrene 18
uPVC foam 25
pPVC foam 22
Polystyrene foam 18
Polystyrene foam with flame retardant 24
Polyurethane foam 19
Polyurethane foam with flame retardant 22
Polyisocyanurate foam 26
aTable based on data from Refs 88, 92, 94 and 95.
b% Oxygen in the standard gas mixture, required to support candle-like
combustion of standard specimen in standard conditions (ASTM 2863).
The performance of PVC compositions in flammability tests falls with

decreasing chlorine content (see Fig. 12.7 here, and Fig. 6.3 in Chapter
6). This is the main reason for the well-known fact that plasticisation
increases flammability, albeit this effect is reduced where chlorinated
extenders or phosphate plasticisers are used, since the former
introduce their own chlorine, and the latter act as flame retardants in
their own right (see Chapter 11, Section 11.5; and Chapter 7, Section
7.6). An expression relating the halogen content of a polymer to its
carbon and hydrogen contents, known as the van Krevelen Composi-
tion Parameter, has been found to correlate well with the oxygen index
for many polymers, including polyvinyl chloride. 92 The flammability of
VI
TABLE 12.12 ~
Standard Burning Tests Relevant to PVC Materials
Material Property or Standard Remarks
or product characteristic determined specifications
Plastics: rigid sheet or Incandescence resistance (be- l. ISO 181-1981 All four specifications closely similar
moulding haviour during and after con- 2. BS 2782: 1970 technically (employ the 'Schramm!
tact with incandescent bar at Method 508E Zebrowski' method)
950°C) 3. ASTM D 757-77
4. DIN 53459-1975 1. and 2. Intended for
thermosetting plastics
3. Recommended for materials
which are self-extinguishing
in the test of ASTM D 635 ~
(see below) ~
Plastics: pellets; sheet Ignition properties 1. ISO 871-1980 1. and 2. technically :::'1
is
or film 2. ASTM D 1929-77 equivalent: self-ignition and ;;
flash-ignition temperatures
determined (in a hot-air
ignition furnace)
Plastics: rigid (self- Flammability 1. ISO 1210-1982
supporting) sheet or 2. BS 2782: 1970
moulding Method 508D
Burning time and/or rate and/ 1. BS 2782:1970: 1. Bar specimen held
or extent Method 508A horizontally
2. BS 2782:1970: 2. Relates specifically to
Method 508B PVC compounds
3. ASTM D 635-81 3. Bar specimen held
horizontally
4. UL subject 94 4. and 5. Closely similar;
Parts A & B vertical bar specimens
5. IBM CMH 6-0430- ignited at lower end;
102 effect of dripping .....
N
(ignition of cotton by
flaming drops) taken into .g~
account; tests more
severe than 1 and 2 ~.
Plastics: film or thin Flammability and/or burning 1. ISO/R 1326-1970 ~
sheet rate, and/or extent of bum 2. BS 2782:1970: 2. Relates specifically to ~
Method 508Ca thin flexible PVC sheeting ~
3. ASTM D 568-77 3. Vertically suspended strip §.:
specimen: test results S'
sensitive to thickness
4. ASTM D 1433-77 4. Strip specimen supported ~
S'
on 45° incline "l:I
Plastics: solid or cellular Oxygen index 1. ISO 4589-1985 r3
(applicable also to 2. BS 2782:Part 1: 2. Restricted to solid ~
non-plastics materials Methods 141 A to (non-cellular) specimens
e.g. wood) C: 1978 NB Method D for electric cable in- ~.
l:;'"
3. ASTM D 2863-77 sulation or sheathing-see below
;::
'"
Smoke generation ASTM D 2843-77 Employing the XP2 smoke chamber "'-
Plastics: cellular Horizontal burning character- BS 4735:1974 ~
istics ~
Smoke generation BS 5111:Part 1:1974 1:;
Vertical burning characteris- ASTM D 3014-76 The 'Butler Chimney' test

tics (flame height, burning
time, mass loss)
2S
lJl
Vl
~
TABLE 12. 12-contd.
Material Property or Standard Remarks

or product characteristic determined specifications
Electrical insulation and Oxygen index BS 2782:Part 1:

