An Overview of Additives and

Modifiers for Polymer Blends:

Facts, Deductions,
and Uncertainties*

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L. Mascia
University of Technology
Loughborough, L E K S LEI1 3TU
United Kingdom
zy
zyxwv M . Xanthos
Polymer Processing Institute
Castle Point on the Hudson
Hoboken, New Jersey 07030

ABSTRACT

Polymer blends with enhanced properties and processability for specific applications

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are modified through the incorporation of a variety of additives. The petformanee of

INTRODUCTION
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these additives is often dificult to predictfrom considerations of their known behavior
in the separate blend constituents. This overview article discusses additives and modi-
jiers in terms of types and specific functions (e.g., impact modifiers, compatibilizers,

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frame retardants, stabilizers) and provides an analysis of the possible effects of their
repartition in the constituent phases and at the interface. 0 1992 John W i e y & Sons, Inc.

favorable economics. Improved mechanical proper-

ties, barrier characteristics, and flame retardancy are
The annual growth of polymer blends worldwide is examples of targets where polyblending may offer dis-

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estimated to be about 8%.] Thus, the 800,OOOtons con- tinct advantages.
sumption figure quoted for 1989 is estimated to in- The growth of alloydblends is also expected to
crease to 1.2 million tons in 1994. Reasons for growth result in increased demand for certain types of plastics
are associated with improved properties and/or pro- additives. Recent estimates of the total U.S. plastics
cessability versus single polymer systems and often additives demand predict an annual growth of 3.6%,

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corresponding to an increase from a total of 5 million
*Based on Presentations at the International Conference on "Advances in
Additives and Modifiers for Polymer Blends," Miami, Florida (February. tons in 1989 to 6.2 million tons in 1994.2Highest in-
1992). creases are anticipated for flame retardants and rein-
Advances in Polymer Technology, Vol. 11, No. 4, 237-248 (1992)
0 1992 by John Wiley & Sons, Inc. CCC 0730-66791921040237-12
ADDITIVES FOR POLYMER BLENDS

concerning flammability and growing structural re-

quirements; antioxidants and process stabilizers
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forcements due, respectively, to stricter legislation TABLE I1
Examples of Additives Which Modify Electrical
Properties and Flame Retardancy
would also benefit as a result of increasing interest in
Flame retardants and smoke suppressants
recycling of single-component and commingled plas- Sb203,Moo3, molybdate salts, zinc borate
tics. The above projections refer only to conventional Chlorinated paraffins, brominated organic compounds
plastics additives and do not include certain important Organophosphate esters
additives that are used specifically to enhance the AI(OH),, Mg(OHh
Conductive additives
properties of a large number of immiscible and techno-
Carbon black, carbodgraphite fibers
logically incompatible polymer mixtures. Metals, metallized fillerslreinforcements
The authors of this article will consider conven-
tional plastics additives as well as compatibilizers for
multicomponent polymer systems in terms of types belonging to groups with the following general func-
and specific functions and will discuss their important
tions:
characteristics which determine compounding require-
ments and performance. Fillers and reinforcements
Mechanical properties modification (fillers and rein-
are not included in this overview. Since the perfor- forcements not included).

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mance of many additives in polymer blends is difficult Electrical properties modification and flame retard-
to predict with certainty from considerations of their ancy .
known behavior in the separate components, an at- Processing behavior enhancement.
tempt will be made to analyze the possible effects of Anti-aging characteristics.
the repartition of additives in the constituent phases
Optical properties modification and density reduc-
and the interfaces. tion.
Surface and interfacial modification.

CLASSIFICATION AND TYPES OF PLASTICS Additives may be further classified according to their
ADDITIVES miscibility in the polymer matrix; for example, inor-
ganics form multiphase systems, whereas organics
Plastics additives are characterized by a diversity of may be miscible, immiscible, or partly miscible. Fi-
chemical structures and compositions, molecular nally, additives may be classified according to their
weight, natural form, shape, etc.; this makes their concentration in the polymeric matrix; for example,
classification according to a general scheme extremely conductive additives, flame retardants, and additives
difficult and often impractical. that modify mechanical properties (with the exception
Following the original scheme suggested by Mas- of cross-linking agents) are commonly employed at
~ i a , additives
~.~ may be classified according to their relatively high concentrations, i.e., often >lo% by
general and/or specific functions. Tables I-VI contain vol. ; other additives, such as antioxidants and stabiliz-
examples of specific families of chemical compounds ers, are used at <lo% by vol. and often below 1 phr.

TABLE I
Examples of Additives Which Modify TABLE 111
Mechanical Properties* Examples of Processing Additives
Plasticizers Stabilizers
Phthalate, trialkylphosphate, adipate esters Primary antioxidants (sterically hindered phenols, sec-aryl
Chlorinated paraffins amines)
High MW polyesters Hydroperoxide decomposers (organophosphites, thioesters)

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Epoxy derivatives Acid absorbers (lead salts, Ca/Ba-Ba/Cd-Ba/Sn salts, or-
Impact modifiers ganotins, epoxidized oils)
EPR, EPDM Lubricants
NBR, NR, various elastomers High MW fatty acids and derivatives
EVA, MBS, CPE Paraffin, ester and amide waxes

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Crosslinking agents Metal soaps
Organic peroxides, coagents Silicones, polyfluorocarbons
Rubber curatives Flow and fusion promoters
PMMA and acrylate ester copolymers, MBS
*Except fillers and reinforcements

