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CHAPTER 11

Some Miscellaneous Components of pvc


Formulations
W. V. TITaw

The major constituents of PVC compositions have been discussed in


some detail in the previous chapters. Others, which may be regarded
as relatively minor but common, and in some cases essential,
formulation components, are dealt with in this chapter, viz. lubri-
cants, polymeric modifiers, colourants, antistatic agents, flame and
smoke retardants. Still other miscellaneous minor additives, some of
which were first mentioned in Chapter 4, are further considered in
other relevant chapters and sections of the book (e.g. blowing agents
in Chapter 25, antioxidants and UV absorbers in Chapter 9, thickening
agents for plastisols in Chapter 21, etc.).

11.1 LUBRICANTS

11.1.1 Functions, Nature and Effects

Lubricants are essentially processing additives-their primary role is to


influence some aspects of behaviour of PVC compositions under the
heat and shear experienced in the processing machinery, so that the
processing is made easier, whilst certain factors promoting thermal
degradation of the polymer are counteracted (see below). For
example, in the extrusion of a rigid PVC composition effective
lubrication can increase output for a given heat and power consump-
tion, or reduce the heating and mechanical power required for a given
output rate. As constituents of a PVC composition, lubricants can also
influence some material properties. for example the thermal stability
359

W. V. Titow, PVC Technology


© Elsevier Applied Science Publishers Ltd 1984
360 w. V. Titow

(either directly or through interaction with other components of the


formulation-see below), impact strength of uPVC, printability (which
may be impaired by the presence of a lubricant). The lubricating action
and effects can be divided into external and internal, but a
corresponding division of the lubricants themselves is not strictly
applicable as a firm classification, since some combine both functions in
varying degrees, and also because other additives in a PVC
composition can have lubricant effects, as well as-in some cases-
strongly affecting the performance of (and requirements for) the
lubricants proper. 1
The principal external lubrication effect is reduction of friction and
adhesion between the hot PVC composition and the working surfaces
of processing machinery and moulds by the presence of the lubricant at
the interface: this makes movement of the composition through the
machinery easier, and prevents deposition of layers of PVC on the hot
metal surfaces.
Note: Avoidance of stagnant deposits is important in PVC process-
ing, as the polymer in them soon undergoes thermal
decomposition, becoming a source of contamination for, and
promoting further degradation in, the rest of the hot stock.
The basic internal lubrication effect is the lowering of internal (i.e.
inter-particle and inter-molecular) friction in the composition through-
out processing, which reduces the effective melt viscosity and
frictional heat build-up under shear.
An additive, especially one of relatively low molecular weight, which
is dispersible in PVC on a molecular level (i.e. capable of 'dissolving'
in the PVC resin) may be expected to have some lubricating action. If
the additive is fully compatible with the PVC composition when
present in the amount appropriate to its purpose in the formulation
(say, for example, 80 phr of a primary plasticiser) then its lubricant
action will be of the internal type.
Note: Those polymeric processing aids and impact modifiers used in
PVC that do not lower (and in fact often raise) the melt
viscosity may be regarded as an exception: their compatibility
and relatively high molecular weight are factors in this
behaviour. It may also be noted that poly-a-methylstyrene (a
polmeric processing aid) and polymeric plasticisers do have an
internal lubricant action in that they lower the melt viscosity
of PVC compositions.
11 Some Miscellaneous Components of pvc Formulations 361

If the compatibility of such an additive is limited in the circum-


stances just mentioned, then it will have an external lubricant effect
(which may be combined with a degree of internal lubrication),
providing that its relevant chemical and physical properties make it an
effective 'slip agent' at the hot metal/PVC interface.
In broad terms, the compatibility of the common additives capable
of lubricant action, and their usual level of addition in PVC
compositions, decrease in the sequence:
primary plasticisers > secondary plasticisers and extenders >
impact modifiers* and processing aidst > stabilisers and
lubricants:j:
Thus the main operative features of additives incorporated specifically
as lubricants are:
(i) generally low compatibility with PVC (lowest for external
lubricants) ;
(ii) chemical nature enabling the lubricant effects to be exerted in
significant measure at the low level of addition (between O· 2 and
about 3·0 phr for the total lubricant system, usually comprising
more than one lubricant).
Since the mode of a lubricant's action (internal or external) is closely
associated with its compatibility with PVC, several studies have been
made of the degree of compatibility of lubricants, measured in terms of
some relevant property of the lubricated PVC composition, with a view
to classifying the lubricants and/or predicting their suitability in
practical applications. 2 The properties measured included the amount
of haze introduced by the additive into a clear PVC compound3 (haze
being a manifestation of incomplete compatibility), and the reduction
of the glass transition temperature (Tg ) caused by its incorporation 4
(lowest Tg with the most highly compatible lubricant). The effect of
lubricants on the fusion behaviour of a PVC composition in a

*Some impact modifiers (e.g. extensively chlorinated polyethylene; nitrile


rubber; VC/EVA graft polymers) are highly compatible with PVC polymer-
see Section 11.2.
t Some processing aids are occasionally used in high proportions to increase
the resistance of PVC to deformation at elevated temperatures-see Section

*
11.2.
Lubricants with internal lubricant action are more compatible with PVC
polymer than typically external lubricants.
362 W. V. Titow

rheometer or an extruder has also been used as the criterion of the


type of lubricant action. In terms of behaviour under suitably
standardised mixing conditions in a torque rheometer the most
characteristic effects are:
Typical external lubrication: Fusion time (i.e. time to reach peak
torque-see also Section 11.1.3 below) substantially increased;5--7
torque value may be reduced (because of decrease in external
friction); NB in an extruder, increase of fusion time and torque
reduction are accompanied by a drop in back pressure.
Typical internal lubrication: Torque significantly reduced (in
consequence of drop in melt viscosity); little or no effect on fusion
time.
However, the effects of an external lubricant on the torque rheometer
fusion times of PVC compositions do not always correlate with the
corresponding melting rates in an extruder, 7 although limited predic-
tion of extrusion characteristics may be possible from plots of
rheometer fusion time against mixing head temperature. 8
An increase of melt flow velocity at the wall face of an extruder die
(slip effect) was observed directly by Chauffoureaux and co-workers9
in the case of a PVC compound containing a lubricant with effective
external action: this effect was absent when the lubricant used was one
with a typically internal behaviour. Various studies directed to
characterising and classifying lubricant effects have been briefly
reviewed by Gale,? and by Logan and Chung. lO
The chemical structure of the lubricant is both the prime factor in its
compatibility with PVC and the link between compatibility and the
mode of lubricant action. Results of experimental studies in this area,
and in particular those of the authoritative work of Illmann l l are
consistent with the theoretical expectation that the molecular size
(chain length) and polarity (nature and number of polar functional
groups) of a lubricant are the main factors determining the compatibil-
ity and lubricant behaviour: broadly speaking, short chain length and
high polarity make for good compatibility and internal lubrication,
whereas relatively long-chain compounds (even with some polar
groups) tend to be poorly compatible and act as external lubricants.
The types of chemical compound used as lubricants in PVC are shown
in Table 11.1: among those, typical examples of low compatibility and
external lubrication effects are provided by, say, the polyethylene
waxes and calcium stearate, whilst relatively high compatibility and
11 Some Miscellaneous Components of pvc Formulations 363

TABLE 11.1
Compounds Used as Lubricants2,4,9
General type Class of compound Examples
Hydrocarbons Natural hydrocarbons Paraffins, paraffin oils
Synthetic hydrocarbons Synthetic paraffins, low
molecular weight
polyethylene

Hydrocarbon Fatty acids Stearic acid


derivatives Fatty alcohols Cetyl, stearyl, octadecyl

Derivatives Metal salts (soaps) Stearates of barium, calcium,


of organic aluminium, and lead
acids
Amides Stearamide
Esters and partial Butyl stearate, glycerol
esters monostearate, glycerol
monoricinoleate;
Wax esters Stearyl esters, montan acid
esters

associated internal lubricant action are exemplified by the partial esters


of glycerol.
Whereas rigid PVC compositions normally require both internal and
external lubricants (unless lubricating stabilisers and/or processing aids
are used-see below) only external lubricants will usually be
considered for flexible compositions, as in those the plasticiser will
provide internal lubrication (some external lubrication may also be
supplied by plasticiser extenders if present). However, an external
lubricant may be useful, or necessary, even in such heavily plasticised
compositions as certain plastisols, especially for intricate mouldings. 2
Because of the need to achieve the right measure of internal and
external lubrication, and to balance-in the particular, individual
composition-the effects of the lubricants with those of the other
additives present, more than one lubricant (i.e. a lubricant system) is
normally employed in rigid PVC formulations (where up to four
lubricants may be combined in some cases) and sometimes also in
pPVC. The mutual effects and interactions of the lubricants with the
other formulation components are important considerations, affecting
both the choice of the lubricant system and the design of the
formulation as a whole.
364 w. V. Titow

11.1.2 Interaction and Co-action of Lubricants with Other PVC


Formulation Components

(a) Lubricant/Stabiliser effects

STABILISING EFFECfS OF LUBRICANTS

Direct stabilising action: Most lubricants of the metal soap type (see
Table 11.1) have some stabilising effect, and some can act as stabilisers
in their own right, albeit their action in this role is not as strong as that
of the more powerful 'primary' stabilisers. Thus certain metal soap
lubricants (e.g. calcium stearate) can be used in either capacity in PVC
formulations (but when employed as the sole stabiliser, a relatively
large amount will be needed to provide a reasonable measure of
long-term stability, and the overall stabilisation will not be as good as
that conferred by a smaller proportion of a strong primary stabiliser).
Lead stearate and dibasic lead stearate are widely used as lubricating
components of lead stabiliser systems.

Synergistic action with stabilisers: Some lubricants can enhance the


effectivity of some stabilisers by a synergistic effect. The synergistic
lubricants are of the internal kind (i.e. comparatively highly compati-
ble with PVC) and usually contain reactive functional groups (in
particular hydroxyl) in the molecule. Typical examples are partial
esters of glycerol with relatively long-chain saturated or unsaturated
aliphatic acids. In those compositions where it occurs, the synergistic
effect depends, in a complex way, on several factors, including the
PVC resin (type and grade), the nature and amount(s) of stabiliser(s)
in the stabiliser system, and the amount of the synergistic lubricant
present. The stabiliser systems which benefit from the effects of
lubricant synergists are those based on sulphur-containing tin com-
pounds (thiotin or tin mercaptide stabilisers) or on lead compounds. In
rigid compositions incorporating calcium stearate as the sole heat
stabiliser (e.g. in some pipe compounds for potable water in Europe)
most lubricants, whether synergistic or 'neutral' in their effects with
other stabiliser systems, can produce some stability improvement. 12
Calcium stearate used as a lubricant synergistically improves heat
stabilisation by antimony mercaptide stabilisers. 13 With BalCd,
Ba/Cd/Zn, CalZn and Ca/Mg/Zn stabiliser systems synergistic effects
are important, but they are provided by epoxy-compound co-
11 Some Miscellaneous Components of pvc Formulations 365

stabilisers, usually in conjunction with an organic phosphite (see


Chapters 4, 9 and 10), and the lubricants used do not make any
significant contribution in this respect. Improvements in heat stability
(mainly long-term) of compositions stabilised with sulphur-containing
tin compounds (e.g. rigid films, calendered or extruded) can be
promoted by the use, as lubricants, of glycerol partial esters (liquid
versions, e.g. glycerol monoricinoleate, are necessary for transparency).
Lubricants of this kind also enhance the stability of compositions
containing lead stabiliser systems (but discoloration can arise,
especially on outdoor exposure, with such inorganic lead stabilisers as
lead phosphite or sulphate*) Pentaerythritollfatty acid partial ester
lubricants can be particularly effective in synergistically enhancing the
long- and short-term stability of lead-stabilised rigid PVC composi-
tions, allowing significant reductions in the amount of stabiliser
necessary in many cases. 12 Negative effects can also arise: for example,
the presence of glycerol partial ester lubricants can reduce the thermal
stability of compositions stabilised with sulphur-free tin stabilisers
(whilst very good stability may be maintained if the lubricant is an
ester of a monohydric alcohol and long-chain fatty acid-e.g. butyl
stearate).
Note: On the other hand, the heat stability of uPVC (dry blend)
compositions stabilised with a butyl thiotin stabiliser can be
impaired if cadmium stearate is included in the lubricant
system. 8
Indirect stabilising action: In discharging their primary functions, the
lubricants also affect the thermal stability of a PVC composition. By
lowering frictional heat build-up (through both internal and external
lubrication) and melt viscosity, and hence the effective processing
temperature, as well as limiting direct contact between the stock arid
hot metal surfaces whilst simultaneously preventing the formation of
stagnant deposits (through external lubricant action), lubricants reduce
the scope for immediate thermal degradation of the PVC in processing
and limit its 'heat history': the first of these two general effects is
equivalent to improving short-term thermal stability, and the second a
factor enhancing the long-term stability of the composition. 5 ,8 The use

* This is attributable to a reaction of these compounds, in the presence of light,


with free glycerol often contained in residual amounts in commercial glycerol
esters. 12
366 W. V. Titow

of an effective lubricant system can thus reduce the demands on the


stabiliser(s).

LUBRICANT ACTION OF STABILISERS


Several stabilisers have some lubricating action (usually mainly of the
external kind). This is greatest with some metal stearates: as indicated
above, certain compounds in this group (e.g. calcium and lead
stearates) may be regarded as lubricants with stabilising properties (see
also Chapters 9 and 10). Some tin stabilisers also exert lubricant effects
(e.g. dibutyltin dilaurate), as do Ba/Cd soap complex stabilisers.
Compositions containing such stabilisers will require less lubricant(s)
overall (none in some cases) and/or a different balance of the lubricant
system.

(b) Mutual Effects of Lubricants and Plasticisers

PRIMARY PLASTICISERS
The internal lubricating action of primary plasticisers has been men-
tioned (see Section 11.1.1 above): this makes the addition of internal
lubricants to plasticised compositions unnecessary in most cases.
However, if the external lubricant used is highly compatible with the
plasticiser(s), its lubricating action in the composition will normally be
reduced, necessitating an increase in the level of addition.

SECONDARY PLASTICISERS AND EXTENDERS


Some of these may exert external as well as internal lubricant effects.
However, the extent (or even the occurrence) of external lubrication
will depend on the nature (and given that, the amount) of the
plasticiser(s) or extender(s) present, and to some extent also on the
process. For example, in calendering compositions many polymeric
plasticisers, even when used near the compatibility limit, provide no
external lubrication so that external lubricants are required to
counteract 'stickiness' in processing: on the other hand, in some
compositions containing a chlorinated-paraffin extender this additive
can provide both internal and external lubrication in sufficient degree.

(c) Effects of Polymeric Modifiers (see also Section 11.2)


The polymeric additives incorporated in a PVC composition, in
relatively minor proportions, as impact modifiers or processing aids,
can, in any individual case, affect the total lubricant requirement
11 Some Miscellaneous Components of pvc Formulations 367

and/or that for the internaVexternal lubricant balance in a composite


lubricant system, if their own compatibility with the lubricant(s)
influences the latter's compatibility with the composition as a whole,
or-as, for example, in the case of some processing aids (see
below)-because of direct lubricant action.

PROCESSING AIDS
Many of these have no lubricant effect, internal or external, in that
they do not reduce the melt viscosity or the external friction and
'sticking' tendency of a PVC composition. However, some acrylic-
based lubricating processing aids with pronounced external lubricant
action are available,14 and poly-a--methylstyrene (of the relatively low
molecular weight grade used as a processing aid) lowers the melt
viscosity of PVC compositions (i.e. has an internal lubricant effect).15

IMPACf MODIFIERS
Most ABS and MBS modifiers have no lubricant action. With those
highly compatible modifiers which may be incorporated in large
proportions to act as permanent plasticisers (nitrile rubber, chlorinated
polyethylene of high chlorine content, VClEVA graft copolymers)
lubricant effects may arise. The presence of some impact modifiers
increases the compatibility of external lubricants with the composition,
so that the external lubricant has to be carefully selected (and a
relatively high amount may have to be used) for optimum results.

(d) Effects of Fillers and Pigments


Fillers and pigments (especially fine-particle grades) can bind lubri-
cants by absorption (ct. plasticiser demand-Chapters 4 and 8) so that
their presence in a PVC (especially uPVC) composition can increase
the lubricant requirement. However, this effect may be reversed-at
least with regard to external lubrication-if the filler carries a stearate
coating (see Chapter 8) as this can not only block absorption of
lubricants at the particle surface, but also actually provide additional
lubrication.

11.1.3 Assessment of Lubricant Effects

Reference has already been made in Section 11.1.1 to the evaluation of


the effects of lubricants in PVC compositions with the aid of a torque
rheometer or in an extruder; capillary rheometers are also sometimes
368 W. V. Titow

employed. The torque rheometer is widely used for this purpose (as
indeed, in general, for practically oriented studies of melt-processing
characteristics of PVC compositions): very popular and well-known
commercial equipment of this kind is the Brabender Plasti-Corder. * In
essence this consists of a thermostatically heated mixing chamber
housing two rotors mounted in a measuring head and driven by a
variable speed motor. The equipment is instrumented for continuous
measurement of the torque on the rotors (which is a function of the
resistance of the PVC composition to the mixing action) and the mix
temperature. A plot of torque against mixing time typically shows a
rise of the torque as the mix is fluxed, and something of a drop when
the fusion point is reached (see Fig. 11.1): the 'fusion time' taken to
reach this point is increased by external lubrication; the torque value
can also reflect lubricant effects. A standard method for carrying out

CJl~
:J

f-
L.