cable sheathing (main- Method 141D:1978
ly plastics) Ignition and/or spread of 1. BS 4066:1969 1. Agrees with lEC 332
flame and/or rate and extent (vertical specimen)
of burning 2. ASTM D 299-82 2. Test for rigid sheet and
plate insulation materials
~
3. ASTM D 876-80 3. Test for non-rigid PVC
:0::::
tubing used for electrical
insulation :::J
c;
;e
Building materials (in- Combustibility ISO 1182-1979 Test for duration of sustained
cluding plastics) flaming
Various combustion charac- 1. ISOrrR 3814-1975 1. Report on tests being
teristics (including smoke developed
generation in some cases) 2. BS 476 2. A multi-part specification
'Fire tests on building
materials and structures'
3. ASTM E 84-81 3. 'Underwriters tunnel furnace
test'. 25 ft specimens
4. ASTM E 286-69(1975) 4. The '8 foot tunnel' test
5. DIN 4102 5. A multi-part specification
'Behaviour of building
materials and components
in fire'
Coated fabrics Duration of flaming and 1. BS 3424:1973: 1. Vertical strip specimen
afterglow, and/or length of Method 17
char (or melt), and/or flam- 2. BS 5790:1979 2. Specification for upholstery
ing drips fabrics, including PVC-
coated woven and knitted .....
N
fabrics: flammability
tests by the Method of 1. ~
3. ASTM D 2859-76 3. Flammability of textile ~
~
floor coverings (relevant ~.
to PVC-backed carpets)
4. DIN 54332-1975 ~
4. Burning behaviour of
textile floor coverings ~
'Materials' (some rele- Various combustion charac- 1. ASTM E 162-81 1. Test with radiant energy
[
vance to plastics) teristics source: 'flame spread ;;-
index' and smoke ~
evolution measured ~
2. DIN 53 438-1977
s·
"ll
Interior materials for Burning rate and extin- ISO 3795-1976 Requirements stated in terms of ~
motor vehicles (includ- guishing characteristics (based on US Federal rate of burning; specification much
ing PVC upholstery Motor Vehicle Safety used for PVC upholstery fabrics
~
~
and mouldings) Standard 302) 5'
l:;-
I:>
a Now superseded by BS 2782:Part 1: Method 140 D:1980. ;::
I:l..
~
~
Vl
~
508 W. V. Titow
45
40
25
0·3 004 0-5 0·6

el, wt fraction
Fig. 12.7 Oxygen index (01) of a PVC composition as a function of its

chlorine content (fraction by weight of the total composition). Formulation of
PVC composition:
PVC resin 100
Plasticiser (DOP) 0-90 phr, as shown
White lead 7 phr
Ca stearate O· 75 phr
A, DOP 90 phr; all additives 97·75 phr; CI content 0·287;
B, DOP 60 phr; all additives 67·75 phr; CI content 0·339;
C, DOP 40 phr; all additives 47·75 phr; CI content 0·384;
D, DOP 20 phr; all additives 27·75 phr; CI content 0·445;
E, DOP 0; all additives 7·75 phr; CI content 0·527;
F, PVC resin alone; CI content 0·568.
a PVC composition may be reduced, despite a reduction in the overall

chlorine content, through the incorporation of a non-combustible filler
(e.g. asbestos fibre), a flame-retardant compound, or a smoke
suppressant. The latter two types of additive and their effects are
discussed in Section 11.5 of Chapter 11.
Much useful information (including an extensive list of literature
references) on all aspects of combustion of polymers is contained in a
recent book by Cullis and Hirschler. 93 A comprehensive (10-volume)
report * by the National Materials Advisory Board of the USA

Academy of Sciences is an important source of reference on subjects
falling within the ambit of its title. A list of flammability test methods
for plastics (containing national standard tests of 18 countries, as well
as some ISO standards and those of the Underwriters Laboratory,
NCB) has been published by the Chemical Industries Association Ltd,
London.
Some data on the evolution of HCI and smoke from PVC (burnt
with wooden cribs) are given by Edgerley and Pettett. 84
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5. Williams, J. G. (1975). 'The fracture mechanics of polymers', Ibid. Paper
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6. Titow, W. V. (1977). In Developments in PVC Production and
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7. Reymers, H. (1970). Mod. Plast., September, 78-80.
8. Titow, W. V. Unpublished work.
9. Wilson, A. S., Biggin, I. S. and Pugh, D. M. (1978). 'The influence of
volatility on the selection of plasticisers to meet new and developing
performance requirements', paper presented at the PRI International
Conference on PVC Processing, Egham Hill, Surrey, England, 6-7 April,
1978.
10. Ranney, M. W. (1975). Irradiation in Chemical Processes: Recent
Developments, Noyes Data Corp.
11. Scalco, E. and Moore, W. F. (1983). Radiat. Phys. Chern., 21(4),389-96.
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15. Meares, P. (1965). Polymers: Structure and Bulk Properties, Van Nostrand,
London, p. 316.
16. Meares, P. (1958). J. Polym. Sci., 27, 391-404.
17. Meares, P. (1966). Eur. Polym. J., 2,95-106.
* 'Fire Safety Aspects of Polymeric Materials' (1979).