238 VOL. 11, NO. 4

_ _ _ ~~ ~
TABLE IV
Examples of Anti-Aging Additives
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During compounding, the important parameters are:

zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
The physical state, chemical nature, and concentra-
Antioxidants
Sterically hindered phenols
tion of the additive.
Sec-aromatic amines The order and site of addition of the feed streams.
Phosphites, thioethers The selection of the mixing configuration, which, in
Metal deactivators turn, depends on the nature of the additive (low
Chelating agents (hydrazones, oxamides, hydrazides, phosphi- viscosity liquid, low MW solid, melt, liquid).
tes, phosphines)
Light stabilizers
The mixing requirements (distributive vs. disper-
Pigments (carbon black, iron oxides) sive).
UV absorbers (hydroxyphenones, benzotriazoles)
Excited state quenchers (organic Ni complexes) Parameters affecting the behavior of additives in
Free-radical scavengers (piperidines, HALS) polymeric matrices have been reviewed by many au-
thors (see, for example, Refs. 4-7). The important
characteristics of most additives may be summarized
as follows:
Additives forming distinct dispersed morphologies
may be deformable or rigid. For deformable additives
POLYMER MODIFICATION THROUGH
(e.g., polymeric impact modifiers), important charac-
ADDITIVES
teristics controlling the degree of dispersion, the re-
sulting morphology, and the final properties are:
General
Within a given concentration range, the perfor- Viscosity and elasticity at processing conditions.
mance of an additive in a polymeric matrix is ulti- Concentration.
mately related to: Interfacial tension.

Its affinity to the matrix; this is controlled by physi- For rigid additives (e.g., inorganic flame retardants,
cal and chemical interactions. conductive additives, pigments), dispersion and prop-
Its distribution in the melt during mixing and subse- erties are controlled by:
quent forming, which, in turn, is related to miscibil-
ity, andlor degree and type of dispersion. Particle size and shape, size distribution, surface
Its final distribution in the molded object and the area, and volume fraction.
stability of the resulting microstructure to coales- Bulk properties, surface tension, and surface reac-
cence and agglomeration. tive sites.

TABLE VI
TABLE V Examples of Surface Modifiers
Examples of Optical Property Modifiers and
Blowing Agents Antistats
Ethoxylated amines and quaternary ammonium salts
Pigments Phosphate esters
Inorganic: Ti, Fe, and Cr oxides, Cd, Ba and Pb sulfides, Glycerides
sulfates, and chromates Antiblocking agents, slip additives
Organic: carbon black, quinacridones, azo pigments Amide waxes, oleamide
Dyes Antifoggers
Anthraquinones Polyethers
Azo and bisazo compounds Antiwear additive
Nigrosines PTFE
Nucleating agents Wetting agents
S O z , talc, sodium benzoate Ionic, nonionic surfactants
Blowing agents Adhesion promoters
Inert gases (COz, NZ) Silanes, titanates
Hydrocarbons, halocarbons Block and graft copolymers*
Chemical blowing agents (azodicarbonamide)
Bicarbonates *Particularly important for immiscible polymer blends (compatibilizers, cou-
pling agents, interfacial agents).

ADVANCES IN POLYMER TECHNOLOGY 239

ADDITIVES FOR POLYMER BLENDS

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Miscible and partly miscible additives are mostly
used at low concentrations and may include various
compatibilizers, crosslinkers, process stabilizers, etc.
For such additives, degree of miscibility is controlled
by:
components. The copolymers may be added sepa-
rately or formed in situ by blending suitably function-
alized polymers. Compatibility may also be enhanced
through the addition of specific low MW compounds
promoting copolymer formation and/or crosslinking.

1. Chemical structure. In Situ Formed Copolymers

2. Molecular weight.
During melt blending of a pair of suitably functional-
3. Concentration at processing temperatures.
ized polymers A and B, interchain block or graft co-
polymers may be formed at various concentrations
Thus, depending on the type of additive, its choice and
through covalent or ionic bonding. The in situ formed
performance characteristics are related among other
compatibilizers have segments that are chemically
factors to the type and magnitude of its specific inter-
identical to those in the respective unreacted homo-
actions with the polymer, the differences in solubility
polymers and are thought to be located preferentially
parameters, and the dependence of solubility and dif-
at the interface; thus, they lower interfacial tension
fusivity on temperature.
and promote mechanical interlocking through inter-

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penetration and entanglements. Examples of some im-
portant compatibilizing reactions”’ that can easily
PERFORMANCE OF ADDITIVES IN take place across polymer phase boundaries involve
POLYMER BLENDS functionalities, such as:
In multicomponent polymer systems, the distribu- Anhydride or carboxyl with amine (e.g., PP-pMA/
tion and/or the response of the blend constituents to a PA 6).
given additive may be different for each component 0 Epoxy with anhydride or carboxyl (e.g., PPE +
and often undesirable. Thus, the proper choice of the SMAIEVA-co-GMA).
additive and the selection of processing conditions is 0 Oxazolin with carboxyl (e.g., OPSIEAA).
even more critical than in single polymers. “Cure 0 Isocyanate with hydroxyl or carboxyl (e.g., PBTI
compatible” co-crosslinked rubber-rubber blends are isocyanate terminated polymers).
examples of systems where phase separation is inhib- 0 Carbodiimide with carboxyl (e.g., PBT/carbodii-
ited by the proper choice of common curatives with mide functionalized polymers).
comparable rates of vulcanization and similar solubili-
ties in the blend constituents9; these blends are charac- Additional reactions that may lead to enhanced
terized by intercrosslinked morphologies with good in- compatibility are:
terphase bonding. In the following sections, an
attempt is made to relate the characteristics of differ- 0 Transesterification (e.g., PC/PBT).
ent types of additives to their performance in multi- 0 Macroradical recombination in polyolefins.
component polymer systems. Interchain ionic salt formation as in sulfonated PS-

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EPDM/PPE blends.