~ ~ - ~-
~ B
- - - - - ----=-=_::"':_=-=_:":_==--=-=-=-=-=_:-

Time

Fig. 11.1 Schematic representation of a 'plastogram' recorded on a


Plasti-Corder chart for a uPVC composition. A, Torque (Nm); B, mix
temperature (0C); C, mixer temperature (0C).

* Marketed by C. W. Brabender Instruments Inc. (in North America),


Brabender OHG (in West Germany), and agents in most countries. The
Plasti-Corder is a larger, more sophisticated version of the original Brabender
Plastograph. Several models are available, with torque ratings between 100 and
400 Nm and different maximum rotor speeds.
11 Some Miscellaneous Components of pvc Formulations 369

this kind of fusion test is given in ASTM D 2538-79 (see Appendix 1,


Section 2.12). For determinations relevant to extrusion characteristics
of a PVC composition extrusion heads can be fitted to the
Plasti-Corder. 16 The RAPRA torque rheometer* is another well-
known instrument of the internal mixer type.
Determinations of melt viscosity (in many cases the value deter-
mined will be the apparent viscosity, if the melt behaves as a
non-Newtonian fluid) in capillary or, generally, tubular die rheometers
may be used to follow the reduction in viscosity brought about by
internal lubrication. A standard method, employing a piston plasto-
meter, is given in ASTM D 3364-74 (1979) (see Appendix 1, Section
3.1(d»; this can be useful for direct comparison of internal lubricant
effects in the same composition (or two closely similar compositions)
but correlation with processing practice may be variable, inter alia
because the shear rates imposed by the processing equipment can be
different (higher) than those in the plastometer, and the effects of melt
elasticity can affect the behaviour differently.
Highly sophisticated equipment has been described by Chauf-
oureaux and co-workers,9 not only capable of demonstrating the
overall effects of lubricants (as well as other constituents) on the
rheology of a PVC composition, but also providing data indicative of
the mechanisms of lubricant action.
The concept of 'lubricant value' (LV) has been put forward 17 as a
means of comparing-in a general, approximate way-the effectivity of
different lubricants and lubricant systems, including the stabiliser/
lubricant combinations formulated for use in particular applications.
To calculate the LV, appropriate data from standard determinations in
a Brabender Plasti-Corder are used in the formula:
LV = (lOOOE)/(T. md)
where: E is the total weight of lubricant additive (phr); T is the stock
temperature in the mixing compartment (0C); and md is the torque
(kgfm).
As can be seen, the LV is highest for the most effective lubricants.
The LV values of many lead-based stabiliser systems (Biiropan SMS
stabilisers-Otto Barlocher GmbH) were found 17 to lie between about
6 and 14.
Various laboratory methods of assessment of lubricants have their

* Developed in the UK by the Rubber & Plastics Research Association.


370 W. V. Titow

place in more fundamental studies as well as in the preliminary


selection and comparison for the purposes of practical formulation of
PVC compositions. In the latter case, however, actual processing trials
should always be conducted. Much of the development work on
lubricant systems for various types of compositions and processes is
done by suppliers of lubricants (and stabiliser suppliers, since
combined stabiliser/lubricant 'one-pack' systems properly formulated
can offer the advantages of optimum compatibility, component balance
and synergistic effects). A further extension of the one-pack concept is
the inclusion of other additives with the stabiliser/lubricant system, so
that the total additive content is tailored for particular requirements.
The advantages and limitations of this approach are mentioned in
Chapters 9 and 10. Another recent, interesting, line of development
has been the introduction of lubricant concentrates in PVC, in the
form of PVC particles heavily loaded (about 50% and over) with
calcium and barium stearates. The principal advantages of such
concentrates are that they are virtually dust-free, can be air-conveyed
and have dry-flow properties very similar to those of PVC resins.
The effects of incorrect balance, or total amount, of a lubricant
system in a PVC composition may include the following, in varying
degrees of severity:
Processing Product
Overlubrication: Excessive slippage (re- Surface bloom; haze (in
(or wrong balance) sulting in lower output clear compounds); im-
or even disruption of paired printability
production); plate-out
Underlubrication: High shear resistance Impaired stability (be-
(or wrong balance) (resulting in lower out- cause of excessive heat
put); degradation of history) or actual de-
polymer in melt gradation
The presence of a slight excess of external lubricant can have some
useful effects. Thus surface gloss may be improved, and surface friction
and tendency to blocking reduced.

11.1.4 Sources of Information on Lubricants and Their Commercial


Suppliers

In addition to the references already quoted in this section, papers


published by Jacobson,18 Riethmayer,19 and Stapfer et al. 20 are
concerned with the nature, application and effects of lubricants.
11 Some Miscellaneous Components of pvc Formulations 371

Many suppliers of heat stabilisers for PVC (ct. Chapter 10, especially
Table 10.1) also supply lubricants. Listings of lubricant suppliers (as
well as those of most other additives) in the Western World will be
found in the publications mentioned in Section 8.5 of Chapter 8. Many
British suppliers are also listed in the Buyers' Guide for Plastics
Additives published by the British Plastics Federation. The following
may be mentioned by way of a few examples.
UK: Ciba-Geigy Plastics and Additives Co. Industrial Chemicals
Division (Irgawax); Diamond Shamrock Ltd (Lankroplast, Lankro-
mark); Croxton and Garry Ltd (Lubriol, Syntewax).
Continental Europe: Henkel International GmbH, West Germany
(Stenol, Ceroxin, Loxiol); Otto Barlocher GmbH, West Germany
(Biiropan); Acima, Switzerland (Metawax, Metaglide).
USA: Emery Industries, Inc. (Emerwax); Interstab Chemicals Inc.
(Interstab); Nopco Chemical Division of the Diamond Shamrock
Chemical Co. (Metasap, Nopcowax); Witco Chemical Corp. (Lubra-
plus); Petrochemicals Co. Inc. (Monolube).

11.2 POLYMERIC MODIFIERS

As has already been mentioned in Chapter 4, the polymeric additives


incorporated in PVC compositions may be broadly classified into two
groups according to their functions, viz. processing aids and impact
modifiers. In general terms, the main differences which form the basis
of this classification are in the nature of the polymers used in each of
the two capacities (see Sections 11.2.1 and 11.2.2 below), in the usual
level of addition (normally substantially lower with the processing
aids), and in the type of effect: processing aids-as implied by their
name-serve to modify the properties of the PVC stock during heat
processing (but have relatively little effect on those of the finished
product), whereas the main function of impact modifiers is to improve
the impact resistance of the product. However, whilst the above
features do typify the group characteristics in a general way, they are
not rigidly definitive. Thus there is some overlap in the types of
polymer used for the two respective purposes; many impact modifiers
have some processing-aid action (albeit this often tends to be
manifested at temperatures somewhat higher than those at which
typical processing aids exert their effect); processing aids can affect
some product properties even at their usual, relatively low level of
372 W. V. Titow

addition. Certain of the polymeric additives are also used in


exceptionally high proportions to upgrade the heat-distortion prop-
erties of uPVC compositions (see Section 11.2.1), or to combine a
toughening effect with plasticisation of virtually ideal permanence (see
Section 11.2.2).
It is very important for its maximum effectivity (and hence also cost
economy) that any additive (and especially one used in relatively minor
proportions) should be dispersed as thoroughly as possible in the PVC
polymer. This applies to the polymeric modifiers discussed in this
section.
In the production of PVC pre-mixes for further (melt) compounding,
and dry blends for use as feedstocks in melt processing, the order of
addition of the formulation components (in conjunction with the
temperature at the various mixing stages) plays a significant part in the
ultimate degree of dispersion and effectivity of action of the polymeric
modifiers. The following guidelines for a particular procedural
sequence and conditions in hot high-speed mixing of a powder blend to
be used as extrusion feedstock,21 illustrate something of the points
important in practice (see also Chapter 13, Section 13.4.1, for a more
complete discussion of high-speed mixing):
-<:harge the PVC powder to the mixer and mix at the appropriate
(high) speed;
-add colourant and stabilisers at 45°C, then impact modifier at
60°C;
-add lubricant(s) at 80°C;
-when the temperature reaches 100°C add acrylic processing aid;
-<:ontinue mixing, and at l1o-112°C discharge the batch into a cold
mixer (e.g. a water-jacketed ribbon blender); run till cooled to
40°C and discharge.
Information on suppliers of polymeric modifiers will be found in the
sources mentioned in Section 11.1.4 above. Some commercial
materials are mentioned, by way of non-selective example, in Sections
11.2.1 and 11.2.2.

11.2.1 Processing Aids

The polymers used as processing aids in PVC are of the following


kinds:
(a) acrylates and methacrylates (acrylic processing aids);
11 Some Miscellaneous Components of pvc Formulations 373

(b) styrene/methacrylate copolymers;


(c) acrylonitrile/butadiene/styrene (ABS) polymers;
(d) styrene/acrylonitrile (SAN) copolymers;
(e) poly-a-methylstyrene (PAMS).
The molecular weight of the PAMS grades marketed as processing aids
for PVC (Amoco Resin 18-Amoco Chemicals Corp., USA) iS,low
compared with those of other processing aids. Some ABS polymers are
used also as impact modifiers (as are some acrylic polymers--see
Section 11.2.2 below). One of their composition-related properties,
viz. the modulus of elasticity, is sometimes cited as a rough index of
the type of their effect in PVC compounds: those useful as processing
aids have the highest moduli, whilst the moduli of ABS impact
modifiers are comparatively low (less than about 1·4 GPa).
Processing aids are employed in rigid PVC compositions, in
relatively low proportions (about 1-6 phr) to facilitate melt processing.
The typical effects of their presence on the stock are: 14 ,21-24

(i) increased rate of homogenisation and fusion, except in the case


of lubricating processing aids which extend fusion time (but
reduce torque and back-pressure in extrusion-cf. (v) below);
(ii) improved strength, cohesion and extensibility of the melt;
(iii) reduction of melt modulus and 'nerve', die-swell, and tendency
to melt fracture;
(iv) increased melt viscosity (except with PAMS by which it is
reduced in most types of uPVC composition);
(v) tendency to increase torque and back-pressure in extrusion,
attributed to the faster, higher-shear character of the fusion
process 14 (PAMS is a partial exception here).
Effects (i) and (v) can be sensitive to the nature and amounts of the
lubricants present in the composition (especially where the processing
aid is PAMS23).
Note: In view of effects (iv) and (v) the practice-occasionally
encountered-of calling processing aids for PVC 'flow promo-
ters' is questionable. It would be preferable to restrict the
latter term entirely to its original use as a name for the group
of additives sometimes incorporated in thermosetting resin
systems to reduce the rate of interaction of reactive groups by
a dilution effect. 25
374 W. V. Titow

Effect (ii) is a contributory factor in the improvement in thermofor-


mability conferred on PVC sheeting by processing aids (especially of
the acrylic type).
The mechanism whereby processing aids produce their effects is not
yet fully understood. In certain respects their action is similar to that of
internal lubricants, but there are also important differences (e.g. the
opposite effect on melt viscosity in most cases): attempts to treat the
action of both these types of additive as a simple case of plasticisation
at high temperature,25 fall short of a complete explanation.
In addition to their role in the processing of uPVC, which is the
primary reason for their use, processing aids present at the normal
levels of addition can also affect some properties of the material.
Typically (e.g. with acrylic processing aids) such effects may include
improved surface finish (freedom from defects; improved gloss), better
colour stability of coloured materials, and improved transparency of
clear compositions.
Incorporation in uPVC compositions of high proportions (up to about
50 phr) of some polymers with processing-aid action (e.g. certain
styrene/acrylonitrile (SAN) copolymers) can improve the heat distor-
tion temperature, increase the Vicat softening point and reduce the
linear thermal expansion. However, impact strength is also usually
reduced, and suitable impact modifiers should be included in the
formulation to counteract this effect. Such compositions may be used
in a number of applications calling for a higher than average degree of
resistance to heat distortion (e.g. some pipes and injection moulded
pipe fittings, some extruded profiles): transparent versions in which the
polymeric modifiers (as well as the other components of the
formulation) are approved for food contact are of interest for the
manufacture of containers (jars, bottles) for food products which are
still hot at the filling stage (e.g. jam, marmalade, some liquids). The
following formulation has been cited (by Sahajpat26 ) as a good general
basis for a transparent composition of this kind, with low haze and
yellowness index, a Vicat softening point (DIN 53 460, 5 kgf load) of
85°C and impact strength (ASTM D 256) of 32·4 kgf cm cm- 2.

Suspension PVC polymer, K value 58 100


Stabiliser: Irgastab 17 MOK (Ciba-Geigy) 1·2 phr
Polymeric modifiers: SAN 20phr
MBS 10phr
Lubricants: Sapchim Lubricant 4150 0·7phr
Sapchim Lubricant 6164 0·5 phr
11 Some Miscellaneous Components of pvc Formulations 375

Some special ABS modifiers, * used in very high proportions, can


confer similar improvements in the temperature-dependent properties,
with good impact resistance and without substantial increase in
flammability.21

11.2.2 Impact Modifiers

(a) Impact Resistance-Its Nature, Significance and Measurement


Most PVC (as indeed other plastics) products are at risk of possible
damage by impact at some point during their lifetime, either through
accidental hits or drops (e.g. PVC pipes during transport and
installation; PVC containers in transport and storage), or in the course
of normal manipulation (e.g. PVC packaging film on high-speed
converting and packing machinery) and service (e.g. PVC swing doors
in factories and storage premises). For these reasons the degree of
resistance to breaking on impact, and its measurement, are of practical
importance in the selection and comparison of plastics materials for
particular applications, product design, and quality assessment and
control. On a more fundamental level, understanding the causes and
mechanisms of failure by fracture on impact of plastics materials and
products is equally important in the context of materials science.
The impact tests in general use measure directly the total energy
needed to break the test specimen by impact. This is one of the two
main general differences between such tests and the regular strength
tests, in which the force (load) which causes the specimen to yield or
break (in tension, compression, flexure or shear) is determined,
normally in conjunction with the load Ideformation curve. t
Note: Thus in this context 'strength' is the force (or the stress) for
failure. It is for this reason that the term 'impact resistance' is
replacing the formerly widely used 'impact strength' in the
titles of standard impact test specifications and references to
their results.

* These polymers are not primarily processing aids, and a formulation


containing even, say, 80 phr of such a modifier can benefit from the inclusion
of 2-4 phr of a good acrylic processing aid, e.g. Aery/aid K-120N (Rohm and
Haas Co., USA-the trade name Para/aid is used by Charles Lenning
Chemicals and affiliates in the UK and certain other countries: the product
coding is universal).
t The values of the stress at failure, and true stress/strain curves, can be
derived from such data.
376 W. V. Titow

The other difference lies in the respective test speeds (and hence
rates of deformation): those obtainable with ordinary strength-testing
equipment are much lower than the ones occurring in impact tests,
where the testing speeds are comparable with the speeds which can be
experienced by freely dropped objects (about 2-7 m S-I). These
differences do not mean that impact tests are fundamentally different
from strength tests. Although not measured directly in the latter, the
total energy to break can be computed from the area under the
stress/strain curve. Whilst the value so obtained will correspond to the
rate of deformation in the strength test concerned, and will thus
normally be numerically different from one furnished by a relevant
impact test (in which the deformation rate will be different), it has
been shown27 that both values can lie on the same smooth curve in a
plot of energy to break versus rate of deformation, if the mode of
failure (see below) is the same in the two tests.
Note: With special apparatus and instrumentation, tensile-strength
testing speeds can be brought up into the range involved in
impact tests. 28 •29 One version of such a high-speed test is
covered by an ASTM standard. 30 However, certain difficulties
attendant upon this kind of testing, and the fact that the
stresses generated differ in state and distribution from those
arising in other impact tests, limit its relevance to impact
properties of plastics largely to the role of a supplementary
technique, of interest predominantly (though not exclusively)
in research.
The concept of toughness of a plastics material (or object) is based
on the definition of this property as the work necessary to break a
suitable specimen of the material (or the object). This is, of course, the
same as the total energy to break (given by the area under a
stress/deformation curve) and hence-in an impact test-the impact
resistance. However, any actual numerical value of impact resistance
obtained in a test is only an arbitrary index of toughness, relating
specifically to the single set of conditions and specimen characteristics
(including its dimensions and configuration) employed in the test. *
This is so because impact resistance is not a fundamental, constant
property of a plastics material (or its parent polymer) with which a
product made from the material may be expected to be fully and

* Such values are often referred to as 'single-point data'.


