Professional Documents
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11.1 LUBRICANTS
*
11.2.
Lubricants with internal lubricant action are more compatible with PVC
polymer than typically external lubricants.
362 W. V. Titow
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
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.
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.
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.
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~
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f-
L.
~ ~ - ~-
~ B
- - - - - ----=-=_::"':_=-=_:":_==--=-=-=-=-=_:-
Time
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).
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
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
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
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
w
00
w
384 w. V. Titow
TABLE 11.4
Conversion Factors for Common Units of Flexural Impact Resistance
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
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).
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.
30
60
~~ 20·C
£20
40
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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
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
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
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
TABLE 11.6
Physical Properties of 'Breon Polyblend 503'
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
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
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
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
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.
* 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
Wet rubbing: As for 'dry rubbing' except that moist cotton is used.
(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-<:ontd. (2) Four-roll laboratory calender ('inverted L' type, rolls
6 in x 15 in).
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
~
Vl
426 w. V. Titow
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.
POLYMER
(or its dlZrivatlvlZ
plastic)
Pyrolysis +- - - - - - - - - - - --
<, HlZat ,/ - -
products (including
/" , I
CO, CO2, H20 and /
various oxidlZS) - - - - - - _ ......
, v
/
/
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
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
REFERENCES