Compatibilizers Copolymers Added Separately

Methods to enhance polymer-polymer compatibil- Nonreactive copolymers. Interfacially active graft
ity have been reviewed by various authors.&” Co- or block copolymers of the type A-B or A-C may
crystallization and co-crosslinking can often result in compatibilize the immiscible polymers A and B pro-
stable morphologies that are resistant to coalescence. vided that C is also miscible or capable of strong inter-
Strong interactions such as acid-base or ion-dipole, actions with B. Examples from the systems reviewed
hydrogen bonding, and transition metal complexation in Ref. 8 include styrene/butadiene or styrene/iso-
have also been shown to enhance thermodynamic mis- prene diblock and triblock copolymers in blends of PS

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cibility of suitably functionalized blend components with polyolefins, EPM or EPDM in PE/PP blends, and
and result in improved compatibility in a variety of PSIPMMA block copolymers in PVDFIPS-PMMA
systems of technological importance. More corn- mixtures.
monly, compatibility is promoted through copolymers Reactive copolymers. Reactive copolymers or func-
(e.g., block, graft) with segments capable of specific tionalized polymers of the type A-C (where C is a long
interactions and/or chemical reactions with the blend reactive segment or a functional group attached to the
240 VOL. 11, NO. 4
 zy
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main chain) may compatibilize a polymer pair A and B
provided that C is capable of chemically reacting with
B. The nonreactive segment of the polymeric compati-
ADDITIVES FOR POLYMER BLENDS

where n = power law index for viscosity and R =

channel radius, the promotion of a slip velocity (Vs),
related to the wall shear stress (7,) by a power law
bilizer often has different chemical and structural iden- function, reduces the shear rate at the wall (rw)
ac-
tity from component A, but is still capable of specific cording to the equation below’*:
interactions leading to a certain degree of miscibility.
The majority of blends in this category employ po- .
yw = (3 nT+ 1 j a
Q
- (3 +
VO
lyamide as the constituent that may react with com-
patibilizers containing anhydride or carboxyl function-
alities to form amide or imide linkages. Other where m = power law index for slip velocity, and V , =
compatibilizing copolymers may contain the highly re- slip velocity at zero shear stress.
active oxazolin, epoxy, isocyanate, or carbodiimide The balance between internal and external lubrica-
groups discussed earlier. tion is determined by the solubility of the lubricant in
the polymer melt at the processing temperature. The
Low MW Compatibilizing Compounds solubilized lubricant reduces the melt viscosity
through plasticization effects while the remainder
The addition of low MW compounds in a polymer
finds its way to the surface of the channel, where it
blend may promote compatibility through the forma-
increases the slip velocity through a hydrodynamic or
tion of copolymers (random, block, graft) or through
boundary lubrication effect.
the combined effects of copolymer formation and
In general, the extent of internal lubrication is very
cross-linking. Low MW compounds are usually added
small, owing to the low level of lubrication generally
at relatively low concentrations (typically 0.1%-3% by
used in polymer formulations (i.e., 0.1%-1.0%). The
wt.); thus, they may offer economic advantages vs.
most insoluble lubricants, e.g., silicone oils, always
polymeric compatibilizers that are usually effective at
provide a hydrodynamic type of lubrication, but are
higher concentrations. Examples from the systems re-
not too widely used because of their relatively high
viewed in Ref. 9 include p-toluenesulfonic acid or
cost and because they may retard the fusion of poly-
phosphites that may catalyze transamidation melt re-
mer particles or granules, say in the feed zone of an
actions in blends containing polyamides and polyes-
extruder. The more conventional lubricants are high
ters, peroxides (often in combination with coagents)
molecular weight fatty alcohols, amines, acids, esters,
that could promote compatibilization through the re-
or salts of calcium, zinc, or sodium (Table 111). Also
combination of polyolefin macroradicals, cross-linking
commonly used are low molecular weight polymers, in
additives in “dynamically vulcanized” thermoplastic
the form of waxes, characterized by varying degrees
elastomers, common curatives in co-crosslinkable rub-
of polarity ranging from paraffinic types to amide oli-
bers, etc.
gomers, and oxidized polyethylene waxes containing a
large number of carboxylic acid groups.
The choice of lubricant is, therefore, determined by
Lubricants the nature of the polymer so that their miscibility can
Lubricants are additives used in polymer com- be minimized, i.e., nonpolar polymers such as po-
pounds to increase the flow rate of the melt through lyolefins would require a polar lubricant, say calcium
the channels of processing equipment and to improve or zinc stearate, an amide, or ester-type wax. In con-
the gloss of the extrudate. A side effect of lubricants is trast, highly polar polymers, such as polyamides, re-
a reduction in die swell and the suppression of melt quire the use of low polarity lubricants, e.g., monta-
fracture. The above effects result from a reduction in nate esters or dioctyl s e b a ~ a t e . ’For
~ the case of

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viscosity (internal lubrication) and from the promotion blends, the choice could be complicated by conflicting
of slip at the walls of the channels in the processing requirements for the individual polymer components.
equipment (external l~brication).~ An obvious example to illustrate this point is a blend of
At a given flow rate or output from the process, polyamide with polyethylene. In this case, a monta-
interfacial slip reduces the shear rate in the flowing nate ester would exhibit a high level of solubility in the
(rw)