11 Some Miscellaneous Components of pvc Formulations 377

directly endowed. In both the material and its derivative products the
impact resistance is influenced-in a complex way-by many factors,
which may be grouped under the following headings:
(i) 'Internal' material factors: composition; morphology; fine struc-
ture (including crystallinity and molecular orientation); pre-
sence of impurities, nibs or gels.
(ii) Effects of processing conditions: modification of the material
properties (e.g. crystallinity, orientation, impurities, etc.) in
processing; heat degradation;* incomplete fusion;* incomplete
interdispersion of formulation components* (and especially
impact modifiers and particulate additives in the polymer); such
process-induced product features as 'skin-and-core' effects in
mouldings, presence of internal stresses (cooling and packing
stresses in mouldings); surface imperfections or faults; and
weak sites (e.g. weak weld lines in injection mouldings, or nip
closures in blow-moulded containers).
(iii) Design factors: In products:t abrupt changes in section
(especially sharp corners); moulded-in metal inserts; machined
holes and screw threads. In standard test specimens: 'geometry';
presence and characteristics of notches. In both: material flow
(direction and pattern) in the course of formation in relation to
the 'geometry' of the object (position and type of gates in
injection mouldings).
(iv) 'External' factors:+ energy and speed of impact (and hence the
rate of deformation); shape and hardness of impacting object;
point of impact; temperature; nature of environment (possible
presence of stress-cracking agents).
Whilst anyone of these factors can affect the magnitude of impact
resistance, and the way in which fracture occurs in a given situation,
the wide scope for their combined action or interactions can also
complicate the fundamental interpretation of impact test results, as the
same values of fracture energy may be obtained for materials or
products fracturing by different mechanisms. Data on the associated
stress/strain characteristics can be a great help in interpretation: some
modern, suitably instrumented impact testers of the falling-weight type
provide such information as well as other dynamic-property data. 31 ,32
* Of special significance in PVC.
t Features creating stress concentration (some .crack-initiating).
:t:Operative in service conditions and/or tests.
378 W. V. Titow

Standard impact tests normally yield single-point data; but even


multi-point data provided by planned variation of the basic conditions
of a standard test, and/or the use of more than one test, cannot provide
a basis for a complete characterisation or prediction of impact
performance (although a well designed, comprehensive test programme
can go a long way in this direction, at least in some cases). Thus,
despite the comparability of the rates of deformation in standard
impact tests with those encountered in service, the degree of
correlation of the test results with impact resistance in service (or
between two different tests) is relatively limited. Nonetheless, a
standard impact test can be of practical value if its limitations in the
particular context are property recognised, and especially where-in
addition-experience of its use and a body of accumulated test data
relatable to service performance are available. It is on this basis that
standard impact tests are mainly employed in the industry.
Where a product or article can be tested in conditions realistically
approximating to the most severe likely service conditions the results
(even in the form of non-quantitative 'pass' or 'fail' information) can
provide valuable means of material comparison and production quality
control, as well as guidance on product design. This applies, for
instance, to drop tests on plastics containers* (some of which are
covered by standard specifications-e.g. ISO 2248 Part IV and the
corresponding BS 4826 Part 4; ASTM 0 2463), bird-impact tests on
aircraft canopies, or bullet-impact tests on safety screens or practice
targets.
Standard impact tests in general use for plastics materials or
products, and hence applicable, inter alia, to PVC, are listed in Table
11.2 (see also Appendix 3, Impact Resistance). Other relevant
standards, relating specifically to PVC materials and products, will be
found in the appropriate sub-sections of Appendix 1. The following
standard specifications give impact tests (all of the falling-weight type)
for extruded PVC products (pipe and cladding):
ISO 3127-1980. Unplasticised polyvinyl chloride (PVC) pipes for the
* Drop tests usually form the basis of impact resistance requirements laid down
by various national and international regulations governing acceptance for
transportation of filled containers (including plastics containers): ct., for
example, the International Maritime Dangerous Goods (IMDG) code; US
Department of Transport (DOT) regulations; International Air Transport
Association (lATA) regulations; or the RID regulations (Department of
Transport, UK) concerning carriage of dangerous goods by rail.
TABLE 11.2
Types of Standard Impact Test in General Use
Test type Relevant standards Applicable to: Expression of results '-
'-

Flexural impact See Table 11.3 Rigid plastics compositions;a See Table 11.3 ~
(Izod and Charpy rigid plastics sheet ::l
type) '"a::
t:;.
Falling weight BS 2782:1970: Methods Rigid plastics compositions;a Energy to break, in
impact 306B and C rigid plastics sheet J; kgf cm; or ft lbf ;:
~
ASTM D 3029-78 Plastics sheet or parts Mean tup weight for ~
failure, in kg or lb 1:;
DIN 53 443-1975 Parts Rigid plastics compositions;a Energy to break, in J ~
1 and 2 rigid plastics sheet ~c
Tensile impact ASTM D 1822-79 Plastics compositionsa ;:
Energy to break in J
~
or ft lbf t:;
ASTM D 2289-69 (1976) Plastics compositionsa Energy to break per ~
(high-speed test) (specimens as in unit cross-sectional "tI
ASTM D 1822) area, in J m- 2 or ~
ftlbfin- 2 ~
(NB Test also gives ~
l':
tensile strength, in S"
Pa or lbfin- )
DIN 55448-1977 Plastics compositionsa Energy to break, in a6'
mJ mm- 2 or kJ m- 2
a In the form of standard moulded specimens.
V.l
~
380 W. V. Titow

transport of fluids-Determination and specification of resistance to


external blows.
BS 5255:1976. Plastics waste pipe and fittings.
ASTM D 2444-70 (Reapproved 1977). Impact resistance of thermo-
plastic pipe and fittings by means of a tup (falling weight).
ASTM D 3679-79. Rigid poly (vinyl chloride) (PVC) siding. *
It is a particular advantage of falling-weight impact tests that-in the
versions employing suitable equipment-actual products (mouldings;
sections of pipe, profiles or cladding; etc.) can be tested. Such tests
carried out on one of the modern testers with microprocessor
instrumentation,t in conjunction with similar tests on suitable material
specimens, can provide a great deal of information on the effects of
design and processing, as well as basic data on the fracture mechanism.
Impact testing of PVC pressure pipes with the aid of explosive
charges33 may be mentioned as an example of the use of a special
technique to obtain information on fracture characteristics under
deformation rates and stresses relevant to conditions which the pipes
may experience in service (e.g. in mines).
Two cardinal aspects of the fracture on impact of a plastics object in a
test or in service are the fracture mechanism and the mode of failure
(brittle, ductile or intermediate-see below).
A plastic (like its parent polymer) fractures through the initiation
and propagation of cracks, and the total energy to break is the sum of
the energies consumed in each of the two processes. A systematic
examination of the effects of notch sharpness in notched specimens on
their impact resistance (energy to break) in suitable impact tests can be
a useful basis for assessing a material's resistance to crack initiation
and propagation. As the sharpness of the notch increases the
proportion of the total energy to failure expended on crack initiation is
reduced:* tests on very sharply notched specimens (notch-tip radius
about l0.um or less) can give a good indication of the crack

* This is a product specification prescribing, inter alia, a falling-weight impact


test on a variable-height impact tester (Gardner Tester Model IG 1120-
Gardner Laboratories Inc., Bethesda, Md., USA).
t e.g. the 'Dynatup' impact tester, marketed by Effects Technology, Inc.,
USA,31 or the CEAST Fractoscope (CEAST S.p.A., Italy).
:j: The ratio of the impact resistance of unnotched specimens to that of notched
specimens is generally referred to as 'notch sensitivity'. Numerical statements
of notch sensitivity should always be related to the particular test (and the
notch radii) used.
11 Some Miscellaneous Components of pvc Formulations 381

propagation energy (as the crack initiation energy is drastically lowered


by the high local stress concentration created by the sharp notch).
Note: Stress concentrations occurring 'naturally' in plastics objects
(including unnotched test specimens) can be caused, inter alia,
by surface faults or damage, as well as the presence of gels,
nibs or large particles (e.g. undispersed aggregates of filler or
pigment particles, adventitious contaminant particles) in the
material. As pointed out by Vincent,34 a notch of 0·25 mm
radius approximates to the most severe defect likely to be
encountered in practice, whilst, at the same time, its use in
extended tests permits coverage of a wider range of tempera-
tures than that of blunter notches which approximate better to
the most common service defects. The 0·25 mm radius notch
is used in several standard flexural impact tests (see Table
11.3).
Evaluation of the effects of an impact modifier in a rigid PVC
composition, or comparison of different modifiers, should be based on
investigations of this kind rather than-as often happens in the
industry~n single-point data from individual impact tests. The
temperature (and-if practicable-also the speed of testing) should
also preferably be varied in such investigations, to ascertain whether a
ductile/brittle transition in the mode of fracture (see below) may be
affecting the impact resistance within the relevant range of conditions.
Finally, supplementary information on the stress/strain behaviour of
the specimens at the rates of deformation and temperatures used in the
test is also relevant and helpful. The validity, as well as the practical
importance, of such investigations is illustrated, if illustration were
needed, by reports which crop up from time to time on the inadequacy
of single-point data from standard tests. The many examples which
could be cited include, for instance, three recent papers35 dealing,
respectively, with the insensitivity of a standard impact test (Gardner)
to the presence of impact modifier in uPVC sheet if crack-promoting
defects are absent; the need to vary the impactor velocity in the
standard (ASTM) Izod test-and to further supplement this by
high-speed tensile tests--for a better assessment of the toughness of
PVC materials; and the use of a three-point bend test on notched
specimens of uPVC sheet in preference to a falling dart test, for a better
evaluation of increased toughness of PVC with increased modifier
loading.
w
ClO
tv

TABLE 11.3
Notch Characteristics and Impact Resistance Units in Standard Flexural Impact Tests
Test type Standard specification Specimen Notch characteristics Impact Remarks
or notch resistance
designation Shape Included Tip radius unitsa
(cross- angle (mm)
section)

Izod ISO 180 (data from current revi- Notch type A b V 45° 0.25} Four specimen types in
ckJ m- 2
sion draft document ISOIDIS Notch type B V 45° 1·00 specification (type 4
180, July 1980) preferred)
BS 2782:1970: Method 306A Specimen type A V 45° 1 J or kgf cm or lbf ft per Notch moulded-in in
Specimen type B V 45° 1 unit width of speci- specimen A,
Specimen type C V 45° 1 men (in m, cm and machined in Band C:
in., respectively) width of specimen C
is half that of A and B
ASTM D 256·78, Methods A - V 45° 0·25 J or ftlbf per unit
andC specimen width (in m
and in., respectively)
Charpy ISO 179 (data from current revi- Notch type A Notch width: d
sion draft document ISOIDIS U Four specimen types in
2mm or 0·8mm Com,,,.dii, *0·1 }
1979, July 1980) specification (size 2
Notch type Bb V 45° 0·25 kJm- 2
preferred)
Notch type C V 45° l-(lO

BS 2782:Part 3: Method Notch type A Notch width:'


351A:1977
U 2mm orO·8mm Com",.iiii, *o.J Three specimen sizes
Notch type B V 45° 0·2 Jm- 2 in specification (size 1
Notch type C V 45° 1·0 preferred)

ASTM D 256-78, Method B - V 45° 0·25 J or it Ibf per m or in.


(respectively) of
specimen width
DIN 53453-1975 Standard bar U Notch width: Com" "d;;'}
2mm :/-0·2 kJ m- 2 or
Small standard U Notch width: Corner radii: mJmm- 2
bar 0·8mm :/-0·1
Dynstat DIN 53 435-1977 Only unnotched specimens kJm- 2

a For unit conversions see Table 11.4.


b This type preferred.
C i.e. energy to break in kilojoules per unit area of cross-section of the part of the specimen under the notch (total cross-sectional area in un-notched specimens).

d Respectively in Specimens 1 and 3.


, Respectively in Specimens 1 and 2.

w
00
w
384 w. V. Titow

TABLE 11.4
Conversion Factors for Common Units of Flexural Impact Resistance

SI unit Other units

kJ m- 2 kgfcm cm- 2 ft [bf in- 2 ft [bf


(per inch of specimen
(notch) width O)

1 1·02 0·476 0,191


0·981 1 0·467 0·187
2·10 2·14 1 0·401
5·24 5·36 2·50 1

° Conversion factors for these units applicable only to rectangular specimens


with notch-tip radius of 0·25 mm and thickness of material under the notch of
1 mm (cf. ASTM D 256), on the assumption that-in general-the energy to
break is proportional to this thickness. 3

In the simplest, broad terms, the way in which a plastic fractures on


impact, i.e. the mode of failure, may be classified into brittle, ductile,
and intermediate (between the first two). The most characteristic
differences between typical cases of these three failure modes lie in the
appearance of the fracture surfaces and in the stress/strain effects as
shown up by the respective load/deformation curves. Typical brittle
failure produces a fracture surface which is smooth and shiny (although
overall it may be fragmented in the general plane of fracture). Fracture
surface typical of ductile failure exhibits ridges or strands of material
standing proud in varying degrees and configurations: these formations
may also show stress whitening. In the intermediate mode of failure
the surface characteristics are part-way between those of the other two
types: in some cases there may be a progressive transition marking the
original path of the developing crack. In terms of typical, basic
load/deformation behaviour, (which may be demonstrated with a
suitably instrumented impact tester 29 ,31) the three kinds of failure
mode are characterised by the following features. Since-by defini-
tion-brittle failure occurs (i.e. a crack initiates and propagates to the
point of complete fracture) before any bulk yielding of the material can
take place, the load/deformation curve is of the kind shown
schematically in Fig. 1l.2(A). In typical ductile failure (Fig. 11.2(B»
the material yields before (in some cases well before) breaking, the
yield point being reflected by a bend or peak on the curve. The shape
11 Some Miscellaneous Components of pvc Formulations 385

o
Fig. 11.2 Load (L)/deformation (D) curves for the three general types of
failure mode. Schematic representation. A, Brittle failure; B, ductile failure;
C, intermediate failure.
386 W. V. Titow

of the curve after the yield point depends on the actual mechanism of
plastic deformation of the material in the particular case (e.g. necking,
cold drawing, etc.). With the mode of failure intermediate between
brittle and ductile there is some yielding in the region of failure before
or during the propagation of a crack (cf. the curve of Fig. 11.2(C)).
Although the diagrams of Fig. 11.2 are schematic, they do illustrate the
typical shape of the load/deformation curves for the different modes of
failure, and the fact that-other factors being equal-the energy to
break (as represented by the area under the curve) increases with the
mode of failure in the sequence brittle ~ intermediate ~ ductile.
Among the 'external' factors influencing impact resistance, the
temperature and the speed of impact (rate of deformation) have a
special significance, in that changes in their values which can occur
within the general range of possible service conditions can alter the
mode of failure of many thermoplastics from ductile to brittle (or vice
versa) and thus sharply reduce (or increase) the energy to failure. The
'internal' and processing factors most strongly affecting this transition
under service conditions (or in tests) are the basic composition (e.g.
presence or absence of impact modifiers in uPVC) , local stress
concentrations, and structural anisotropy. Lowering the temperature of
a thermoplastic which initially breaks in the ductile mode will normally
eventually result in a change to brittle fracture. Where the change is
sufficiently sharp, * the temperature at which it occurs is the
ductile/brittle transition temperature (Tb ), sometimes also referred to
as 'brittleness temperature', 'brittle temperature' or 'brittle point'. Its
value in any given circumstances is influenced by the various factors
affecting impact resistance (see above), and in particular by the
presence and magnitude of stress concentrators (surface faults or
damage in service, presence and tip radius of notches in tests): even
when all the main factors are kept constant the value assigned to the Tb
can be affected by the choice of criterion for identifying the change of
failure mode (e.g. whether sudden drop in impact strength, appearance
of fracture surface, load/deformation curve, etc.), and even by the
sensitivity of assessment under the same criterion (e.g. examination of
fracture surface with the naked eye, under the microscope, or by
electron scan). 29 However, these considerations do not invalidate
* With some plastics materials the drop in impact resistance with temperature
(and the associated evidence of transition from ductile to brittle deformation
on the fracture surface) may be very gradual, so that no definite Tb can be
established. 29
11 Some Miscellaneous Components of pvc Formulations 387

either the concept or the relevance of Tb in connection with the


understanding and assessment of impact behaviour of plastics,
providing that the limitations of its applicability are properly
understood.
Note: Bucknall et al. 29 use the Tb (in conjunction with notch sharp-
ness) as the basis of a classification of plastics materials (into
five categories*) relevant to their impact behaviour in service.
Where no brittle/ductile transition occurs in the particular test or
service situation, the impact resistance of a plastic may remain constant
over a wide temperature range. This is demonstrated by the curves for
polystyrene and poly(methyl methacrylate) in Fig. 11.3: both polymers
251--~· ----------., - - - - - -- pc------- ---------.
I
I
i
20~
I