510 w. V. Titow
18. Crank, J. and Park, G. S. (Eds) (1968). Diffusion in Polymers, Academic

Press, London.
19. Stafford, G. D. and Braden, M. (1968). J. Dent. Res., 47(2), 341.
20. Carman, P. C. (1956). Flow of Gases Through Porous Media, Butter-
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21. Scheidegger, A. E. (1974). The Physics of Flow Through Porous Media,
3rd Edn, University of Toronto Press, Toronto.
22. Rodebush, W. H. and Langmuir, I. (1942). 'Smokes and filters', US
OSRD Report No. 865.
23. Davies, C. N. (1948). 'Fibrous filters for dust and smoke', Proc. of the IX
International Congress on Industrial Medicine, London, 13-17 Sept., John
Wright and Sons Ltd, Bristol.
24. Iberall, A. S. (1950). J. Res. Nat. Bur. Stds, 45, 398-406.
25. Thomas, D. J. (1952). J. Inst. Heatin!{ Ventilating Engrs. 20(201), 35-70.
26. Hopfenberg, H. B. (Ed.) (1974). Permeability of Plastics Films and
Coatings, Plenum Press, New York.
27. Lebovits, A. (1966). Mod. Plast., 43 (March), 139-46, 150, 194-213.
28. Hennessy, B. J., Mead, J. A. and Stenning, T. C. (1966). The Permeability
of Plastics Films, Plastics Institute.
29. Pye, D. G., Hoehn, H. H. and Panar, M. (1976). J. Appl. Polym. Sci.,
20(7), 1921-31.
30. Salame, M. and Pinsky, J. (1962). Mod. Packag., (September) pp.
153-223.
31. Wilson, G. A. R. (1965). Plastics, (May), pp. 86-115.
32. Brydson, J. A. (1961). Plastics, (December), pp. 107-10.
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35. Kambour, R. P. (1968). Polym. Engng. Sci., 8(4),281-5.
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37. Ziegler, E. E. (1954). SPE J., 10(4),13-16.
38. Dempsey, L. T. (1967). Polym. Engng. Sci., 7(2),86.
39. Titow, W. V. (1975). Plast. Polym., 43(165),98-101.
40. Faulkner, P. G. and Atkinson, J. R. (1972). Plast. Polym., 40(147),
109-117.
41. Wolf, J. (1967). Gas, 87 (November), 433.
42. Szabo, E. and Lally, R. E. (1975). Polym. Engng. Sci., 15(4),277-84.
43. Caryl, C. R. and Helmick, W. E., US Patent No.2 945 417: Apparatus
and Mechanism for Concentration of Solar Rays on Objects to be Tested,
19th July, 1960.
44. Ives, G. c., Mead, J. A. and Riley, M. M. (1971). Handbook of Plastics
Test Methods, Iliffe Books, London.
45. Caryl, C. R. (1967). SPE J., 23(1),49.
46. Kuist, C. H. and Maxim, L. D. (1968). SPE J., 24(7), 46-51.
47. Grossman, G. W. (1977). J. Coatings Technol., 49(633),45-54.
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49. Summers, J. W. (1976). 34th ANTEC SPE Proceedings, pp. 333-5.

50. Kinmonth, R. A., Jr (1964). SPE Trans., 4(3),229-335.
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53. Wypych, J. (1976). Ibid, 20(2),557.
54. De Coste, J. B. and Hansen, R. H. (1962). SPE J., 18(4), 431-9.
55. Rabek, J. F., Shur, Y. J. and Ranby, B. (1975), J. Polym. Sci. Polym.
Chern. Ed., 13(6), 1285-95.
56. Anon. (1979). Eur. Plast. News, 6(3), 40.
57. Katz, M., Shkolnik, S. and Ron, I. (1976). 34th ANTEC SPE Proceedings,
p.511.
58. Allara, D. L., Ibid, p. 245.
59. Scullin, J. P., Girard, T. A. and Koda, C. F. (1965). Rubb. Plast. Age,
46(3), 267-8.
60. Sahajpal, V. K. (1978). 'PVC compounding for low organoleptics and
controlled bacteriological growth', paper presented at the PRI Internation-
al Conference on PVC Processing, Egham Hill, Surrey, England, 6-7
April, 1978.
61. Mascia, L. (1974). The Role of Additives in Plastics, Edward Arnold,
London.
62. De Coste, J. B. (1968). Ind. Eng. Chern., 7(4), 238-47.
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Engng. Sci., 10(4),241-6.
64. Wessel, C. J. (1964). SPE Trans., 4(3), 193-207.
65. Anon. (1965). Mod. Plast., 42(5), 168.
66. McGinty, L. (1979). New Scientist, 183 (9th Aug.), (1167), 433.
67. Socrates, G. (1979). Plast. Rubb. Wkly, (9th March), p. 10.
68. Anon. (1975). Ibid, (21st February) p. 70.
69. Anon. (1974). Chern. Engng. News, (16th December), pp. 24-5.
70. Draft German Standard DIN 53743-1977. Testing of plastics:
Gas-chromatographic determination of vinyl chloride (VC) in polyvinyl
chloride (PVC).
71. Anon. (1979). Plast. Technol., 25(9), 13.
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Health Precautions', Temporary Format (February 1975).
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Processing-I, (Eds A. Whelan and J. L. Craft), Applied Science
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512 W. V. Titow
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CHAPTER 12