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melt. For instance, while the wall shear rate of a polyethylene phase, while zinc stearate could be solu-
polymer melt in a cylindrical channel is related to flow bilized in the polyamide phase through coordination of

Yw = zyxwvutsrqponm
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rate ( Q ) by the well-known expression

3n+l
(7)
ADVANCES IN POLYMER TECHNOLOGY
Q
the cation with the amide groups.I4
The question arises as to whether, for such an in-
compatible blend, the lubricant selected on account of
its intermediate polarity may find a more suitable resi-
24 1
ADDITIVES FOR POLYMER BLENDS zyxwvu
dence in the interphase regions between the two poly-
mers rather than at the surface of the metal channel
wall. The probability for this to happen is even greater
certain amount of cross-diffusion of ions and molecu-
lar segments is expected. In this respect, it is likely
that the polyolefin phase may suffer from an even
if the blend has been compatibilized, say by grafting greater extent of degradation owing to the devastating
reactions between an anhydride functionalized poly- effect of even a few ppm of copper ions on the autoxi-

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ethylene with the polyamide. In this case, the in situ dative decomposition reactions. Any attempt to over-
formed graft copolymer compatibilizer would form an come this effect by the addition of a chelating agent,
interlayer between the two phases, which is likely to normally used to stabilize polyolefins for wire and ca-
miscibilize the lubricant and will therefore create less bles applications, will inevitably defeat its objective,
favorable conditions for its migration to the walls of as it would destroy the activity of the copper ions for
the flowing channel. the protection of the polyamide phase.
Restrictions for the stabilization of blends, as a
result of antagonistic effects of stabilizers for one com-
ponent toward the protection requirements for the
Heat Stabilizers
companion polymer, can be experienced also for the
To illustrate the difficulty that one may face in se- case of compatible polymers. An example of such a
lecting heat stabilizers for polymer blends, the same situation can be quoted for blends of PVC and nitrile
combination of polymers discussed earlier, i.e., po- elastomeric modifiers. The first polymer requires sta-
lyolefins and polyamides, is chosen as an example. bilization primarily against dehydrochlorination reac-
Stabilization of polyolefins (see Table 111) is normally tions while the second needs protection against autoxi-
carried out by means of synergistic mixtures consist- dative degradation. These conflicting requirements put
ing of a phenolic antioxidant (the primary stabilizer/ constraints on the use of cadmium or tin compounds
radical quencher) and a dialkyl dithio propionate or for the stabilization of the PVC component, as they
tris alkyl phenyl phosphite (the secondary stabilizer/ would have a deleterious effect on the stability of the
hydroperoxide decomposer). nitrile elastomer through a redox-assisted autoxidative
Polyamides are also stabilized by the use of mix- mechanism. There can be little use also for mercaptide
tures of hindered phenolic antioxidants and tris alkyl costabilizers for PVC, as they would react preferen-
phenyl phosphites. Dialkyl dithio dipropionates are tially with the butadiene unsaturation in the butadiene

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not widely used because of their relatively high volatil- chains of the nitrile copolymer owing to the much
ity and intrinsic lower resistance to thermohydrolysis. larger number of double bonds in the latter component
To enhance the stabilization efficiency of the above than in the dehydrochlorinated segments of the PVC
combination of stabilizers for polyamide composi- chains.
tions, use is made of very small amounts of mixtures
of copper acetate (50-500 ppm) and potassium iodide
(1000-2OOO ppm).I5 The exact mechanism for the pro-
tective action of the latter additives is not well under- UV Stabilizers
stood, but their chemical nature suggests that an ionic
With respect to UV-induced polymer degradation,
mechanism may be involved, or that the Cu cations,
the most damaging radiation is in the range 293-419
by forming associations with the amide groups of the kJ/Einstein (1 Einstein = 1 mole photon = 6 x
polymer chains in the amorphous regions, will reduce photons). The energy associated with the photons in
the rate of homolytic cleavage of the -NH-CO- groups. this wavelength region is significantly higher than the
The role of the potassium iodide is probably to provide binding energy of chemical bonds found in polymers
I- counterions for the coordinated copper cations. (Table VII).I6
The direct addition of copper iodide would be less The groups concerned, however, only absorb a
effective than the above-mentioned combination of small portion of the energy in the damaging wave-

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salts, owing to its lower solubility in polyamides than length regions, and, furthermore, the absorbed energy
copper acetate. Larger quantities of copper ions would may be transformed into a less harmful radiation be-
have an adverse effect on the stability of polyamides fore bond rupture takes place. The quantum yield (the
as they would accelerate the free radical oxidative re- percentage energy absorbed causing bond cleavage) is
actions by a redox mechanism. quite low, i.e., 3%-5% for C-H and C-C bonds and
In blends of polyolefins with polyamides, the stabi- ca. 10%for the C-C bond, the most vulnerable groups
lizers are likely to dissolve entirely in the polyamide II
phase, leaving the polyolefin component virtually un- 0
protected, except in the interphase regions where a being peroxide, for which the quantum yield is 100%.
242 VOI-. 11. NO. 4
These groups are present as chain defects and are
formed primarily during processing.
The effect of UV radiation in polymers is the gener-
zy
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ADDITIVES FOR POLYMER BLENDS