PPO

....cen-
c
~ 10
ti
...
..
u
a.
~
5

OL-_
~~~;;~;;;;:===::::=~:==::::::-
= _.....L L-_ _...L._ _---' PSPMMA
-:'::-_ _----:::-:---_~
_200 -150 -100 -50 0 50 100 150
Tast tamparatura. 'C

Fig. 11.3 Impact resistance (in a Charpy-type test on notched specimens with
0·25 mm notch radius) as a function of temperature for five polymers. PC,
bisphenol-A polycarbonate; PPO, poly(2,6-dimethyl paraphenylene oxide);
uPVC, unplasticised polyvinyl chloride; PMMA, poly(methyl methacrylate);
PS, polystyrene. (Reproduced from Ref. 34 with permission of the copyright
holder, ICI, and the publisher, John Wiley and Sons Ltd).

* In order of increasing impact resistance: brittle, blunt-notch-brittle, sharp-


notch-brittle, tough but crack-propagating, very tough, crack-arresting.
388 w. V. Titow

are in the glassy state, and below their brittle temperatures (which
roughly coincide with the glass-transition temperatures), throughout
the entire temperature range covered, and hence break in brittle
fashion, with low energy to break.
Note: In contrast with the impact resistance, the tensile strength of
thermoplastics increases with decreasing temperature. * The
brittle point may be defined in terms of this property as the
temperature at which the yield strength is just equal to the
brittle strength (and below which the latter becomes
higher).34
The effect of increasing the speed of impact is similar to that of
lowering the temperature; it has been suggested that, with thermoplas-
tics, a ten-fold increase in impact speed may be regarded as roughly
equivalent to a lOoC drop in temperature. 36
A full discussion of the impact behaviour of thermoplastics would be
outside the scope of this section (and not essential to its purpose).
Further information can be found in Refs 28, 29, 34 and 37, all of
which list numerous book and literature sources. A useful brief
summary of the main aspects of impact resistance relevant to the
design and service performance of plastics products is given in Ref. 36.

(b) The Impact Resistance of pvc


With PVC products the possibility of fracture by impact in service is of
much greater concern in the case of unplasticised compositions than
with pPVc. Whilst some plasticisers (notably tricresyl phosphate) can
make the plasticised material prone to embrittlement at temperatures
within a moderate range for service (even above O°C for some
TTP-plasticised compositions), this can easily be avoided by suitable
formulation. Thus, in general, flexible PVC compositions are tough
materials, which do not normally fail by fracture on impact in service
or in tests (and give typically ductile breaks on failure in tension),
although plasticised sheeting-particularly thin films-may be punc-
tured by falling weights (especially sharp-ended ones, like, for
example, dart impactors used in some tests).

* The tensile strength of a rigid PVC composition tested by Dyment and


Ziebland 38 increased from 7·7 x 103 1bf in- 2 at 20°C to 19·7 x 103 1bf in- 2 at
-196°C (with a corresponding increase, by a factor of 2·13, in Young's
modulus).
11 Some Miscellaneous Components of pvc Formulations 389

30
60

~~ 20·C
£20
40
:::.
.:L
111 N
CI
'-
.0
'E
....,
.:L
E
~10 20
'-
CI
C
W

o 0·02 0·04 0·06 008


Notch radius, in
(05) (1·0) (1-5) (2·0)
(mm, approx)

Fig. 11.4 Impact resistance of a uPVC composition as a function of notch-tip


radius in a Charpy-type test at various temperatures.

Note: Embrittlement in consequence of changes in the material


through loss of plasticiser, heat degradation, weathering, or
ageing is not directly relevant in the present context.
Rigid PVC is not intrinsically a brittle material at ordinary
temperatures: the brittle point of properly made un-notched uPVC
specimens in a flexural impact test can be as low as - 50°C. 34
However, the material is sensitive to the presence of stress-
concentrating features (as evidenced by its notch-sensitivity in impact
tests-see Fig. 11.4), and also to the rate of deformation, in the sense
that these factors-when operative at levels encountered in service
conditions and in tests-ean, singly or jointly, bring about a
ductile/brittle transition and thereby cause brittle failure to occur in
impact situations even at room temperature. A plastics material
susceptible in these two ways is sometimes referred to as 'notch-brittle'
and 'shock-brittle'.
This situation is illustrated by the curve for uPVC in Fig. 11.3: the
rapid drop in the impact strength of notched specimens within a
390 W. V. Titow

relatively narrow range of common service temperatures, is attribut-


able to the onset of brittle fracture brought about by the relatively
severe 0·25 mm notches at the speed of impact employed in the test.
As has been mentioned, the effects of both these factors are
reasonably representative of those of stress-concentrating faults and
impact speeds which may occur in service.
Note: Notches, or 'natural' faults, in a polymeric material can raise
the Tb and thus promote brittle failure not only by causing
stress concentration, but also by limiting the amount of plastic
deformation which can take place locally before fracture
occurs, through a modification of the stress field at the
incipient crack tip (transition from plane-stress to plane-strain
conditions29 ). Contributory factors which can arise in practice
include incomplete fusion (gelation) of the PVC composition
(in consequence of inadequate heat processing), or degrada-
tion of the polymer (excessive heat processing).
Incorporation of impact modifiers in PVC compositions is a practical
way of increasing their impact resistance. The room-temperature
impact strength (notched Izod, ASTM D 256) of an unmodified PVC
based on a relatively low molecular weight polymer may be as low as
0·4 ft lbf in -], and perhaps about twice that with a polymer of high
molecular weight. Inclusion of, say, 15 phr of a suitable impact
modifier can raise these values to about 20 ft lbf in-lor even higher in
some cases, with considerable improvement also in low-temperature
impact resistance. In terms of the PVC graph in Fig. 11.3 such
upgrading amounts to a displacement of the curve upwards and to the
left.

(c) The Nature, Effects and Applications of Polymeric Impact


Modifiers for pvc
The following types of polymer are in industrial use as impact
modifiers in PVC:
(i) acrylonitrile/butadiene/styrene (ABS) polymers; *
(ii) methacrylate/butadiene/styrene (MBS) polymers;
(iii) ethylene/vinyl acetate (EVA) copolymers and EV ANC graft
copolymers;
* Normally of relatively high butadiene content (and hence comparatively low
modulus-see Section 11.2.1).
11 Some Miscellaneous Components of pvc Formulations 391

(iv) acrylic polymers (all-acrylic modifiers);


(v) chlorinated polyethylene (CPE);
(vi) acrylonitrile/butadiene copolymers (nitrile rubbers);
(viii) polyurethane (PUR) elastomers.

Other polymers, generally of an elastomeric nature, have been


patented, examined, or used as impact modifiers for PVC, including
butadiene/2-vinyl pyridine, butadiene/methyl isopropenyl ketone,39
butadiene/fumaric ester copolymers,39,4o and Hytrel 3495 (a co-
polyester thermoplastic elastomer produced by Du Pont).41
The normal levels of addition for straightforward impact modifica-
tion of uPVC range between 5 and 20 phr (commonly 10-15 phr) but
some modifier polymers are sometimes used in very high proportions
to impart special properties to PVC compositions (see below).
Some fine-particle fillers (especially calcium carbonate-see Chapter
8, Sections 8.3.4 and 8.4.1) and pigments (e.g. titanium dioxide-see
Section 11.3 below) can, when properly dispersed, also improve the
impact resistance of uPVC.
At the normal levels of addition polymeric impact modifiers function
by forming a disperse phase in the matrix of the PVC polymer
(containing also those constituents of the composition which are fully
soluble in it, e.g. processing aids, internal lubricants, some stabilisers):
this interferes with crack development in the matrix, and can act as
internal energy absorber (the more effectively, the more rubbery the
nature of the modifier), in ways analogous to those in which
elastomeric modifiers function in toughened polystyrene. 25 Useful
early summaries of the mode of action of impact modifiers in PVC
have been published by Bramfitt and Heaps39 and Sisson. 42 The
impact-modifying particulate additives mentioned above have a
broadly similar action. Where, as with ABS and many other modifiers,
the refractive index of the continuous phase (PVC polymer matrix) is
appreciably different from that of the modifier, the latter has an
opacifying effect on the composition: hence in uPVC compositions for
clear products (e.g. blow-moulded bottles, packaging films) the
refractive indices should match as closely as possible at the appropriate
service temperature (the respective refractive index values, and hence
the closeness of match, can vary with temperature 21 ). Selected MBS
modifiers are widely used in clear compositions. In cases where the
refractive indices of modifier and matrix are close but not completely
matched (and where all other formulation components are chosen for
392 W. V. Titow

maximum clarity), if the refractive index of the disperse phase (which


may also include such components as, for example, some external
lubricants and stabilisers) is lower than that of the matrix the
composition will be yellowish and hazy in a degree proportional to the
difference in refractive indices: if the disperse phase has the higher
refractive index, blueing ('colour reversal') will result.
Some polymeric impact modifiers are highly compatible with the
PVC polymer, and are sometimes incorporated in very high propor-
tions. Of these, those which interact strongly with (have a close
chemical affinity for) the PVC polymer act as true plasticisers of very
high permanence (e.g. EVNVC graft polymers rich in the VC
component; highly chlorinated polyethylene). Others, like, for exam-
ple, nitrile rubber and some ABS polymers, also modify considerably
the properties of the blends they form with PVC at the high levels of
loading.
Side effects on the properties of uPVC materials exerted-in varying
degrees-by most polymeric impact modifiers at the normal levels of
addition, include the following: reduction of hardness, modulus,
strength (tensile and flexural), deflection temperature under load, and
chemical resistance; increased permeability; and impaired weathering
resistance (except with some acrylic and EVA/VC impact modifiers
which, whilst not positively improving the weathering properties, do
not affect them adversely in uPVC compositions formulated for good
weathering resistance). Some impact modifiers promote stress-
whitening in uPVc. This phenomenon is usually attributed to the
formation of microscopic voids or crazes through local separation of
the disperse phase (including fillers-cf. Chapter 8, Section 8.3.3) from
the polymer matrix under strain; it is particularly undesirable in clear
compositions: modifiers for such compositions are selected, inter alia,
for minimum effect in this respect-several suitable MBS modifiers are
available.
Note: As measured in tests on transparent compositions, stress
whitening may be defined on the basis of the relationship
SW = 100 [1 - (Is/I)]
where: SW is the stress whitening (%), Is is the % light
transmission after stressing, and I is the % light transmission
before stressing.
In processing, many impact modifiers act as processing aids,
11 Some Miscellaneous Components of pvc Formulations 393

albeit-as has been mentioned in Section 11.2.1-this action is often at


its maximum at temperatures somewhat higher than those at which
regular processing aids are effective. In most cases the presence of an
impact modifier also increases die-swell in extrusion (except for some
acrylic modifiers, which have relatively little effect).
Polymers used as impact modifiers in rigid PVC may also be
incorporated in flexible compositions, where they can improve the melt
properties in processing as well as modify the material properties at
service temperatures, in ways which include reduction of brittle
temperature, increased stiffness, and improved surface properties and
emboss retention.
The effects of different impact modifiers on some properties of a
PVC composition are compared in Table 11.5.
The following further points may be mentioned about the individual
classes of polymeric impact modifiers.

ABS MODIFIERS
These modifiers are widely used in opaque, rigid compositions for
products not required to withstand weathering (e.g. pipes and pipe
fittings): in such compositions they can give high room-temperature
impact resistance and improved low-temperature resistance, with
relatively little effect on heat-distortion temperature and softening
point. Commercial compounds containing ABS modifiers in substantial
proportions are sometimes referred to as 'PVC!ABS alloys'.
Note: Typically, such commercial compounds may combine room-
temperature impact resistance (notched Izod) of about
10 ft lbf in-I with v-o rating in the UL94 flammability test,
and tensile strengths of about 5000lbfin- 2 .
Extrusion compounds of this kind are used, for example, for profiles,
and sheets for thermoforming (with particular suitability for deep draw
forming) into such products as panels, casings (e.g. computer
housings), and battery covers; injection moulding compounds are used,
inter alia, for electronic equipment covers and housings, television
cabinets and the like. Good surface finish and low SG are among the
useful features of these materials.
In semi-rigid sheeting ABS modifiers can also substantially improve
thermoformability and reduce post-forming shrinkage.
Very high proportions of suitable ABS polymers can be incorporated
in flexible PVC compositions (e.g. 65/35 ABS/PVC in some cases) if
TABLE 11.5
...,
Q
'R
Effects of Different Impact Modifiers on some Properties of a Rigid PVC Composition
(Summary of selected data from Ref. 26)
Modifier Amount Notched impact Heat stability at Vicat softening point C

(phr) resistanceb 2000C (min) CC)


(kgf cm cm- 2 )

at -36°C at 23°C oven Brabender 1 kg load 5 kg load


rheometer,
30 rpm
ABS (Blendex 31- 10 5·8 13-8 88 72
Borg-Warner Chemicals) 15 6·2 32·5 30-35 43 91 73
MBS (Blendex 436) 10 5·4 22·0 83 70 ~
15 6·1 37·0 30-35 44 82 70 :<:::
Chlorinated 10 4·5 10·1 83 70 :::;j
polyethylene 15 4·8 15·2 20-25 d 37 d 82 68 <:;
~
EVA/VC 10 4·8 6·4 82 70
15 4·9 8·2 30-35 42 85 69
CaC03 filler 10 3·6 5·1 82 69
15 3·4 7·2 30-35 41 81 68
Q PVC polymer (S grade, K value 65) 100
Modifier: as listed 10 or 15 phr
Stabilisers: Ba/Cd 3'Ophr
chelator 0·5 phr
epoxidised soyabean oil 3·0phr
Lubricants 1·3 phr
b Charpy type: DIN 53453.
cOIN 53460.
d Determined for a composition based on 20: 80 CPE:PVC blend.
11 Some Miscellaneous Components of pvc Formulations 395

the plasticisers are chosen for compatability with the ABS component.
In such compositions it is the PVC which may be regarded as the
modifier for ABS, improving the latter's tear and abrasion resistance,
hardness and tensile strength, and reducing flammability.21

MBS MODIFIERS
Whilst modifiers of this class can be used in opaque formulations, they
are of particular interest for clear compositions (e.g. bottle, film and
sheeting compounds), as many have refractive indices in the right
range to promote good clarity: with several MBS modifiers this may be
combined with good colour and surface gloss as well as resistance to
stress whitening, good heat stability and low degree of odour and taste
transfer in containers. Increases in the room-temperature impact
strength of rigid compositions obtainable with some MBS modifiers can
be as high as 25-fold (e. g. from about 1 ft lbf in -1 to about 25 ft lbf in- 1
with Blendex 436 (Borg-Warner Chemicals) in a notched Izod-type
test).

EVA MODIFIERS
This group comprises EVA copolymers, and graft copolymers of vinyl
chloride with EVA. In general, the impact-modifying effect of EVA
copolymers in PVC increases with increasing vinyl acetate content.
Room-temperature impact strengths of about 20 ft lbf in-1 (notched
Izod, ASTM D 256) can be attained in some compositions at 10-15 phr
loadings.
The vinyl chloride component in EVAlVC polymers promotes
compatibility with PVC. Some graft copolymers of this kind (e.g. Du
Pont's Elvaloy resins 741 and 742) can be used as solid plasticisers of
exceptionally high permanence, in amounts as high as 80 phr. 13 ,43
Like some all-acrylic modifiers (e.g. Aeryloid KM 323B-Rohm and
Haas) EVA modifiers (e.g. Levapren 245O-Bayer; Hostalit H-
Hoechst; Elvaloy 836 and 837-Du Pont) do not appreciably impair
the retention of physical properties (and, in many cases, colour) on
weathering of uPVC compositions which contain them: they are
therefore applicable in such products as window frames, cladding and
fencing profiles for external use, and rainwater goods.
Note: As has been mentioned in Chapter 1, a suitable EVAIVC
graft copolymer can be used on its own (instead of a PVC
resin/modifier combination) in uPVC products of this kind.
396 W. V. Titow

Similar uses are being developed for graft copolymers of vinyl


chloride on ethylene/propylene (E/P) copolymers and
ethylene/propylene/diene monomer (EPDM) terpolymers;44
the graft polymers form the basis of commercial PVC
compounds (Rueodur-Ruco Division of Hooker Chemical
and Plastics Corp., USA)45 for injection moulding, extrusion
and blow moulding which combine impact resistance in the
range 15-20 ft lbf in -1 with a UL94 flammability rating of
V-O.

ACRYLIC MODIFIERS
This group provides impact modifiers which, in addition to their
principal function in uPVC compositions, offer some processing-aid
effects, low die-swell in extrusion, and in service little impairment in
weatherability of products in which this is of primary importance (see
preceding paragraph). The acrylic modifiers are well represented by
the relevant products in the Aeryloid (Paraloid*) range of Rohm and
Haas in the USA and associate companies elsewhere.

CHLORINATED POLYETHYLENE
The chlorinated polyethylenes used as polymeric additives in PVC are
based on high density polyethylene. They are produced by chlorination
of this polymer, which may be carried out in suspension, solution, or
even in the solid phase. 46 The solution process gives the greatest
uniformity of distribution of the CI atoms in the polymer chains. 47 The
distribution is a contributory factor in the compatibility of CPE with
PVC polymer, which is mainly governed by the chlorine content.
Other factors influencing the compatibility and effects of CPE in a
given PVC composition are the molecular weight and degree of
crystallinity of the modifier. 48 Impact-modifier grades have chlorine
contents in the range 25-40%: they are used at incorporation levels
normal for polymeric modifiers in uPVC (up to about 20 phr, with
maximum impact resistance often reached at about 15 phr). Room-
temperature impact resistance (notched Izod ASTM D 256) of 20 ft lbf
in -1 can be attained (even higher in some cases), with considerably
improved low-temperature toughness: the modifier also has some
processing-aid action, and lubricant effects have been reported. 49

* The trade name Paraloid is used by Charles Lenning Chemicals and affiliates
in the UK and certain other countries: the product coding is universal.