Miscellaneous Properties ofSpecial Interest

All properties of a PVC material depend, in a more or less complex

12.2 LOW-TEMPERATURE PROPERTIES

W. V. Titow, PVC Technology

temperatures. It is necessary, therefore, that their properties should

ASTM D 759-66 (Re-approved 1976): Conducting physical property

ASTM D 746-79: Brittleness temperature of plastics and elastomers

The method of this standard is technically similar to that of ISO/R

BS 2782:Part 1: Method 150 D:1976: Cold crack temperature of film

ASTM D 1790-62 (Re-approved 1976): Brittleness temperature of

ASTM D 3029-78: Impact resistance of rigid plastic sheeting or parts

The main effects of cooling of flexible PVC are stiffening, hardening,

It is clearly important to have tests available, the results of which can

12.2.1 Cold Flex Temperature (Clash and Berg)

This is the lowest temperature at which a standard strip specimen can

12.2.2 Cold Bend Temperature

This is determined by the method of BS 2782:Part 1: Method

12.2.3 Low-Temperature Extensibility of Flexible PVC Sheet

U.3 HEAT RESISTANCE

This section is concerned with heat resistance of PVC materials and

Fig. 12.1 'Percentage retention' of selected property as a function of heating

'percentage retention' (i.e. the value after a given heating time as a

Reciprocal of absolute temperature, 11K

Fig. 12.2 Time to reduce percentage retention of selected property to 60%,

Methods of this type are used in deriving the 'temperature index'

ISO I137-I975. * Plastics-Methods of test for the determination of

ASTM D 2115-67 (Re-approved 1980): Standard recommended

ASTM D 3045-79: Standard recommended practice for heat ageing

It may be noted in passing that some mechanical properties of

The performance of pPVC sheets, films and fabric coatings in tests

where: L is the volatile loss; n is the thickness of the PVC sheet or

* See Appendix 1, Section 4.2.

covered by the tests must be ascribed to experimental error (or some

(i.e. up to about 40% volatile loss from this particular composition-

* Verband Deutscher Elektrotechniker (specification of the German Electrical

Fig. 12.4 Effect of temperature on tensile strength and BS softness number of

Fig. 12.5 Permeability of a uPVC (homopolymer) film to water vapour as a

Fig. 12.6 Effect of fibrous reinforcement on the temperature dependence of

In the broadest sense permeability may be thought of as the ease (or

* Du Pont trade name for a group of modified ethylene/vinyl acetate

tions of PVC are films (e.g. packaging films, rainwear, inflatables),

The results of such determinations can normally be interpreted in

also because the distribution of the various additives in the polymer

where P is the permeability coefficient (as in eqn (2)), D the diffusion

Penetrant Plastics Index of permeability Data required Relevant determination

Any Walls of Permeability (J.L)/A p1 g.cm Temperature ASTM D 2684-73

a Fixed in terms of the RH in standard determinations.

b cm 2 Pressure" cmHg b cm 3 (cm Hg) cm 2 s (cm Hg)-l

Water g (24 h)-I m2 Pressure" mmHg cm g (mm Hg) g cm (24 h)-I ~

coefficient (assumed to be constant or dependent only on concentra-

mechanism will be 'straight' diffusion, or movement under a

J/A = K[~p/(L1])] (4)

where 1] is the viscosity of the penetrant, K is the permeability

and Thomas 25 may be referred to for further information on flow of

concept, first developed-largely on an empirical basis-in the 1950s in

Permeability to other penetrants depends strongly on their chemical

made. Other things being equal, PVC compositIOns based on

a Units: cm 3 (at STP).cm.cm- 2 .s- I.(cm Hg)-I.

for comparable uPVC compounds.

may have no effect on permeability, or it may reduce or increase it,

12.5 ENVIRONMENTAL STRESS CRACKING AND

Plasticised PVC is not normally susceptible to failure of this kind.

Cracking is a type of complete, local brittle failure. The term 'crack'