nation polyamides/polyphenylene ethers. Polyamide

chains undergo molecular cleavage at wavelengths of
absorbed light below 300 nm and will undergo photo-
ation of free radicals, which will then induce oxidative sensitized oxidation above 300 nm. Polyphenylene
degradation reactions. Protection against UV-induced ethers absorb strongly at 380 nm, but may contain a
degradation by means of additives (see Table IV) can considerable quantity of hydroperoxide impurities.
be achieved in a number of ways, more specifically According to the above, PPE can provide some pro-
through the following mechanisms: tection for the photooxidation of PA by virtue of its
preferential UV absorbing mechanism. The usual dif-
Absorbing UV light in order to reduce the number ferential solubility arguments will also favor the repar-
of photons that will be available for the chromo- tition of most of the previously mentioned additives in
phore groups in the polymer chains. These addi- the polyamide phase. Zinc dithiocarbamate or
tives are simply known as UV absorbers and in- dithiophosphate will certainly find more favorable sur-
clude carbon black, iron oxide, and soluble organic roundings in the polyamide phase through coordina-
compounds, such as hydroxybenzophenones and tion reactions with the amide groups.
hydroxyphenyl benzotriazoles. Piperidine compounds are also more likely to favor
Deactivating the excited species by energy transfer associations with the amide groups and are therefore
so that less of the energy absorbed by the polymer more likely to concentrate in the polyamide phase than
will be available for breaking chemical bonds. in the polyphenylene ether phase. Similar arguments
These additives are known as excited state quench- can be made with respect to nickel complexes for their
ers and are typically nickel chelates of both aro- choice as excited state quenchers. All the above argu-
matic and aliphatic compounds. ments make the polyphenylene ether component of
Radical scavenging in order to reduce the rate of the blend very vulnerable and difficult to protect
propagation of autoxidative reactions. Typical ad- against UV-induced degradation by means of soluble
ditives are hindered amines derived from piperi- additives, making the use of pigment type of absorbers
dine. an unavoidable choice.

The use of carbon black or iron oxide is expected to

Chemical Blowing Agents
be as effective in blends as for individual polymers
insofar as the distribution of particulate additives will These are additives (see Table V) capable of releas-
not be affected by any differences in the chemical na- ing large quantities of gas by thermal decomposition
ture of the two polymers, but only, to some extent, by over a relatively narrow range of temperatures.
the difference in viscosity. In the production of foams, the gas evolved from the
As regards other types of additives, the usual argu- decomposition of the blowing agent dissolves in the

zyxwvuts
ments on differential solubilities are valid, and, again, polymer melt under pressure and exerts its blowing
it is possible that the chosen additive will dissolve pri- action only when the pressure is suddenly reduced as,
marily in one phase of the blend, leaving the other less for example, during mold filling in injection molding or
well protected. after emerging from the die in extrusion.
For this discussion, an interesting example of di- The foaming process occurs in two stages, i.e., nu-
lemma in the UV stabilization of blends is the combi- cleation of the cells followed by their growth and si-
multaneous stabilization. Nucleation occurs as a result
of the desorption rate of the dissolved gases exceeding
TABLE VII their rate of diffusion into the surroundings when the
Comparison of Radiation Energy at Different external pressure on the melt is removed. Stabilization

zyxwvutsrq
Wavelengths of the UV Spectrum with the Binding of the subsequent cell growth process gives rise to the
Energy of Chemical Bonds in Polymers16 formation of cells of uniform size by a mechanism
which permits the smaller cells to shrink in size and,
Wavelength Energy Bond Bond Energy eventually, to disappear while the larger ones continue

zyxw
zyxwv
(mm) (kJiEinstein) Type (kJ/mole)
to grow. In the most simple terms, the cells begin to
290 419 C-H 380-420 grow when the work of expansion exceeds the total
300 398 c-c 340-350 surface energy of the cell walls.
320 315 c-0 320-380 The balance of energy for a single cell is:
350 339 c-CI 300-340
400 291 C-N 320-330
P dV = ydA

ADVANCES IN POLYMER TECHNOLOGY 243

 zyxwvu
zyxwvutsrq
zy
zyxwvutsr
zyxwvutsrq
ADDITIVES FOR POLYMER BLENDS

zyxwvut zyxwvuts
where P = pressure; dV = infinitesimal volume incre-
ment of the cell; y = surface energyhnit area; dA =
second decomposes at around 230°C producing 140
ml/g of gas.