11 Some Miscellaneous Components of pvc Formulations 397

CPE grades of higher chlorine contents are fully compatible in all


proportions with PVC polymer, due to the close chemical similarity.
They do not increase the flammability of PVC compositions, as do
polymeric additives without chlorine (or with relatively low CI
contents). The highly chlorinated CPEs can be used at very high
incorporation levels in PVC compositions to function as plasticisers of
excellent permanence.
In both capacities CPE is an additive which does not substantially
impair property retention on weathering of PVC compounds properly
formulated for weathering resistance. An important factor in this
desirable feature is the absence of double bonds (present in the
molecular chains of rubbery modifiers) which constitute vulnerable
sites in weathering and ageing situations (ct. also acrylic and EVA-type
modifiers).
Note: In an early evaluation of a CPE impact modifier (Modifier
PIM lOl-Allied Chemicals Corp.-a non-crystalline CPE
with 40% CI content) O'Toole and co-workers found,49 inter
alia, a 100% impact-resistance retention, with little deteriora-
tion of other properties, after natural weathering of a PVC
sheet containing this impact modifier. However, incorporation
of CPE modifiers does, in general, lower the strength
properties of PVC in comparison with unmodified material.
In such products as, for example, rigid profiles for outdoor use (and
especially in cellular versions) a CPE modifier can promote filler
acceptance. 13 The use of chlorinated polyethylene as plasticiser for
flexible sheeting for horticultural applications or reservoir lining can be
beneficial (but is restricted by cost considerations). Chlorine-rich
non-crystalline CPE grades are compatible with most plasticisers, and
can be incorporated-in moderate proportions-to increase the
modulus and reduce brittle temperature of pPVc. Crystalline grades are
said to be beneficial in plasticised flooring compositions. 50

NITRILE RUBBERS
Nitrile rubbers of suitable acrylonitrile content can be blended in
virtually any proportion with PVC homopolymers. Depending on the
proportion, on whether the composition has been vulcanised, and also
to some extent on the application, the material based on such a blend
may be regarded as rubber-modified PVC or PVC-modified rubber. In
a blend the two components modify each other's properties, and the
398 W. V. Titow

properties of the blend (and any composition in which the blend is the
base polymer) will reflect this mutual effect. The ratio of the compo-
nents is the most important single factor governing the extent of
modification in a given case, but other factors also play a significant
part, e.g. the acrylonitrile content and Mooney viscosity of the rubber,
and the molecular weight of the PVC polymer,5! as well as the nature
and content of any other constituents of the composition (e.g. plasticis-
ers, fillers). As a broad generalisation it may be said that in the blend
the PVC polymer contributes ozone, oil and fuel resistance, strength
(tensile and tear), and stiffness, as well as weatherability (with proper
stabilisation), abrasion resistance, flame resistance (which may be
enhanced by the presence of phosphate plasticisers and/or chlorinated
plasticiser-extenders in the composition) and higher electrical resistiv-
ity. Thus these properties of a nitrile rubber will be upgraded by
modification with PVC.
Note: The increase in strength (and especially tear strength) can be
maximised in vulcanised PVC-modified nitrile rubber com-
pounds if the vulcanisation system is based on the total
polymer blend (not the rubber component alone).
The properties of PVC mainly upgraded by incorporation of nitrile
rubber are toughness (impact resistance), flex-crack resistance, low-
temperature flexibility, and resilience. Some of these effects are
illustrated by the curves of Fig. 11.5.
Nitrile rubber of grades used in blends with PVC is often regarded as
a plasticiser (highly permanent, non-extractable and non-migratory
because of its polymeric nature). In the practical context this is
consistent with its complete miscibility with PVC polymer, and its
principal effects on the properties of PVC compositions. The question
whether nitrile rubber indeed acts as a true plasticiser is therefore
more of theoretical than practical interest. It may be noted, however,
that-as observed by several investigators52-intimate blending (by
melt-compounding) of this modifier with PVC polymer in 'plasticising'
amounts does not result in a shift of the latter's Tg to a lower
temperature (as in the classic case of plasticisation) but gives rise to a
single, broad glass-transition region spanning the whole range between
the individual Tgs of the two components of the blend. Moreover, the
fine structure of the most intimate blends prepared by melt-
compounding has been reported to be heterogeneous, with rubbery
domains of sub-micron size revealed by electron microscopy.39,52 With
11 Some Miscellaneous Components of pvc Formulations 399

40

(A) (B)
o 10 20 30 40 50 60 70 o 10 20 30 40 50
°'0 PVC 0'. PVC
Fig. 11.5 Some effects of PVC content in blends of PVC homopolymer with
nitrile rubber. (A) Tensile strength (TS) and modulus (M) of nitrile gum stock.
(B) Oil resistance of medium-acrylonitrile rubber.

regard to the toughening effect of nitrile rubber in PVC, the point has
been made39 that, whilst a rubbery additive capable of being dispersed
in PVC polymer on a molecular level could increase the impact
resistance by reducing the yield strength (promoting ductile failure) in
the same way as a plasticiser, a two-phase system is more effective in
producing a high degree of toughening.
In the production of blends of PVC polymer with nitrile rubber,
melt-compounding is necessary for maximum uniformity and complete-
ness of inter-dispersion. However, availability of the rubber in powder
form enables it to be included in PVC compounding processes at the
pre-mix (dry blend) stage. Ready-made blends (in slab, chip, or powder
form) are also available from commercial sources: e.g. the Breon
'Polyblend' 500 series (BP Chemical International Ltd-blends of
butadiene/acrylonitrile copolymers of medium-to-high acrylonitrile
content with PVC homopolymer). The blends may be compounded
with additional nitrile rubber or PVC polymer (to adjust the ratio of
the two components to a value required for a particular purpose),
and/or with other materials appropriate to the intended application
400 w. V. Titow

(PVC stabilisers, plasticisers, lubricants; vulcanising curatives and


reinforcing filler for the rubber; general fillers for the composition).
The main advantages claimed for the use of the commercial blends
vis-a.-vis direct blending of commercially available nitrile rubber and
PVC polymers, are better processing properties and reduced need for
high-temperature mixing. Some typical properties of Polyblend 503*
(sheet) are given in Table 11.6.

TABLE 11.6
Physical Properties of 'Breon Polyblend 503'

Tensile strength (lbf in -z) 1850


Elongation (%) 430
100% modulus (lbf in- Z) 1100
Hardness (Shore Durometer A) 93
Specific gravity 1·18
Crescent tear (lb in-I, ASTM D 624-54) 320
Rectilinear tear (lb in-I) 328
Low temperature brittleness (OC, ASTM D 746-64T) -51
DC volume resistivity (Q cm) 2·6 x 109

Typical formulation for black press polished sheetings


Parts
Breon Polyblend 503 100·0
Black (added as MB) 1·5
Acrawax C (Glyco Chemicals Inc.) 0·5-1·0
Lead stearate 0·2-0·3

Rubber-type processing of nitrile rubber/PVC blends and their


compounds can be carried out on ordinary rubber equipment, at
temperatures slightly higher than those typical for unmodified nitrile
rubber compounds. Compounds based on PVC-rich blends which are
not to be vulcanised are processed in ways normal for PVC
compositions-by extrusion, calendering, moulding, etc.
The use of nitrile rubber/PVC blends was pioneered by the cable
industry, where vulcanisation of the rubber component of cable-sheath
compositions based on the blends was an early development. Wire and
cable coverings, which continue to provide a considerable outlet for

* Described as a colloidal blend of medium acrylonitrile butadiene rubber and


a PVC homopolymer in the ratio of approximately 48 pbw rubber to
52pbwPVC.
11 Some Miscellaneous Components of pvc Formulations 401

the blends, are nowadays the subject of several standard specifications


(see Section 9 of Appendix 1). Other applications of nitrile
rubber/PVC blend compositions include integral covers for fuel hoses,
conveyor belting, and rollers, shoe soles, and flexible containers.

POLYURETHANE ELASTOMERS
Like nitrile rubbers, appropriate grades of these elastomers are widely
compatible with PVC, but the position with regard to their use in
combination with PVC differs somewhat in two respects from that in
the case of PVC/nitrile rubber blends. Thus, whereas the presence of
PVC polymer in nitrile rubber can substantially upgrade the latter's
resistance to ozone, oil, fuels and abrasion, the corresponding
resistance of some PUR elastomers is inherently good, so that
modification with PVC may not make much difference (although it
might cheapen some types of composition). Conversely, as an impact
modifier for uPVC, a PUR elastomer-even when potentially very
effective-has to compete on price with cheaper alternative materials.
Nevertheless, PUR modifiers for PVC are on the market (e.g. those in
the Landex range of the Story Chemical Corp., USA, Ultramoll PU of
Bayer and Durelast 100 of Briggs and Townsend, UK) and commercial
PUR/PVC blends have been used for the production of shoe soles and
moulded industrial boots (e.g. Ekalit M and Kombipur-VEB
Chemiekombinat, Bitterfeld, E. Germany): see also Chapter 7,
Table 7.4.

11.3 COLOURANTS

11.3.1 General Nature and Functioning

Colourants may be broadly divided into pigments and dyes. Both terms
can have somewhat differing connotations in different industries, but
for the purpose of this section-and without attempting a comprehens-
ive description-the following working definitions are valid. Pigments
are colouring materials which are insoluble (i.e. not dispersible on a
molecular level) in the base polymer of a plastics composition, and
therefore remain in particulate form when incorporated in the
composition by proper compounding procedures: dyes are colouring
materials which are soluble in the above sense.
402 W. V. Titow

Note: The primary particles of a typical organic pigment may range


in size between about 0·5 and 5 ,urn, and may be made up-or
consist-of pigment crystals of sizes 0·005-1,um. The
primary particles may form aggregates up to several tens, and
agglomerates up to several thousands, of micrometres in size:
these should be broken up into their constituent primary
particles in the compounding operation.
The colour of a coloured substance is due to selective absorption by
its molecules of some wavelengths from the incident light; the actual
colour seen by the eye is determined by the wavelengths remaining in
that part of the light which is transmitted or reflected. To be useful as a
colourant, a substance must be of a colour sufficiently intense to impart
it in the desired degree to the material to be coloured when
incorporated in relatively low proportions (in PVC compositions the
colourant contents normally range from fractions of a phr to a few phr
except for the special case of comparatively much higher loadings of
titanium dioxide or carbon black in certain compounds-see below): it
must also be compatible with the material and suitable in several other
respects (see below).
Where a colourant has an opacifying effect in a basically transparent
plastics composition, this is due to the scattering of light at the
colourant/plastic interface within the composition. It follows that the
effect will arise only if the colourant is insoluble in the composition,
and hence present in particulate from (i.e. acts as a pigment, not a
dye), and if-in addition-the particles are:
(i) large enough in relation to the visible light wavelengths
(0·750-0·400,um, respectively, for the extremes of the red and
violet spectrum bands) to permit scattering, as well as
(ii) either opaque or sufficiently different in refractive index from
the composition to enable significant internal scattering to occur.
It is because they do not entirely meet condition (i) that some
pigments of sufficiently small particle size can be used in translucent-
to-transparent compositions.
Note: Similar considerations apply to other formulation components
(fillers, flame retardants, impact modifiers): MBS modifiers
provide an illustration of the case where condition (ii) is not
fulfilled, i.e. where an additive forming an essentially discrete
disperse phase of effective particle size large enough for
11 Some Miscellaneous Components of pvc Formulations 403

interference with light, has no opacifying effect because its


refractive index matches that of the composition (cf. Section
1l.2.2(c)).

11.3.2 General Classification

As has been indicated in Chapter 4 (Section 4.4.1(g)) the following


general classification of colourants used in plastics may be made on the
basis of their nature and chemical composition:
Dyes (organic compounds)
Pigments
Organic pigments: substantially insoluble organic compounds; also
carbon blacks which consist essentially of elemental carbon,
occasionally tinted with an organic colourant.
Toners: Ba, Ca, or Mn salts of azo dyes.
Lakes: complex salts of basic dyes with certain acids, especially
phosphomolybdic, phosphotungstic, and phosphotungstomolybdic
acids.
Inorganic pigments: predominantly salts or oxides of certain
metals; this group includes the important white pigment, titanium
dioxide.
Several chemical types and combinations are represented among the
special effect pigments, which include: (i) metallic colourants (metal
flakes, usually aluminium for silver effects and copper or bronze for
gold; may be tinted with organic colourants for metallic colour effects);
(ii) pearlescent colourants (often based on bismuth and lead com-
pounds; some on titanium/mica combinations, e.g. some Mearlin
Luster pigments of the Mead Corporation, USA, for which superior
weatherability is claimed); (iii) glossy and nacreous colour pigments (as
represented, for example, by the [riodin range of E. Merck, West
Germany); and (iv) fluorescent pigments, whose recent commercial
representatives have much improved heat resistance (up to about
300°C in some cases) and light stability (cf., for example some Swada
Z/N and Day-Glo VC fluorescent colourants of, respectively, Swada
(London) Ltd, in the UK, and the Day-Glo Colour Corp. in the USA).
Most of the common dye classes (including azo, anthraquinonoid,
basic, nigrosine, indoline, quinophthalone, and aniline-black dyes) are
represented among dye colourants for plastics. Virtually all these
colourants have some solubility in common solvents, oils, fats and
404 W. V. Titow

plasticisers. For this reason they are relatively little used in flexible
PVC compositions in which their solubility can give rise to troubles
associated with migration ('bleeding', 'marking-off', 'blooming'). As
organic compounds with high degree of unsaturation the dyes (and
many of the closely related organic pigments) are fairly sensitive to
light (prone to fading or changes of shade). Their molecular state of
dispersion in PVC compositions also makes them more accessible to
light, and thus accelerates any photochemical effects they may suffer in
both pPVC and uPVc. Examples of commercial dye colourants for PVC
include Red HHR and Blue B (Hoechst) used in coloured gramophone
record compounds; Amaplast Yellow RRT (American Colour and
Chemical Corp.)-an azo yellow for use in rigid compos~tions; and
quinaphthalone yellows for uPVC (Mitsubishi Chemical Industries).
Rhodamine B has been evaluated53 as a fluorescent colourant for PVC
traffic cones, vacuum-formed emblems, point-of-sale displays, and the
like.
Commercial pigment colourants for PVC are discussed in Section
11.3.5; the main groups are listed, with some property data, in Table
11.7. In addition, the following general points may be noted. As with
other additives, the highest possible degree and uniformity of
dispersion* of a pigment in the PVC composition is very important, in
this case for maximum colour value and uniformity of coloration:
hence the form in which the colourant is used (see Section 11.3.3)
should be considered, inter alia, from the point of view of dispersibility.
Stability of PVC compositions may be reduced by some pigments
containing iron and zinc (especially salt-type pigments in which ions of
these metals are present, or pigments containing such ions as
impurities). Pigments containing barium, cadmium, lead, tin, or
calcium may have the opposite effect. Some pigments (notably carbon
black and titanium white-see Section 11.3.5) can improve weathering
resistance (d. also Chapter 12, Section 12.6, and Chapter 4, Section
4.4.1(g». Occasionally an interaction may be possible between certain
dyes and fillers: this effect is not very common, but in case of doubt
reliable advice can be had from the colourant supplier on this point.
Any colourant used should also be resistant to HCI which may be
liberated in the composition in processing or service: for example some
* A standard specification of interest in this connection is ASTM D 3015-72
(reapproved 1978). Microscopical examination of pigment dispersion in plastic
compounds.
11 Some Miscellaneous Components of pvc Formulations 405

iron oxides are susceptible to attack by Hel. Stability of the colourant


to the other formulation components, especially at processing
temperatures, is another relevant consideration. Some organic pig-
ments, as well as the dye components of toner or lake pigments can
migrate, especially in plasticised compositions. For example, the older
monoazo pigments often caused trouble by migrating to, and
accumulating on, the surface of products, sometimes shortly after
manufacture or early in service: such effects are known as 'blooming',
'bleeding', 'chalking' or 'bronzing'. They occur usually where the
pigment is not sufficiently insolubilised, and can dissolve in the
polymer/plasticiser system. In such cases, by and large, the higher the
plasticiser content the worse the effect. Some monoazo pigments are
still notorious in this connection, but there are newer ones which are
sufficiently insolubilised to be fully suitable. Where the tendency
exists, high processing temperatures will accentuate 'blooming' and the
other effects; with rigid and semi-rigid products the problem would be
less acute because of the absence of, or the low, plasticiser content. It
may sometimes appear that where 'bleeding' occurs, transparent
compounds do not bleed as much as opaque ones. However, this is not
a basic difference and may be due simply to the fact that the
transparent compounds will normally contain less colour.

11.3.3 Forms in which Colourants are Available

A colourant is usually available in different physical forms. In any


given case the choice of a particular form-like that of the kind of
colourant to be used-will be made in the light of the various
considerations summarised in Section 11.3.4. The following forms are
available:
(i) 'Dry colours': These are colourant powders with no additives,
except for small amounts of lubricants, wetting agents, or
dry-flow promoters (anti-caking agents) which may be present in
some cases. Nowadays most dry colours are available in special
non-dusting powder grades or in granulate form.
(ii) Colour concentrates: A colour concentrate is a compound
consisting of a high proportion of colourant dispersed in a
carrier. Depending on the nature of the carrier the concentrate
will be either solid or liquid.
406 W. V. Titow

Solid concentrates in which the carrier is the same polymer as that of


the composition for which the colourant is intended, are known as
masterbatches. The term is also often applied to solid concentrates
whose carriers are polymers compatible, but not identical, with those
of the compositions to be coloured. Such 'universal' polymeric carriers
in some colour concentrates suitable for use in PVC can be vinyl
chloride/acetate copolymers (as, for example, in the Hoechst Hosta-
vinyl pigment concentrate series) or EVA copolymers. A widely
compatible carrier is a feature of the Siscoversal concentrates (BASF)
which are suitable for use in PVC, inter alia, at up to 3 phr loading.
Non-polymeric carriers are also used in some concentrates (e.g. a fatty
acid or a lubricant wax, respectively in the Ciba-Geigy Microlith and
the Hoechst Remafin ranges). The solid masterbatch concentrates are
available in the form of standard pellets containing up to about 50%
colourant. Powder forms are also supplied-e.g. the Microspin dustless
concentrate powders of the Hilton Davis Chemical Co. in which the
colour (or titanium white) loading can be as high as 70% (in a
low-melting, heat-stable 'universal' carrier). In comparison with a dry
powder colourant the masterbatch offers ease and economy of
handling, freedom from dusting, and ease of dispersion in processing
(powder-form concentrates are, moreover, suitable for dry blending).
However, whilst the colourant in a masterbatch pellet or particle is
already 'wetted out' by, and intimately dispersed in, the resin carrier,
because of the high colourant content the viscosity of the molten
masterbatch in melt compounding is liable to be higher than that of the
composition to be coloured: thus, although problems in dispersing the
colourant as such are reduced, attention must be paid to ensuring that
the masterbatch compound is thoroughly blended with the composi-
tion. Since compounding a masterbatch with a composition to be
coloured amounts to a dilution of the former, it is common to refer to
the operation as 'letting down' the masterbatch: let-down ratios may
range from 100: 1 to 3: 1 (uncoloured composition or polymer to
masterbatch). Liquid concentrates of interest for PVC are normally
dispersions of colourants in plasticisers, often referred to as paste
concentrates.

(iii) Combinations of colourants with other formulation components


(stabiliser/lubricant systems and occasionally also other addi-
tives, e.g. antistatic agents, fillers) in single-pack systems;
'tailored' by the supplier for particular, specified types of PVC
compositions (see also Chapters 9 and 10). The main advantage
11 Some Miscellaneous Components of pvc Formulations 407

of such polyfunctional systems to the user is convenience (with


elimination of individual-component storage and metering or
weighing-out operations, and some pre-dispersion of col-
ourants, fillers, etc., where present). The principal limitation is
on formulation flexibility; the price of proprietary single-pack
systems also reflects the supplier's blending, handling and
packaging costs.
Note: Broadly speaking, similar considerations apply to the use of
coloured compounds available from suppliers for direct
conversion into products by appropriate processes.

11.3.4 Choice of Colourant-Main Considerations

The principal considerations influencing the choice of colourant or


colourant system for a PVC composition (as for most plastics
compounds in general) may be grouped under the following headings.

(a) General Appearance and Colour Requirements


The relevant elements here will be the optical properties of the
composition (i.e. whether transparent, translucent, or opaque: ultra-
fine particle pigment grades may be suitable for all three categories),
the actual colour required, colour strength and brightness, and any
special effects (e.g. fluorescence, metallic or pearlescent effects).
Where various levels of colour strength may be required but
preservation of the same shade is important, the possibility of spurious
shade changes associated solely with differences in colourant concen-
tration level should not be overlooked: such changes-which can occur
in PVC compositions coloured with commercial pigments-have been
attributed to dichroic effects. 54 Sophisticated microprocessor-based or
computerised colorimeters and colour analysers are available nowadays
to assist the plastics processor with colourant quality control, rapid
colour matching* and adjustments in formulation development, and

*Standard colours for matching are listed in the Dictionary of Colour


Standards originally contained in BS 543:1934, which no longer exists as a
standard, Other BS standards of interest are BS 381C-1964 (Colours for
specific purposes) and BS 4800:1972 (Paint colours for building purposes).
Colours for cables are given in BS 6746C:1969: in formulating coloured cable
compounds the possible effect of the colourant on the volume resistivity and
power factor should be considered; colourants specially produced for this
application are available.
408 W. V. Titow

the monitoring and control of colour quality and uniformity, and shade
consistency in production. The following equipment may be mentioned
by way of non-selective examples: the Gardner XL-80S colorimeter
system;55 the Vibrochrom FFR 2 colorimeter with companion compu-
ter (Chemiefaser Lenzing AG, Austria);56 the 7842 Color Analyzer II
(IBM Instrument Systems, USA); Match-Mate 3000 (Diano Corp.,
USA); and ACS 500 (Applied Color System, USA).57

(b) Processability and Stability in Processing


Considerations here will include ease of handling, conveying and
metering of the colourant; suitability for, and ease of dispersion in, the
relevant process(es) and type of PVC composition; own stability under
processing conditions (especially chemical and colour stability to heat
at PVC processing temperatures-general range approximately 170-
220°C) and absence of adverse interactions with composition
constituents (or their decomposition products-e.g. HCI from PVC
polymer) under these conditions. An experimental scheme for the
evaluation of the suitability of pigments for use in polymers processed
at high temperatures proposed by Sonn58 is of interest in connection
with PVC (although the author does not include it among his 'high
temperature polymers').

(c) Stability and Permanence in Service


The points relevant under this heading will include permanence of
colour (no fading or shade changes) associated with resistance to such
environmental influences as heat, photochemical action, and other
weathering or ageing factors: resistance to migration and extraction
(e.g. on contact with such agents as detergents, polishes, oils); no
adverse interactions of the colourant (including any impurities therein)
or its decomposition products with the PVC polymer or other
constituents of the composition. Examples of pigments developed with
a view to compatibility with appropriate stabilising systems, and own
good weathering resistance in dark shades in such outdoor uPVC
products as window frames, cladding and profiles, are the BASF
Sicotan yellows and some pigments in the Ciba-Geigy Cromophtal
range. The former are Ni/Ti and CrlTi compounds which may be
combined with appropriate organic or inorganic pigments to produce
dark shades. The Ciba-Geigy materials (as represented, for example,
by the widely used Cromophtal Brown SR) are mainly organic
pigments with low IR absorption which limits heat build-up on
11 Some Miscellaneous Components of pvc Formulations 409

exposure to sunlight. Iron-free pigments recommended for outdoor


applications in PVC are available from several suppliers.

(d) Health and Safety Considerations


These include: (i) general safety in handling and processing (e.g.
possible explosion hazards associated with fine powders); (ii) possible
toxic or carcinogenic effects in handling and processing; and (iii)
similar effects on direct body contact or food contact with the PVC
product containing the colourant. With most colourants used on any
scale in PVC (and especially when in the form of concentrates or as
components of single-pack systems) (i) is not normally a cause for
special concern.
In the area of exposure hazards to processing operatives, and
possible hazards associated with use of end products (especially in
beverage and food contact applications), attention has been focusing
on three topics: inorganic pigments containing heavy metals which may
act as potential cumulative poisons; polychlorinated biphenyls, present
as impurities in organic colourants of the phthalocyanine and diarylide
type, and regarded as potentially carcinogenic; and organic colourants
based on benzidine, now widely recognised as a carcinogen.
Of the heavy metals present in colourants, lead is already subject to
stringent exposure limits in the USA and other countries: the
regulations thus affect lead chromate and lead molybdate pigments
(see Table 11.7) as well as lead-based stabilisers and lubricants. The
lead chromates are additionally suspect as a result of recent work in
the USA on the potential hazards of chromium (especially hexavalent
chromium).59,6o The question of the degree of hazard associated with
cadmium compounds affects both cadmium pigments and stabilisers.
Whilst the issue of appropriate official restrictions is still under
debate, any limitations (or outright bans as currently proposed in
Sweden 61 ) will adversely reflect on the usage of the cadmium reds and
yellows (see Table 11.7) so valuable technically for their heat and light
stability: many manufacturers are already looking into alternatives for
cadmium pigments and stabilisers. As with other PVC formulation
components, information and guidance on the latest thinking, and any
specific regulations, concerning the possible health hazards associated
with colourants are available from the various official and professional
bodies mentioned in Chapter 7, Section 7.12 and Chapter 12, Section
12.9. Organisations directly concerned with colourants include the
USA Dry Colour Manufacturers Association, the UK Society of Dyers
410 W. V. Titow

and Colourists, and Oil and Colour Chemists Association, and the
German Mineralfarben-industrie eV.

(e) Cost
This is an important consideration, applicable no less to the colourants
than to any other constituents of a PVC formulation.

11.3.5 Some Commercial Pigments*

There are many world-wide manufacturers of pigments and many


different chemical types; it would be a formidable task to list them.
Most of the manufacturers issue copious data on their products but
correlation of one range with others is not easy, nor is it a simple
matter to relate trade names with chemical constitution. Test data on
the other hand are fairly well standardised. Thus a simple compound is
used, e.g.
PVC polymer (e.g. Corvic H65/33-ICI Ltd) 100
Plasticiser: e.g. DOP or Reomol D79P (Ciba- 50phr
Geigy)
Stabiliser: either basic lead carbonate paste or a 8-10phr
Baled soap and epoxidised oil in functionally
equivalent proportion
Colourant and titanium dioxide as indicated
to evaluate the various properties as follows. t

Heat stability: A cut of hide from the mill is pressed between


polished steel plates for 30 min at 170°C and the resulting sheet is
compared with one pressed for 5 min. Alternatively, portions of sheet
pressed for 5 min are further heated in a thermostatically controlled air
oven for 30 min at 170°C or 10 min at 200°C. Any difference is assessed
on the SDC Geometric Grey Scale (BS 2662: 1961) on a 5 to 1 rating,S
equalling no change, 1 equalling very considerable change. These
relatively long times are used to cover extremes of direct heating or the
cumulative effects Of reworking.

* This section, edited and supplemented for the present" edition, was originally
contributed (to the previous edition) by Mr H. G. White of ICI.
tThese tests were used by the compiler of Table 11.7. Other tests (some more
stringent) can be applied, e.g. those detailed by Ciba-Geigy in connection with
that company's rating of its pigments for PVc. 63
11 Some Miscellaneous Components of pvc Formulations 411

Migration: A specimen of coloured sheet is held in contact with a


piece of white PVC under a weight of 1·0Ibfin- 2 . The assembly is
placed .in an oven for 24 h at 70°C and the degree of staining assessed
on a 5-1 scale.

Dry rubbing: A piece of coloured sheet is rubbed with a piece of dry


cotton fabric.

Wet rubbing: As for 'dry rubbing' except that moist cotton is used.

Soap fastness: A specimen of coloured sheet is placed between a


piece of cotton and a piece of wool. The assembly is rolled and
immersed in soap solution for 1 h at 60°C. Staining is assessed on the
1-5 scale. (Solution prepared by dissolving 5 g soap flakes and 2 g
anhydrous sodium carbonate in 1 litre of water.)

Light stability: Coloured specimens are exposed to daylight and


assessed according to BS 1006: 1978 using the Blue Scale of Standards
against which the light fastness is rated (upwards) from 1 to 8.

The chemistry and properties of pigments available for and used in


PVC have been reviewed by White62 who originally compiled Table
11.7. The salient characteristics of the main chemical classes into which
the pigments have been grouped in the table may be summarised as
follows:

A. Toners: Alkaline earth metal salts of organic azo dyestuffs;


they give bright strong colorations but only moderate light fastness,
whilst the salt linkage gives susceptibility to colour change if the PVC
compound is changed. Newer types are giving better light fastness.

B. Disazo pigments: Mainly derived from substituted benzidine,


these are strong yellow to red pigments of good to very good light
fastness but may show a trace of solubility and colour change if
processed at high temperatures and low concentrations.

C. Condensed disazo pigments: These are made by condensing two


monoazo pigments, giving weaker but brighter colorations than
conventional disazo types with better light fastness and less solubility.
TABLE 11.7
Pigments for PVC and Some of Their Properties
Chemical type Brand name C.l. Ref. (Pt 1)0 Amt % in Light Heat
for! patterns b fastness C stabilityd
ISD
(%) F P F P F P

(A) Toners
Barium-2B Vulcafor Red AS P.Red 48 0·15 0·5 0·01 4 1-2 5 4Y
0 0
Strontium-2B FW Rubine Toner BOS PoRed 48 0·15 05 0 01 5-6 2-3 3-4 4Y
Manganese-2B Rubine Toner 2BRS PoRed 48 0·10 0·5 0·01 6D 3 5 4Y
Calcium-2B Irgalite Red RC P.Red 48 0·10 0·5 0·01 5 3 2Y 3Y
Calcium-4B Vynamon Claret YS P.Red 57 0·10 0·5 0·01 4 1-2 3Y 3Y
Ca-monoazo Irgalite Red HGL P.Red 134 1·0 1·0 0·02 6 - 5 5
Ba-monoazo Irgalite Red HBL P.Red 133 0·5 1·0 0·02 6-7 - 5 5
0
Ca-ONPSA Irgalite Yellow WSC N.L. 0·5 2·0 0 04 6-7 - 5 5
Ba-ONPSA Irgalite Yellow WSR P.Yellow 62 0·5 2·0 0·04 7 - 5 5
Ba-monoazo P.V.Red H4B P.Red 151 0·25 0·5 0·01 6 5-6 5 4
(B) Disazos
TCB/AAMX P.V.Fast Yellow HlOG P.Yellow 81 0·50 0·5 0·01 6-7 6 5 4
DCB/AAOA Irgalite Yellow 2GP P.Yellow 17 0·10 0·5 0·01 7 6 5 4B
DCB/AAMX Vynamon Yellow GRES P.Yellow 13 0·10 0·5 0·01 6-7 5-6 5 4B
Irgalite Yellow BAF N.L. 0·10 0·5 0·01 7 6 4 2B
DCB/AA2MCA P.V.Fast Yellow HR PoYellow 83 0·05 0·5 0·01 7 6 5 5
DCB/PMP Vynamon Orange GS Po Orange 13 0·10 0·5 0·01 6 4 4-5 4-5
Irgalite Orange F2G N.L. 0·075 0·5 0·01 6 4 4-5 2Y
DCB-DA/PTMP Vynamon Red GES P.Red 111 0·05 0·5 0·01 5 3 5 2Y
DCB/PCP Irgalite Red PYE P.Red 38 0·05 0·5 0·01 5 3 5 2Y
(C) Condensed Disazos
See: JOCCA (1963), Cromophtal Yellow 6G P.Yellow 94 0·5 0·5 0·01 7 7 5 5
p. 13, and (1968), Cromophtal Orange 4R P.Orange 31 0·1 0·5 0·01 6-7 5 5 5
p.580 Cromophtal Red GR P.Red 139 0·1 0·5 0·01 7 6 5 4-5
Cromophtal Red BR P.Red 144 0·1 0·5 0·01 7 6 5 4-5
Cromophtal Red R P.Red 140 0·1 0·5 0·01 6-7 5-6 4-5 4Y
Cromophtal Rubine B P.Red 142 0·1 0·5 0·01 6-7 5 5 4Y
(D) Insolubilised
Monoazos P.V.Red HFG P.Orange 38 0·20 0·5 0·01 6-7 6 4-5 4Y
No disclosures P.V.Carmine HF4C P.Red 185 0·10 0·5 0·01 6-7 6 5 4-5
P.V.Fast Bordeaux HFR P.Red 183 0·10 0·5 0·01 7 7 5 5
P.V.Fast Maroon HFM P.Red 171 0·08 0·5 0·01 7 6-7 4-5 4-5
P.V.Brown HFGG N.L. 0·25 0·5 0·01 7 6-7 5 4Y
Vynamon Yellow 8GS P.Yellow 105 0·40 0·5 0·01 7 6-7 5 4-5
P.V.Carmine HR P.Red 150 0·10 0·5 0·01 5 3 5 3-4
P.Y.Pink FL P.Red 187 0·22 0·5 0·01 6 5 5 3Y
(E) Polycyclics
Indanthrone Vynamon Blue 3RS P.Blue 60 0·08 0·5 0·01 7 7 5 4
Dioxazine Vynamon Violet 2BS P.Violet 23 0·05 0·5 0·01 7 7 5 5
Dioxazine Irgazin Violet BLT P.Violet 35 - 0·5 0·01 7 6 4-5 1
Thio indigoid Cromophtal Bordeaux RN P.Red 88 0·16 0·5 0·01 7 6 5 3Y
Perylene P.V.Fast Red B P.Red 149 0·08 0·5 0·01 7 7 5 4-5
Perinone P.V.Fast Orange GRL Vat Orange 7 0·20 0·5 0·01 7 6-7 5 3Y
Flavanthrone Cromophtal Yellow A2R P.Yellow 112 0·30 0·5 0·01 7 6-7 5 4-5
Quinacridone {3 Cinquasia Violet RT 795D P.Violet 19 0·13 0·5 0·01 >7 6-7 5 4D
Quinacridone a P.V.Fast Red E5B P.Violet 19 0·50 0·5 0·01 >7 7 5 4Y
(F) Isoindolinones
7th FAT/PEC Irgazin Yellow 2GLT P.Yellow 109 0·40 0·5 0·01 7D 6-7D 5 4B
Congress Irgazin Yellow 3RLT P.Yellow 110 0·50 0·5 0·01 7D 7D 5 5
(1964), p. 61 Irgazin Orange RLT P.Orange 42 0·25 0·5 0·01 7D 7D 5 4Y
Irgazin Red 2BLT P.Red 180 0·25 0·5 0·01 7D 7D 5 4Y
TABLE 11.7-eontd.
Chemical type Brand name C.l. Ref. (Pt l)a Amt %in Light Heat
for! patterns b fastness C stabilityd
ISD
(%) F P F P F P

(G) Phthalocyanines
CPC, ll'form Irgalite Blue BLP P.Blue 15 0·06 0·5 0·01 >7 >7 4-5 3Y
CPC, stable ll' Vynamon Blue LBS P.Blue 15 0·07 0·5 0·01 >7 >7 5 4Y
CPC, f3 form Monastral Fast Blue BGS P.Blue 15 0·08 0·5 0·01 >7 >7 5 3-4Y
Chlorinated CPC Vynamon Green BES P.Green 7 0·16 0·5 0·01 >7 >7 5 4-5
Brominated CPC Vynamon Green 6YS P.Green 41 0·20 0·5 0·01 >7 >7 5 5
(H) Other Organics
Iron nitroso-f3-napthol Vulcafor Green LS P.Green 8 0·10 0·5 0·01 6 5 4-5 3
Aniline black Monolite Fast Black LS P.Black 1 1·0 0·5 0·01 7 7 5 5
Carbon black Kosmos 70 P.Black 7 0·05 0·5 0·01 >7 >7 5 5
(I) Cadmiums
Cadmium sulphide Cadmium Yellow P 3680 P.Yellow 37 1·0 5 0·1 7 6-7 5 5
Cadmium Primrose P 500 1·0 5 0·1 7 6-7 5 5
Cadmium Lemon Yellow P 3682 1·0 5 0·1 >7 6-7 5 5
Cadmium Light Orange P 4701K 0·75 5 0·1 7 6-7 5 5
11 Cadmium Deep Orange P 4702K 11 0·75 5 0·1 7 6-7 5 5
Cadmium Light Red P 4703K 1·0 5 0·1 7 6-7 5 5
Cadmium Scarlet P 4704K 1·0 5 0·1 7 6-7 5 5
11 Cadmium Red P 4705K 11 0·75 5 0·1 >7 7 5 5
Cadmium Deep Red P 4706K 0·75 5 0·1 >7 7 5 5
Cadmium selenide Cadmium Crimson P 4707K P.Red 108 0·75 5 0·1 >7 7 5 5
Cadmium Maroon P 4708K 0·75 5 0·1 >7 7 5 5
(J) Chromes
Lead chromate Vynamon Yellow 6GNS P.Yeliow 34 1·0 5 0·1 7D 7D 5 5
Supra Lemon Chrome 4GS 1·0 5 0·1 7D 7D 5 5
Vynamon Yellow CRNS 1·0 5 0·1 7D 7D 5 5
II Supra Orange Chrome HYS II 1·0 5 0·1 7D 7 5 5
Lead molybdate Supra Scarlet Chrome YS P.Red 104 1·0 5 0·1 7 7 5 5
Supra Scarlet Chrome MS 1·5 5 0·1 7 7 5 5
(K) Other Inorganics