zyxwvuts
infinitesimal increase in surface area of the cell; and On the basis of what was said earlier, the fine parti-
r = radius of the cell. V = 4/3 r r 3 ; d V = 4.rrr2dr; cles of blowing agent can be distributed quite uni-
A = 4.rrr2;and dA = 8.rrr dr. formly in both phases, but the repartition of dissolved
Substitution in the equation above gives: gas after their decomposition will take place propor-
tionally to their respective solubility. Consequently,
p=2y nucleation of the cells in the two phases will not take
r place simultaneously and is probably likely to occur
preferentially in the interphase regions. The growth of
That is, the pressure in a cell is inversely proportional the cells is also expected to cause rupture of the walls
to its radius. because of the relatively low interfacial bond between
The pressure differential between small and large the two polymers, giving rise to the formation of open
cells causes a transport of gases by diffusion from the cells, nonuniform in size and irregular in shape.
small cells (high pressure) to the large cells (low pres-
sure), which stops only when all the cells have reached
equal size.
Plasticizers
In practice, the work of expansion of the cells has to
overcome also the viscous forces and elastic forces These are additives normally used in glassy poly-
exerted on the walls of the cells by the polymer melt, mers to reduce their glass transition temperature. The
so that the pressure is not exactly inversely propor- most common example of commercial products is
tional to the radius, but it is still inversely related to it, plasticized PVC, where the levels of plasticizers used
and, consequently, the mechanism for the stabilization are sufficiently high to bring the Tg of the polymer to
of the cells is still applicable. below room temperature, thereby producing a rubbery
The most common blowing agents used for the pro- product.
duction of polymer foams are azo compounds and hy- For the case of semi-crystalline polymers, an effi-
drazine derivatives, which decompose to produce cient plasticizer would not only reduce the Tg of the
mostly nitrogen, carbon dioxide, and ammonia. Their amorphous domains, but would also depress the melt-
decomposition temperature is determined by the sub- ing point of the crystalline phase. The best example of
sequent groups, and can vary from 45-90°C for azobis- such systems is plasticized nylon compounds with en-
dibutylnitrile to about 275°C for trihydrazinotriazine. hanced flexibility.
Blowing agents are mostly in the form of fine powders Plasticizers are normally liquids and therefore have
having a very high melting point (i.e., above their de- to be fully compatible with the polymer to avoid phase
composition temperature) and are insoluble in the separation, which would cause migration to the sur-
polymer. Both features result from the strongly hydro- face.
gen-bonded molecules in their crystal lattice. The resi- While the glass transition temperature of the poly-
dues left after decomposition will probably provide fa- mer decreases monotonically with increasing concen-
vorable sites for the nucleation of cells. tration of plasticizers, this is accompanied by a de-
The choice of blowing agents for different polymers pression of the /3 relaxations and a concomitant
is largely dependent on their decomposition tempera- reduction in the p transition temperature. As a result,
ture in relation to the processing temperature and the properties of the polymer over the temperature
other collateral considerations, such as color, toxicity, range between the a and p transitions change in the
etc. From the foregoing discussions, it is inferred that opposite direction to the behavior at around and above
the nature of the gas evolved will determine their solu- the glass transition. For instance, the modulus in-
bility in the melt and, accordingly, also the rate of creases while the coefficient of thermal expansion de-
nucleation and cell growth. creases.
Taking again as an example the case of blends of This phenomenon is known as antiplasticization. As
LDPE with polyamides, it is possible to deduce the a consequence of antiplasticization, the critical craz-
likely difficulties encountered in the production of ing strain of the polymer decreases, and the polymer
foams from blends. becomes more brittle.

zy
The literature suggests that trihydrazinotriazine or In Figures 1 and 2, it is shown that, in approaching
p-toluene sulphonyl semicarbazide are suitable for the T a and T p values starting from room temperature,
both p01ymers.l~The first has a decomposition tem- the extent of antiplasticization decreases and vanishes
perature of 275°C and a gas yield of 225 ml/g, while the altogether in passing through these transitions. Conse-
244 VOL. 11, NO. 4
 G'
z
zyxwvutsrq ADDITIVES FOR POLYMER BLENDS

zyxwv
6'

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a 1 I
-55-c 85'C
I

I f

POLYSULFONE 10%
AROCHLOR 5442 30% - I
t
f
I
c
-
010 - , - 10.00

zyxwv
LOG C'
SHEAR
MODULUS

- 9.80 -
DYNES
006 - CM2

- 9.60

- ---- - -
I
*--
I
---- - ----- ---- -
I I I
___- 1 I I
b

zyx
-160 -w 0 80 160

T E MPE RATURE "c

FIGURE 1 Elucidation of antiplasticization phenomena from dynamic mechanical spectra. (a) PVC plasticized with TCP (after Ref.
18); curves 1, 2, and 3, anticipated behavior. (b) Polysulfone plasticized with Apochlor 5442 (after Ref. 19).

quently, antiplasticization phenomena are not neces- hand, the addition of a plasticizer is likely to produce a
sarily experienced at ambient temperatures but will homogeneous mixture exhibiting the same behavior as
always occur at temperatures below the glass transi- a single polymer system. Some reservations can be
tion temperature. expressed, however, with respect to the less known
In considering the behavior of plasticizers in incom- effects on the p transition, particularly if this occurs
patible or semi-compatible blends, one has to take into below the lower critical solution temperature (LCST)
account, therefore, the level of plasticizer dissolved in of the binary polymer mixture. A practical example of
the two phases and to determine whether these will such uncertainty is to be found for the case of plasti-
exhibit a Tg above or below ambient temperature in cized blends of PVC and nitrile rubber.
order to deduce whether antiplasticization is likely to If, on the other hand, one considers an impact-
occur and what would be the consequence. modified PVC composition, the consequence of add-
For the case of compatible blends, on the other ing a small amount of plasticizer (say, to improve its
ADVANCES IN POLYMER TECHNOLOGY 245
 zyxwvu
zyxwvutsrqp
zyxwv
ADDITIVES FOR POLYMER BLENDS

I ', E c = 1.0%

t
I
persed particles, and the high level of stress intensifi-
cation at the interface, result in the formation of
cracks propagating through the matrix, thereby only
I

I
I
affording modest increments in toughness.
to

Flame Retardants
A simplified but reasonably clear picture of the
mechanism available for reducing the susceptibility of
polymers to burn is illustrated in Figure 3.
From an analysis of the scheme presented, it can be
inferred that fire-retardant additives can intervene to
reduce the ignition susceptibility and associated flame
propagation by either promoting char formation or in-

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hibiting the autoxidative reactions in the ignition zone.

zyxwvutsr
-60 -30 0 30 60

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TEMPERATURE (OC)
The latter can be achieved by reducing the ratio of
combustible gases to oxygen andlor by providing an
FIGURE 2 Antiplasticization of PVC manifested as a reduction effective competition for oxygen in the reactions lead-
in critical crazing strain between the a and p transition ing to the ultimate state of oxidation of the products of

zyxwvutsrqp
temperatures (after Ref. 20).
the pyrolysis.
The formation of a charjust below the ignition zone,
on the other hand, provides an effective thermal shield
for the polymer in the pyrolysis zone, thereby reduc-
processability through internal lubrication effects) is
ing the rate of formation of combustible gaseous frag-
that the PVC matrix will suffer from antiplasticization
ments.
effects and will exhibit a lower critical crazing strain.
Although there is no single mechanism for a given
It cannot be anticipated, however, whether this will
fire-retardant additive or mixture of additives, it is
also result in an embrittlement of the system insofar as
possible to broadly divide them into: (a) ignition inhibi-
the ensuing enhancement in multiple craze formation
tors; (b) self-extinguishing additives; and (c) smoke
around the rubber particles could well have a benefi-
cial effect with respect to the energy dissipation if the
interparticle distance and the interfacial adhesion are
adequate to impose an effective craze stopping mecha- SMOKE ZONE
nism.
An effective example of the possible adverse effects
of antiplasticization phenomena in two phase systems
FLAME ZONE
can be found in considering the use of aromatic ther-
moplastic polymers in epoxy resins.
In order to retain the high Tg of the matrix, it has IGNITION ZONE
often been suggested to dissolve in the epoxy resin an
aromatic linear polymer exhibiting a high Tg, such as
polysulphones or polyether h i d e s . In the early stages
of the curing schedule, the resulting increase in molec- R a d i a n t heat
ular weight in the resin raises the upper critical solu-
tion temperature (UCST) threshold and causes the ar- v v v v i
omatic polymer to precipitate out as small particles
incorporating small quantities of dissolved epoxy CHAR
resin, acting as a plasticizer. While the favorable solu-
bility parameters for the two phases are expected to
give rise to a reasonably high level of interfacial adhe- PYROLYSIS ZONE
sion, antiplasticization phenomena within the aro-
matic polymer particles cause them to acquire very
low critical crazing strain values. The lack of an effec-
tive mechanism for craze stopping within the dis-
246
COLD POL YMER

zy
FIGURE 3 The activity zones of a burning polymer.

VOL. 11, NO.4

 ADDITIVES FOR POLYMER BLENDS zy
zyxwvu
suppressants. Although the latter do not exhibit a place in the gas phase, as, for instance, with the use of
flame retardation action per se, they contribute to the aluminum trihydrate or magnesium hydroxide. Misci-
safety of the product by reducing the hazards associ- bility is important, on the other hand, if the additive
ated with fires. Equally important in reducing fire haz- can intervene in the pyrolysis stage, as in the case of
ards is the elimination of toxic gaseous products. Ex- mixtures of halogenated compounds and antimony ox-
amples of flame retardants may be found in Table 11. ide. Any discussion on the use of fire retardants in
Additives acting primarily as ignition inhibitors are polymer blends will have to be focussed primarily on
mixtures of organic halogenated compounds and anti- the question of whether the additive is likely to be
mony trioxide. These form volatile oxychlorides capa- more soluble in one of the components of the blend or
ble of providing a bamer for the diffusion of oxygen whether a more complex mixture of additives would
into the ignition zone and, at the same time, can react have to be used to meet the best requirements for each
directly with hydrocarbon fragments, thereby reduc- component of the blend.
ing the rate of reactions leading to COz and HzO. More important considerations on the use of fire
Occasionally, aromatic phosphates are also used as retardants for blends are related to the question of
fire retardants, but their use is restricted to very spe- maximum loading that can be tolerated with respect to
cific polymers, e.g., polyphenylene ether and plasti- possible deteriorations in mechanical properties and
cized PVC. Additives like aluminum trihydrate, mag- processibility. On the other hand, the incorporation of
nesium hydroxide, zinc borate, and melamine another polymer into a fire-retardant formulation may
derivatives exert a fire retardant action primarily by be advantageous as a means of improving the so-called
emitting incombustible gases and by transporting heat “filler receptivity,” i.e., to prevent an excessive dete-
from the substrate through endothermic vaporization rioration in toughness of the composition at the level
or sublimation phenomena. of additive necessary to achieve the required level of
Because the mechanism involved is primarily a dilu- fire retardancy. In other words, the use of a blend is
tion of the combustion mixture, large quantities of ad- often called upon to resolve a problem brought about
ditives are required to provide an effective fire-retard- by the addition of the fire-retardant additives.
ant action. This is particularly true for the case of Normally, a flexibilizing semi-compatible polymer is
aluminum trihydrate and magnesium hydroxide where selected for the purpose outlined above, e.g., the in-
the diluent gas is water, which constitutes only a frac- corporation of an ethylene propylene elastomer to a
tion of the total weight of the additive used. The at- thermoplastic polypropylene composition. In other
traction, on the other hand, is the much reduced level cases, the addition of another polymer may provide
of toxicity in the resulting products of combustion. better wettability and adhesion to the fire-retardant
Very few additives are known to exert a fire-retard- filler. An example of this is the use of an EVA or an
ant action through char formation, albeit aromatic ethylene acrylic acid copolymer or terpolymer to a
polymers and in particular polyimides and polypheny- fire-retardant polyethylene composition.
lene sulphide are intrinsically fire retardant by virtue What is not certain is the question of whether the
of their char formation characteristics. morphology of a two-phase polymer system can be
As it is not feasible to alter the pyrolysis mechanism affected by the presence of filler particles. Would, for
of a polymer in the direction leading to the formation instance, the higher internal shear stresses affect the
of a char, the only possible route available for the use dimensions of the dispersed polymer phase?
of additives to increase the amount of char on the
surface is by means of coatings. These are known as
“intumescent coatings,” consisting basically of mix- CONCLUDING REMARKS
tures of polyhydric alcohols, blowing agents, and de-
hydrating agents. As they do not enter in the realm of With the prospect of polymer blends dominating the