Chromic oxide Chrome Green DC 3593 P.Green 17 2·0 5 0·1 >7 7 5 5
Ultramarine - P.Blue 29 0·75 5 0·1 7 7 5 4Y
Iron oxide P.V.Fast Brown G P.Brown 6 0·3 5 0·1 >7 7 5 5
a Colour Index (Part I) Ref: N.L. = Not listed.
b Patterns: F = Full Shade; P = Pastel Shade in white plasticised PVC; D = Darkening.
C Light fastness: Daylight, Blue Scale 8-1 ratings BS.

dHeat stability: 10 min at 200°C in air oven. Grey Scale 5-1 ratings.
416 W. V. Titow

Plate A Laboratory-scale equipment for PVC processing (Farrel Bridge


Ltd.). (1) Two-roll mill (swing-side, variable friction, rolls 6 in x 13 in).

D. Insolubilised monoazo: These are types in which heavy substitu-


tion of the simple monoazo pigment has suppressed solubility to very
acceptable levels; usually this is obtained at appreciable financial
expense.
E. Polycyclic compounds: These are offshoots of the vat dyestuffs
used on textiles; this highly selected group of colours give very high
strength, fastness and brilliance but at a very high cost.
11 Some Miscellaneous Components of pvc Formulations 417

Plate A-<:ontd. (2) Four-roll laboratory calender ('inverted L' type, rolls
6 in x 15 in).

F. Isoindolinones: These form a new group from the polycyclic class


with a shade range greenish yellow to bluish red of very good light
fastness and insolubility.
G. Phthalocyanines: These are a very old specialised type of
polycyclic giving the most stable blue and green pigments at
comparatively very low cost.
H. Carbon black: This term is often used as a general name for the
group of particulate carbon pigments, whose members are known
under names derived from the methods of their preparation (which
also affect the particle size, surface 'chemistry,64 and degree of
blackness), e.g. furnace blacks, channel blacks, lamp blacks (various
grades). Carbon blacks are characterised by small particle size,
outstanding tinting power and hiding strength, heat and light
resistance. The fine-particle furnace blacks have been increasingly
widely used in PVc. As indicated in Chapter 8, Section 8.4.3, apart
418 w. V. Titow

from its action as a black pigment carbon black improves the


weathering resistance of plastics compositions and-in sufficiently high
loadings-eounteracts static electricity collection and can confer
conductive properties (see Section 11.4 below). A useful monograph
on carbon black, covering both the scientific and technical aspects of
the subject, has been produced by Donnet and Voet. 65
I. Cadmium sulphide and selenides: These form the main group of
yellow-orange-red-maroon inorganic pigments of very high light and
heat fastness with no solubility, but they are both expensive and
tinctorially weak.
J. Chrome pigments: For example, lead chromate and lead molyb-
date form a much less expensive greenish yellow to scarlet range of
pigments in which recent improvements have given light fastness
comparable with cadmium pigments, but they remain susceptible to
strong alkalies and to darkening by hydrogen sulphide.

K. Other inorganics: These include ultramarine, iron oxides and


chromic oxide, which are, respectively, the cheapest brightest reddish
blue, a source of very cheap and fast fawn to brown colours provided
very high processing temperatures are not involved, and the best base
for green colorations for the production of camouflage effects.

The above points are illustrated in terms of numerical data in Table


11.7, in which representative members of the pigment classes discussed
are listed with disclosures of their chemical constitution by reference to
the Colour Index or literature. A comparison of relative tinctorial
strength has been included by indicating the dosage of pigment
required in a clear plasticised PVC composition with 1% titanium
dioxide to give a uniformly strong coloration to 1/3 International
Standard Depth (BS 1006:1978). The light fastness and heat stability
ratings of the pigments as full and pastel shades in the same PVC
composition (with BalCd soap-epoxidised oil stabiliser system) are
then compared.
Titanium dioxide, the most widely used white pigment, has not been
included in Table 11.7. It is available in two crystalline forms-anatase
and rutile. In general rutile is the more stable to light (and hence,
broadly, preferable as a pigment for plastics, especially for outdoor
applications), whilst anatase has a stronger blue undertone. Both forms
are available in various grades differing in particle size and size
11 Some Miscellaneous Components of pvc Formulations 419

distribution, and in the presence (and nature) of surface treatments, so


that the supplier's advice should be sought regarding the choice of
grade for a particular application, although continuous development to
improve the ease of dispersion, blueness of undertone, durability and
resistance to moisture pick-up has made it possible to combine all these
features in a fine-crystal rutile grade.
In addition to its use as a white pigment, titanium dioxide is also
widely employed to enhance the brightness of a colourant. In
proportions appropriate to these two purposes (up to a few phr) this
pigment has no appreciable effect on the physical properties of PVC
compositions. At higher loadings (about 10-15 phr) it can enhance the
weathering properties of some PVC products (e.g. flexible films for
swimming pool and reservoir linings), or-especially when of the finest
particle size-improve the impact properties of rigid materials. 34
Useful information, respectively on the nature of organic pigments,
extractability of colourants (and some other additives) from PVC
compositions, and on all important aspects of the colouring of plastics
(including PVC), is contained in publications by Inman,66 Brighton,67
and Webber. 68

11.4 ANTISTATIC AGENTS

Like many other plastics materials, PVC products and articles may
readily accumulate static electricity charges under certain conditions.
Friction against, and separation after surface contact with, other
surfaces are common ways of charge generation. Since surface charges
leak away more easily in moist conditions, the highest and most
persistent charges result at lowest relative humidities. Charge build-up
is drastically reduced at relative humidities above approximately 80%.
Accumulated static charges can represent a serious potential hazard.
For example, when present on the cover or carcass of a PVC conveyor
belt, the charge may-on discharge-produce a spark which can cause
a fire, or an explosion in a dust-laden atmosphere: such circumstances
can arise in mines, where PVC conveyor belting is used. Charge
accumulation on PVC sheeting can constitute similar hazards in other
environments (including atmospheres containing flammable vapours or
gases). Charges built-up on PVC polymer particles (in conveying,
metering, etc.) can be troublesome; as can those acquired by dry blend
particles in the course of high-speed mixing (in that they can atfect the
420 w. V. Titow

bulk density and handling properties, although they often eventually


dissipate in storage). Finally, attraction of dust and other atmospheric
pollutants to charged plastics surfaces (mouldings, etc.) can result in
dirty marks.
For all these reasons it is necessary to have methods of preventing
static electricity charge build-up. In general the methods employed
may be divided into two broad groups: chemical treatments and
physical treatments. The former treatments involve the incorporation
in the PVC material, or external application thereto, of a chemical (an
'antistatic agent') which will prevent the build-up of charge. The latter
are essentially means of ionising the atmosphere (either with the aid of
a radioactive source or electrical discharge) to enable any charge
build-up to be neutralised. These physical methods are mainly
applicable in the handling and processing of sheet materials. It will be
clear that they do not impart any antistatic properties to the material
itself, and require special apparatus. For all these reasons they are not
of great importance to the present subject and will not be considered
further here.
A recent BS Code of Practice 69 provides useful basic information on
the generation of static electricity, its measurement and control.

11.4.1 Static Electricity Charges on PVC: Phenomena and Tests

In common with many other plastics PVC is a good electrical insulant:


the volume and surface resistivities of the polymer (and many rigid
compounds) are, typically, in the range 1015 _10 17 Q cm and Q,
respectively (at room temperature and about 60% RH).7o Thus, as
mentioned above, the material can readily acquire static charges,
particularly in dry conditions, and retain them for long periods. The
charges on PVC are predominantly negative: as with other plastics, the
charge distribution may be 'patchy' and in some areas a local positive
charge may be present. In their discussion of charge distribution on the
surface of a plastic (polystyrene), Woodland and Zeigler71 suggest,
inter alia, that the widely accepted use of surface resistivity measure-
ments as an indication of the 'static properties' of a compound is not
fully justified. However, in the PVC industry, surface resistivity
measurements still provide the most popular way of assessing the
effects of antistatic agents. Since conduction over the surface of the
material is the principal mechanism of electrostatic charge dissipation,
surface resistivity is indeed the most important single factor in 'static'
11 Some Miscellaneous Components of pvc Formulations 421

phenomena in plastics. Other ways in which static charge may be


dissipated are conduction within the material itself, and ion discharge;
the latter is in fact the mechanism of the previously mentioned physical
methods of combating static in some processes.
The scale and undesirable effects of static phenomena of interest in
practice are closely associated with the magnitude of the charge and
the rate of charge build-up and dissipation. Each can be measured
and-in any but a superficial investigation-they should be evaluated
jointly.
The magnitude of static charge can be measured, in terms of field
strength, by field meters and electrometers of various types. 69 ,72,73
With the proper instrumental arrangement, the field strength measured
is related to the charge density by the expression: 69
a=EoK
where: ais the surface charge density (Cm- 2), K is the field strength
measured (V m- 1), and Eo is the permittivity of free space (8,85 x
1O- 12 Fm- 1).
Field meters can also be used qualitatively to detect the presence of
a charge or locate the point(s) of highest density. A convenient hand
instrument is the 'Statigun',7° a gun-shaped, valve electrometer. The
rate of charge decay can be measured with the aid of electrometers,
but the important point that the charging method must be standard and
reproducible is frequently overlooked. In more fundamental investiga-
tions charging by rubbing is not satisfactory. Measurement of charge
decay in, say, factory conditions (e.g. on sheeting charged in the
course of a particular process) can be meaningful in the limited context
of that process and can give an indication of the efficiency of antistatic
agents and treatments. The figure usually quoted in connection with
charge decay results is the 'half-time', i.e. time required for the charge
to be reduced by a factor of 2.
Good reviews of the generation, nature and measurement of
electrostatic charges on plastics have been published by Quackenbos,74
Ferraris,75 and Gale and Pacitti. 7o
As already mentioned, in practice the 'static' properties of a plastic
are most often gauged and indicated in terms of surface and volume
resistivity, and several standards lay down their requirements in those
terms. Thus, for instance, the maximum resistivity (as determined in
prescribed tests) of PVC conveyor belting for underground use in coal
mines is laid down as 3 x 108 Q by both BS 3289:1960 and the
422 W. V. Titow

appropriate National Coal Board specification (NCB 158/1971), whilst


upper limits for antistatic products for use in hospitals (e.g. anaesthetic
tubing, trolley wheels, mattresses) and industry (e.g. flooring,
footwear, hose) given by BS 2050:1978 are, in many cases, about 106 Q
(5 X 104 Q for flooring in explosive-handling areas). The minimum
volume resistivity requirements for ordinary flexible PVC compounds
covered by BS 2571: 1963 range from 5 x 109 to 1 X 1014 Q (at 23°C).
Standard specifications dealing with general methods of determining
resistivities of plastics are listed in Appendix 3. Methods suitable for
antistatic and conductive plastics (volume resistivities up to about
105 Q cm) are given in ISO/DIS 3915-1980 and BS 2050: 1978, and for
rubbers in BS 2044: 1978. The determination of antistatic properties of
plastics films (three methods, including one based on charge decay) is
covered by BS 2782: Methods 250 A, Band C: 1976.
The attraction of particulate dirt or dust by charge-bearing plastics
surfaces is the basis of a group of tests which, whilst not very precise,
do give some visual indication of the magnitude of the charge. Because
of their low accuracy and limited reproducibility their use should,
however, be confined either to rough, practical pointer assessments or
to strictly routinised checks under standardised conditions. Two
common tests of this kind are the ash test and the 'dirt chamber' test. 71
In the former the plastics material is charged by rubbing and the
amount of cigarette ash picked up by the surface is observed. In the
popular Procter and Gamble version of the dirt chamber test the
plastics article or material charged by rubbing is placed in a cabinet at
80°F (27°C) and 15% RH, and smoke (produced by burning a piece of
filter paper saturated with toluene) is introduced into the chamber.
The pick-up of the particulate combustion products by the material is
observed.

11.4.2 Nature and Use of Antistatic Agents

Antistatic agents .are chemicals which are either incorporated in a


plastics material, or applied externally, to reduce static charge build-up
and promote charge dissipation, by lowering the resistivity of the
material. They are cationic, anionic or non-ionic in nature, and
commonly belong to one of the following groups of compounds:
Amines and amides, e.g. Lubrol PE (ICI); Lankrostat LDN (Lank-
ro Chemicals Ltd)
11 Some Miscellaneous Components of pvc Formulations 423

Quarternary ammonium compounds, e.g. Ethoquad e12 (Armour


Industrial Chemical Co. (USA) or Armour Hess Chemicals Ltd
(UK»; Lankrostat QA T
Polyethylene glycol derivatives, e.g. Gafstat AE 610 (GAF Corp.)
Sulphates and sulphonates e.g. Querton 14 ES or 16 ES (Guest
Industrials Ltd)
Miscellaneous ethers and esters

Conductive polymers are also offered from time to time as antistatic


agents, for example, Resin QX2611 (Dow)-a copolymer of a
quaternary ammonium compound with styrene, or Ionac PE 100
(Ionac Chemical Co.).
Typically, about 2-5 phr of an antistatic agent may be incorporated
in internal application (but up to about 10 phr with some agents-see
below). External application (normally to semi-products, e.g. film, or
mouldings by spray, wipe or dip) is usually from solution of 0·1-2·0%
concentration; but soaking the pellets of a moulding compound in a
50% solution and drying has also been recommended (e.g. with
Ex-Static-Guinness Chemical Co., UK).
In both kinds of application the aim is to form a layer of the
antistatic agent on the surface of the product, which in turn attracts a
layer of moisture, ultimately responsible-in conjunction with the
conductivity of the agent-for conducting away charges. It is because
of this that the effectiveness of antistatic treatments drops at low
relative humidity.
Internal application of antistatic agents gives more permanent
results, because if the surface layer is removed (e.g. by friction against
another surface, or contact with liquids) it can be reinstated by more
reagent diffusing to the surface from the mass of the material. It has
been claimed that this process is detectable by measurement of the
contact angle of water on the plastic's surface. 76 An externally applied
layer of antistatic agent, if removed, can only be restored by
re-application. However, the external method may be reasonably
convenient and useful in appropriate cases: inter alia it affords the user
a simple means of keeping in check dust contamination of gramo-
phone records.
It is well known that most antistatic agents reduce the thermal
stability of PVC (especially uPVC) compositions in which they are
incorporated. However, careful formulation, particularly the selection
of stabilising systems, can minimise the effect in many cases. Analytical
424 W. V. Titow

studies are claimed to indicate that nitrogen-containing antistatic


agents have the strongest adverse effect on heat stability. 77
The incorporation of a conductive filler (most commonly carbon
black, although metal powders-e.g. aluminium, * nickel-may be
used) produces an antistatic effect, or conductivity at sufficiently high
loadings. The use of carbon black for these purposes is old, having
originated in rubber processing. The proportions of the filler used are
high, up to about 35%. Various grades of carbon black differ in their
own conductivity: in general conductivity increases with decreasing
particle size, and with increasing structure, surface purity and
crystallite size and orientation. High-structure furnace blacks are
therefore particularly suitable. 78 t Whilst excellent permanent antistatic
effect or conductivity can be achieved, the method is obviously limited
to compositions acceptable in black.
Two further points may be mentioned. Firstly, plasticisers, and to
some extent also other constituents of PVC compositions, can affect
resistivity, and this should be borne in mind both from the point of
view of the resulting effect on static accumulation, and the insulation
properties in electrical applications. Secondly, certain antistatic agents
which have to be used in substantial proportions for their maximum
effect can have an appreciable plasticising action: examples are Antistat
A (Albright and Wilson) and Irgastat 51 (Ciba-Geigy), both used in
flexible compositions in amounts of up to 10 phr. The effect of Antistat
A on some properties of a flexible composition (Breon P13011+
plasticised with TXP and Pliabrac 987§ in the ratio 70: 30) is illustrated
in Table 11.8

11.5 FLAME AND SMOKE RETARDANTS

11.5.1 General Mechanism of Burning of Polymers and Plastics

The mechanism of burning of polymers, alone or as base constituents


of plastics compositions, comprises two processes-pyrolysis and
* Conductive thermoplastic compounds (including PVC) filled with aluminium
alloy flake are commercially available, e.g. Emiblend (Howard Industries Inc.,
Clark, NJ, USA).
t Special proprietary brands are available for use in thermoplastics, including
PVC, e.g. Conductex 975 (Columbian Chemicals Co., Tulsa, OK, USA).
:j: Emulsion PVC polymer, K value 70-74 (BP Chemicals International Ltd).
§ Nonyl ester of saturated CC C6 dibasic acids (Albright and Wilson Ltd).
......
......
~
::i
'"~
!:;"
TABLE 11.8
Some Effects of 'Antistat A' in a pPVC Compound ~;::
~
Plasticiser (total content) 70 phr 80 phr 90 phr 100 phr 1:;

Addition of Antistat A, (phr) 0 5 10 0 5 10 0 5 10 0 5 10 i


Surface resistance (Q x 107 ) 2500 20 10 1000 15 7 450 11 5 300 7 4 §