zyxwvutsr
additives, discussions on their use for polymer blends market for plastics and rubber products in the not-too-
will not be considered. distant future, the question of performance and selec-
From the foregoing analysis, it is noted that fire- tion of additives is likely to become an even more
retardant additives are generally particulate solids dis- important issue than has been the case for the single

zyxwvu
persed in the polymer, albeit a certain level of solubil- polymer compositions of the past.
ity with the polymer matrix is sometimes experienced, In order to satisfy some opposing requirements for
as for instance in the use of chlorinated paraffins in individual polymers, the choice of additives has to be
PVC. made with much greater care and will undoubtedly
The lack of compatibility, however, is not a draw- result in even more complex formulations.
back in situations where the fire retardant action takes With increasing market pressures for safer products
ADVANCES IN POLYMER TECHNOLOGY 247
ADDITIVES FOR POLYMER BLENDS

in use and less hazardous environmental conditions in

zyxwvu 19. L. M. Robeson, Polym. Eng. Sci, 9, 280 (1969).
20. L. Mascia, P. G. Wooldridge, and M. J. Stokell, J. Mat. Sci., 24, 2775

zyxwvutsr
compounding and processing workplaces, it is neces- (I 989).
sary to place research on additives and modifiers for

zyxwvutsr
polymer blends high in the list of priorities of industrial
laboratories. Whether this need will translate, how- LIST OF ABBREVIATIONS
ever, into an attractive area of research in academic
institutions remains to be seen. CPE = chlorinated polyethylene
EAA = poly(ethy1ene-co-acrylic acid)
REFERENCES

zyxwvutsrqpo
zyxwvutsrqpo
1. L. E. Smith and B. M. Fanconi, “Polymers, Technical Activities 1991,”
EPDM
EPM
EVA
= poly(ethy1ene-co-propylene-co-diene)
= poly(ethy1ene-co-propylene elastomer)
= poly(ethy1ene-co-vinyl acetate)

zyxwvutsr
p. 56, NlSTlR 4696, US. Dept. of Commerce, National Institute of Standards
and Technology, October, 1991.
GMA glycidyl methacrylate
=
2. Anonymous, Plast. Compounding, 13, 6, 12 (1990). MA maleic anhydride
=
1972.

zyxwvutsrqpo
3. L. Mascia, The Role ofAdditiues in Plastics, Edward Arnold, London,

4. L. Mascia. Thermoplastics Maferials Engineering. 2nd Ed., Elsevier. Lon-

don, 1989.
5 . C. D. Han, Mvltiphasr Flow in Polymer Processing, Part 1, Academic
Press, New York. 1981.
6. L. A. Utracki, Polymer Alloys and Blends: Thermodynamics and Rheol-
ogy. Part 3, Hanser Publishers, Munich, 1990.
7. R. P. Sheldon, Composite Polymeric Materials, Applied Science Pub-
MBS

NR
OPS
poly(methy1 methacrylate-co-butadiene-co-
=
styrene)
NBR = poly(butadiene-co-acrylonitrile),nitrile
rubber
= natural rubber
= oxazoline modified PS
lishers, London, 1982.
8. M. Xanthos, Polym. Eng. Sci. 28, 1392 (1988).
PA = polyamide
9. M. Xanthos and S. S. Dagli. Polym. Eng. Sci.. 31, 929 (1991). PBT = polybutylene terephthalate
10. S. B. Brown, in Reactiue Extrusion: Principles and Practice (M. Xanthos.
Ed.). Chap. 4, Hanser Publishers, Munich, 1992. PC = polycarbonate
I I . N. C. Liu and W. E. Baker. Adu. Polym. Techn.. 11, 249, 1992. PE = polyethylene
12. See Ref. 4, p. 390.
13. W. Brotz, in Plastics Additiues. 2nd Ed. (R. Gachter and H. Muller. Eds.).
PMMA = poly(methy1 methacrylate)
Hanser Publishers, Munich. 1987. PP = polypropylene
14. R. Lundberg and H. S. Makowski. J. Polym. Sci: Polym. Phys., IS, 1821
(1980). PPE = polyphenylene ether
15. K. Schwarzenbach, in Plasfics Addifiues Handbook (R. Gachter and H. PS = polystyrene
Miiller. Eds.). Hanser Publishers, Munich, 1987.
16. F. Gugumus. in Plastics Additives Handbook (R. Gachter and H. Miiller,
PVC = polyvinyl chloride
Eds.). Hanser Publishers. Munich, 1987. PVDF = polyvinylidene fluoride
17. H. Hurnik. in Plasfics Additives Handbook (R. Gachter and H. Miiller,
Eds.). Hanser Publishers, Munich, 1987.
SMA = styrene-maleic anhydride copolymer
18. N. Kingio and T. Nakagawa, Polymer J.. 4, 143 (1973). TCP = tricresyl phosphate

248 VOL. 11, NO. 4