Modulus at 100% elongation 830 720 630 640 580 520 530 480 430 480 420 390 ~
(lbfin- Z) to
Cold flex temperature ~
"t:l
eC, Clash and Berg) -25 -29 -33 -31 -34 -37 -36 -38 -40 -39 -41 -43
ri
~
3l::
i:>

a

~
Vl
426 w. V. Titow

combustion. Pyrolysis is the breakdown (thermal degradation) of the


solid polymer material to products of lower molecular weight,
including simple, volatile, hydrogen-rich compounds, and conjugated
linear and cyclic compounds. Combustion is the process of exothermic
oxidation of the pyrolysis products. Both processes involve, inter alia,
the formation and re-combination of free radicals: it has been
suggested25 ,79 that flammability is considerably influenced by the ease
and rate of formation of HO* radicals. Both processes are complex,
and need suitably elevated temperatures to initiate and sustain them:
combustion additionally requires oxygen (pyrolysis can proceed
without it, although its absence will affect the temperatures involved
and the nature of degradation products formed). Pyrolysis starts first
(with many organic polymers the rate is appreciable at about 300°C in
air), but once the amount of breakdown products generated and the
rate of their continued formation are sufficient for combustion to
commence (Le. for those constituents of the pyrolysate which are
present in gaseous, vapour, or fine-mist form to be ignited) and to
proceed, the two processes run concurrently, with the heat produced
by combustion actuating, or contributing to, further pyrolysis, which in
turn provides more degradation products for the combustion process
(see Fig. 11.6).
The pyrolysis products may be first ignited (Le. the combustion
process started) by contact with an external source of intense heat
(normally a flame, but, for example, incandescent-or simply very
hot-electric wires can also be the source in fire situations): this is
sometimes termed 'flash ignition'. Spontaneous ignition (self-ignition)
may also occur when the concentration and temperature of pyrolysis
products have reached suitable values. For a given polymer or plastic
these values will depend on the composition of the material and the
conditions (cf. Chapter 12, Section 12.10): 450°C is fairly representa-
tive as the flash ignition temperature for rigid PVC (normal impact
strength grade) in the test of ASTM 1929-78 (cf. Chapter 12, Table
12.12). In general, as has been mentioned in Chapter 12, the burning
behaviour of a plastic is cardinally dependent on the conditions, to
which any descriptive terms (like 'non-flammable', 'slow-burning',
self-extinguishing', etc.) must relate. However, in many tests and
actual service situations where the plastic is not in continuous contact
with an 'external' flame, it may be properly described as self-
extinguishing if the burning process is not self-sustaining in the sense
that the heat generated by the material's own combustion is not
11 Some Miscellaneous Components of pvc Formulations 427

sufficient to maintain the high temperature required for, and the rate
of, pyrolysis at a level necessary to provide enough pyrolysate (in
suitable form-i.e. gaseous or fine mist) to keep the combustion going.
Any of the products of both pyrolysis and combustion (see Fig. 11.6)
may find their way into the smoke emitted by a burning plastic. In
terms of its physical nature smoke is a suspension of particles in a
mixture of air and the gases and vapours generated in the burning
process (and remaining uncondensed into liquid droplets or layers on
existing particles).8D-82 The particles of the particulate phase may be
solid or liquid (or some of each); some at least may have a solid
carbon 'skeleton'.83 Gases and vapours are invisible: hence, in any
given case (i.e. for a fixed total amount of matter in the smoke) the
smoke density, usually defined in terms of obscuration of light, will be
determined by the proportion of constituents present in the particulate
phase, and to some extent also by the particle size and size
distribution. In general, the greater the amount of pyrolysis products in
the smoke (i.e. the less complete the combustion) the greater the
visible smoke denisty (because the pyrolysis products tend to have
higher molecular weights than the final products of combustion and
hence condense more readily into droplets when mixed with relatively
cool air). In any particular case the actual nature and proportions of
the chemical constituents of the smoke will depend, in a complex way,
upon the chemical composition of the burning plastic and, given that,
upon the burning conditions (especially the temperature and the supply
of oxygen): the same factors also influence the parameters governing
smoke density.

11.5.2 Flame Retardance and Smoke Suppression in PVC


Compositions

It is the large proportion of chlorine they contain that is responsible for


the low intrinsic flammability of PVC polymers and those of their
compositions in which the overall chlorine content has not been
reduced too far by 'dilution' of the polymer with the additives used,
especially flammable plasticisers (see Chapter 7, Section 7.6, and
Chapter 12, Section 12.10). In terms of the mechanisms outlined
above, the presence of chlorine hinders burning through the formation
(mainly in the course of pyrolysis) of hydrogen chloride, which
interferes with the burning process in two ways: being incombustible
itself it prevents, or at least reduces, access of oxygen to the
428 w. V. Titow

POLYMER
(or its dlZrivatlvlZ
plastic)

Pyrolysis +- - - - - - - - - - - --

Liquid or GaslZous (vapour Solid or


SlZmi-liquid phaslZ) dlZgradation SlZml-solid
dlZgradation products dlZgradatlon
products products
('tar') (primary 'char')

FurthlZr pyrolysis +- --i


I
I
I
Solid I
carbonaclZous I
Combustion rlZsidulZ I
\ (slZcondary 'char') I
\ I
\ I
\\ I
\ I
~ I
Combustion

<, HlZat ,/ - -
products (including
/" , I
CO, CO2, H20 and /
various oxidlZS) - - - - - - _ ......
, v
/
/

Fig. 11.6 Simple, schematic representation of the general mechanism of


burning of polymeric materials.
11 Some Miscellaneous Components of pvc Formulations 429

combustion zone; it also reacts with free radicals (especially HO*)


thus acting as terminator for the combustion propagation
reactions. 25,84
Thus, by virtue of its chemical nature, PVC achieves the kind of
flame-retardant effect that in other plastics has to be induced by the
addition-as flame retardants-of halogen derivatives of organic
compounds (sometimes in proportions so large that they affect
adversely the mechanical and other properties).
The effectivity of the flame retardancy mechanism just mentioned
can be preserved in soft and semi-rigid PVC compositions (i.e. those
containing substantial proportions of additives) by the use of
chlorinated paraffin plasticiser extenders or chlorinated polyethylene.
It can also be further improved by the synergistic effect of 'antimony
oxide' (antimony trioxide, Sb20 3) incorporated in relatively minor
proportions (up to about 10 phr). The improvement is usually
explained in terms of the following effects. The antimony trioxide
reacts with the hydrogen chloride generated by burning PVC polymer
(and any chlorinated additives)t to form antimony trichloride, volatile
at the combustion temperature. This is not only more effective than
HCI as a 'barrier' against oxygen, but can actually react with oxygen in
the flame zone (thus reducing the amount available even further). The
reaction products are antimony trioxide-regenerated in the form of a
fume (suspension of very fine particles in the combustion gases)-and
atomic chlorine. The presence of the Sb20 3 particles suppresses
somewhat the generation of the highly active HO* radicals by
reducing the excitation energy for the oxidative process (the so-called
'wall effect'25): the particles also generally catalyse the re-combination
of free radicals in the flame. 82 The chlorine is available to form more
HCl.
The action of zinc and tin oxides is similar to that of Sb20 3 but less
effective. Zinc oxide also functions as a smoke suppressant, but it
tends to impair the thermal stability of PVC. Zinc and barium borates
are sometimes used in flame-retardant products, mainly in conjunction
with Sb20 3 (as cheaper part-replacements13 ); synergistic effects can
arise in such combinations (notably with zinc borate85 ), which may also
have smoke-suppressing effects.
The borates are believed to inhibit burning in a manner similar to

t In other polymers flame retardancy can be conferred by Sb20 3 in a similar


way if a chlorine-containing organic compound is also incorporated.
430 W. V. Titow

that of borax (historically one of the earliest flame retardants, first used
in textiles), i.e. by fusing to form a protective layer which impedes
access of oxygen and heat to the PVC material;25,84 the fusion also
abstracts some heat from the system.
As particulate additives insoluble in PVC compositions the metal
oxides and borates just mentioned all have some opacifying effect
(rather lower in general with the latter compounds): this is minimised
with ultra-fine (sub-micron) particle grades (d. Section 11.3.1 above)
which are becoming increasingly widely available.
Note: The opposite approach to the same end is represented by a
version of Sb 20 3 of particle size considerably larger than in
the common, regular grades (1O-40/lm as against 1-3/lm):86
this is offered as a low-reflectance 'non-opaque' grade on the
basis that the comparatively lower number of coarse particles
present at a given level of loading by weight causes a lower
overall amount of interference with light.
Save for phosphate ester plasticisers in flexible compositions,
antimony oxide is the traditional flame retardant for PVC, still most
widely used today. However, its high cost has been providing incentive
for development of more economical alternatives. Some examples of
those already available commercially are 13 ,86 antimony-based additives
cheaper than Sb20 3 (e.g. antimony and antimony/zinc silicate composi-
tions in the Oncor and Ongard ranges of Anzon America Inc;* d. also
CLarechem CLA-150o-Claremont Polychemical Corp.), and molyb-
denum-based compounds (e.g. a Mo/phosphate combination, MoLy
FR 36-Climax Molybdenum Co; and zinc molybdate/zinc oxide
combinations like MoLy White 101-Sherwin-Williams Co.). The
smoke-suppressant effect of molybdenum oxide, alone or in mixtures
with antimony oxide, has been known for some time (see below).
As has been mentioned in Chapters 7 and 12 the phosphate ester
plasticisers (especially the aryl phosphates which are primary plasticis-
ers) are widely used to reduce the flammability of flexible PVC: they
are particularly useful in transparent compositions where Sb20 3 and its
above-mentioned combinations are unsuitable because of the opacify-
ing effect. It is common to employ an aryl phosphate plasticiser in

* Associated with Anzon Ltd in the UK; now owning the PVC stabiliser and
fire retardant/smoke suppressant operations formerly belonging to National
Lead Co., USA.
11 Some Miscellaneous Components of pvc Formulations 431

conjunction with (as part replacement for) a cheaper primary


plasticiser (often DOP) or a plasticiser/extender combination, be-
cause-apart from the cost aspect-the low-temperature properties of
phosphate-plasticised compositions are relatively poor, whilst their
smoke emission on burning is rather high. The flame-retardant effect
of phosphorus compounds in polymers (including phosphate ester
plasticisers in PVC) is believed to operate mainly through the
formation of phosphoric acid residues, phosphorus pentoxide and its
hydrates, all of which strongly promote the generation of char during
pyrolysis and thus reduce the amount of matter available for
combustionZ5 ,84 (ct. Fig. 11.6). Chlorinated phosphate esters with
flame-retardant and general plasticising action similar to those of alkyl
phosphate plasticisers, but with lower smoke generatiOn and-in some
cases-better low-temperature properties, are also noteworthy (ct. e.g.
Fyroflex 2704 and 280o-Stauffer Chemical Co.): see also Chapter 6,
Section 6.6.4.
Cost is always a factor in the selection of a flame-retardant agent or
system for a particular PVC composition: in practice it is most often
flexible PVC that has to be 'flame retarded', as uPVC is inherently
resistant (see above). In the absence of special requirements (e.g. high
clarity), combinations of a chlorinated paraffin (plasticiser extender)
with antimony oxide (alone or in conjunction with, say, zinc borate as
cheaper part-replacement) can offer cost economy in pPVC composi-
tions with good performance in flammability tests. 87 Where a
phosphate plasticiser forms a substantial part of the flame-retardant
system a smoke suppressant is also desirable: in filled compositions this
function may be discharged in a sufficient degree by the filler-for
example, calcium carbonate and talc can reduce the smoke generation
(and, as inert materials, also flammability) of PVC compositions. A
few outline examples of flame-retardant/smoke-suppressant systems of
the above kind are given in Table 11.9.
As has been mentioned in Chapter 8 (Section 8.4.2) alumina
trihydrate (AI(OHh or Al z0 3 .3HzO) is another additive, with both
flame-retardant and smoke-suppressing actions, of considerable use in
flexible PVC compositions. The main mechanisms whereby these
actions are exerted are considered to operate as follows. 88 ,89
The water of hydration present in high proportion (about 34%) in
alumina trihydrate is securely retained under PVC processing condi-
tions (the amounts lost after heating for 10 min at, respectively, 170°C and
220°C, represent about 0·5% and 2·5%88). However, at the high
W
"'"
N

TABLE 11.9
Outline Examples of Flame-retardant/Smoke-suppressant Systems for Flexible and Semi-rigid PVC
Semi-rigid
Flexible formulations (phr) formulations (phr)
1 2 3 4 5 6
DOP 60 60 50 24 24
Q
Plasticisers Epoxidised oil 5 5 5 ~
{ Aryl phosphate ester 25 60 :'"
Flame Chlorinated paraffin (52% Cl)b 25 25 32 :::'1
retardants { Antimony trioxide 2 2 5 2 3 o;;:
Zinc borate 4
Smoke Molybdenum complex c 2
suppressants { Zinc/magnesium complex d 2 1
Q Used for its stabilising rather than plasticising action.
b Cereclor S52 (lCI).
c Kem-Gard 91lA (Sherwin-Williams Co., Chemical Division).
d Ongard 2 (Anzon Ltd).
11 Some Miscellaneous Components of pvc Formulations 433

temperatures obtaining in burning it is rapidly split off as vapour or


steam, which obstructs the access of oxygen to the polymer, thus
hindering the combustion process.

Ah03 + 3HzO - 71·6 kcal


h' h
2 AI(OH)3 18
temperature
)

The action is supplemented by the insulating effect of the solid


alumina liberated in the decomposition. The alumina also acts as a
heat barrier which, in conjunction with the heat absorption in the
endothermic decomposition reaction, lowers the temperature and
suppresses pyrolysis, reducing smoke generation. It is also likely that
adsorption of smoke constituents (especially HCI) by the finely divided
alumina contributes to the reduction of smoke emission. 13
The double, flame- and smoke-retardant action of alumina trihy-
drate, and the fact that, weight-for-weight, it is cheaper than the main
flame retardants for pPVC, are considerable advantages. However, high
loadings are necessary for effective functionality (e.g. about 100 phr
may be required to raise the Oxygen Index of a typical composition
containing 50 phr DOP from about 22 to about 2788). At such loading
levels the effects on viscosity in processing and on physical properties
of the product can be substantial (see Chapter 8, Section 8.4.2).
The mode of action of the mineral fibre Dawsonite (d. Chapter 8,
Section 8.4.1) resembles that of AI(OHh- The material of the fibre, a
hydrated sodium aluminium carbonate, decomposes at combustion
temperature with essentially similar effects (supplemented in this case
by the evolution of non-combustible carbon dioxide in addition to
water vapour).
Magnesium carbonate is another smoke suppressant used at high
loading levels (up to about 40 phr) , at which its side-effects as a filler
become significant. It is a component of some proprietary flame-
retardant/smoke-suppressant compositions, e.g. Monsanto's Phosgard
LSV in which it is combined with a phosphate ester plasticiser
(Santiciser 148). The compositions are recommended for use in
compounds for electrical wire coatings, carpet backings and wall
coverings.
Molybdenum trioxide (molybdic oxide, Mo0 3) combines strong
smoke-suppressant action in pPVC at all plasticiser contents with some
flame-retardant effect: the latter is roughly comparable to that of
antimony oxide at low levels of plasticisation (e.g. 20-30 phr DOP),
but less at higher levels. The use of Mo0 3 in conjunction with Sbz0 3
434 W. V. Titow

(at 3 phr each) in medium-plasticised compositions can give good flame


retardancy and smoke suppression. 13 ,82 Mo0 3 is less dense than Sb20 3
(SG respectively, 4·5 and 5,7) and has lower pigmenting strength (in
comparable particle size grades); however it is an expensive additive.
The smoke-suppressant effect of Mo0 3 is associated with the
promotion of dehydrochlorination of the PVC polymer, and drastic
reduction in generation of benzene. 82 However, the actual mechanism
of its action is apparently different from that of Sb20 3 , as Mo0 3 has
been reported not to yield volatile metallic species in burning PVC. 82
Molybdates (e.g. combinations of calcium and zinc derivatives) also act
as smoke suppressants.
Note: Selected zinc compounds, especially in combination with
others, do not promote decomposition of PVC to the extent to
which zinc oxide does. Such combination, therefore, most
often forms the basis of commercial zinc-containing smoke
suppressants (e.g. Ongard 2-ef. Table 11.9) despite the
reasonable price and strong smoke-suppressing action of the
oxide.
Certain derivatives of ferrocene represent another group of smoke
suppressants effective in uPVC compositions. 82
Determination of the intensity of smoke generation (either by
measurement of 'optical density' in a standard chamber, or by
weighing the smoke substance collected on a filter in standard
conditions) is covered by several of the standards listed in Table 12.12
(Chapter 12). However, only one of these-ASTM D 2843 90-is
specifically and exclusively concerned with determination of smoke
evolution: the others merely feature this as one of the aspects of
burning behaviour under the test conditions. Another directly relevant
standard (centered on the so-called NBS smoke chamber) is ASTM
E 662,91 whilst an ISO standard, similar in principle, is in
preparation. 92 A useful review of smoke test methods has been
published in ASTM Standardisation News (August 1976, pp. 18-26).
Two other useful general sources of information ~n methods of
testing the flammability of, and smoke generation by, plastics materials
are Flammability Test Methods for Plastics: An International List,
published recently by the Chemical Industries Association Ltd, * and
ISO Technical Report 3814-1975 The Development of Tests for
Measuring 'Reaction to Fire' of Building Materials.
* Alembic House, 93 Albert Embankment, London SEl 7TU, England.
11 Some Miscellaneous Components of pvc Formulations 435

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