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21  Plastics Additives

Ernest A. Coleman
Society of Plastics Engineers, Plastics Engineer & Chemist, C P Technology, PA, United States

21.1 Introduction Based on these examples and many similar ones,


polymer additives or modifiers are necessary to per-
Plastics make useful complex shapes as well as in- form three essential functions. First, additives are
expensive high-volume items. In order to meet these required in order to process or fabricate many poly-
diverse demands, commercial polymers are modified mers. Several as made polymers have thermal sta-
with additives to make plastics. bility limitations that force the producers to find and
Compounding of polymers with additives and utilize stabilizers that allow melt processing.
modifiers to make commercially useful plastics is a Once this obstacle is addressed, room temperature
business that is constantly changing due to new mate- storage can be a concern. Many polymers must be
rials, price changes, improved processing machinery, stabilized from the effects of oxygen, ozone, and oth-
changing customer needs, environmental laws and er gases in the air. Exhaust gas from forklift trucks
concerns, etc. Some needs are persistent such as the has been associated with odor problems in polypro-
requirement to fabricate parts, ways to upgrade prop- pylene food contact items.
erties, how to correct for problems introduced by the Another example involves some polymers (and
use of additives to accomplish the first two items, and monomers) that will not wet reinforcing glass fibers;
controlling costs. The following remarks deal with so wetting agents are used, in order to process the
additives from these points of view. No perfect solu- mixture into a useful plastic. These additives are
tions exist, so polymer additives and modifiers is a usually put onto the glass by the glass manufacturer.
truly dynamic field of study. Sometimes, the plastic compounder adds his own
wetting agent to gain a competitive advantage, but
in all cases, these additives are necessary to make the
21.2 Overview plastic function properly.
The second type of additive is for property en-
Polymers as made are usually not suitable for hancement. In the previous example, a wetting
industrial use as plastics, so industry uses additives agent may be necessary to process the polymer, but
and modifiers to adjust the properties of the as made a coupling agent can be added as an enhancement
polymers to make most of the plastics used today. to provide long-term durability. Fillers improve the
The first polymers that became available are natu- flexural modulus and deflection temperature under
ral products like cellulose, natural rubber, or simple load (DTUL). Color, odor, surface gloss, and other
chemicals like phenol and formaldehyde that make properties are improved by additives of this second
“bakelite.” In order to shape cellulose—the most category. Rubber improves impact resistance. Fibers
abundant polymer on earth—into useful products, improve both impact and modulus in many cases.
two things must happen. Flame retardants (FR) enhance properties of a plastic
First cellulose is modified by chemicals, such as, and make it more valuable. Additives of this second
acetic or nitric acid to make it easy to process. Then type pay for themselves by giving much more per-
these chemically modified cellulose materials are formance value than the added cost of the additive.
cast into thin sheets or films, but thick shapes will The third type or class of additive corrects the
crack, and even the thin forms have stiffness prob- flaws of the first two classes. Plasticizers are required
lems. Plasticizers like camphor and fillers like sand to fabricate flexible PVC. Some of these plasticizers
or sawdust corrected these problems. provide food for organisms, such as, mildew and fun-
Many thermoset materials like the phenolics gus. An additive is needed to correct this.
(bakelite) have large shrinkage that will cause crack- Additives are the essential ingredients that con-
ing. Fillers reduce this shrinkage and solid crack-free vert raw polymers into commercially useful plastics.
parts can be fabricated. Plastics that are fabricated into complex and useful

Applied Plastics Engineering Handbook. http://dx.doi.org/10.1016/B978-0-323-39040-8.00021-3


Copyright © 2017 Elsevier Inc. All rights reserved. 489
490 Applied Plastics Engineering Handbook

shapes that meet so many needs of the modern world 21.3.3 Polyolefins


would not be possible without additives.
PP and HDPE represent two extreme cases of a
wide variety of commercially important polymers.
21.3  Thermal Stabilizers PP and HDPE behave differently when thermally
stressed during the melting process. PP decomposes
to low MW products and HDPE crosslinks; increas-
21.3.1 Overview ing MW. Both polymers have carbon chain back-
Some synthetic polymers have chemical bonds bones and hydrogen is the only other atomic species:
that are less thermally stable than the chemically the difference is in chemical structure.
pure backbone of the perfect structure. These “weak HDPE is a linear chain of carbon and hydrogen
links” often fail during melt processing and lead to re- in the form of methylene (─CH2─) groups. There
duced performance of the resultant plastic part. Some is a methyl group (CH3) on the chain ends. PP is
commercial polymers contain chemical impurities, like HDPE, but every other hydrogen in the chain is
such as, catalyst residues and thermal decomposition replaced by a methyl group.
products that further reduce thermal stability of the This change makes a big difference in thermal sta-
backbone chain of atoms that create the polymer. bility and many other properties as well. Considering
Thermal stabilizers minimize molecular weight only thermal stability, PP will undergo carbon-to-
(MW) change during melt processing by blocking the carbon chain breaks that accelerate with temperature.
adverse effects of polymer flaws and impurities. The At the melting point, chains break so rapidly that the
most thermally sensitive polymers are PVC, polypro- process results in a solid polymer becoming a wax,
pylene (PP), and POM (polyoxymethylene), but even liquid, or even a gas. All this is related to the struc-
high-density polyethylene (HDPE) can change MW tural differences between HDPE and PP. In short, PP
during melt processing. cannot survive melt processing without thermal sta-
bilization.
HDPE does not decompose like PP. HDPE carbon
chains are not destabilized by methyl groups; so the
21.3.2 PVC HDPE resists decomposition by heat better than PP.
Several different chemical classes of additives are On the other hand, because the carbon chain is so sta-
used for thermal stabilization of PVC. These include ble, it will undergo crosslinking. Hydrogen atoms will
divalent lead compounds, tin and antimony based be replaced by carbon chains, both short and long.
chemicals, and mixed compounds of cadmium/ This results in an increase in MW. To minimize this,
barium, calcium/zinc, and many others. In general, HDPE must be stabilized against this type of change.
the lead based thermal stabilizers are used in electri- In short, HDPE needs some thermal stabilization.
cal applications, the tin based ones are used for ex- If the same thermal stabilizers are used for both
ternal uses in siding and other extruded shapes, and polymers, the amounts required to survive one melt-
mixed compounds are used in plastisols and injection ing cycle without excessive change of MW are quite
molded parts. different; PP takes 3 to 10 times the stabilizer, as does
Thermal stabilization of PVC is complex because: HDPE. Polymers that are between PP and HDPE in
the number of side groups (methyl or alkyl groups
• different base polymers are used commercially that behave like methyl) require amounts of thermal
• use of various plasticizers alters the amount stabilizers between the extremes noted.
and type of stabilizer The companies that manufacture these hydrocar-
bon-based polymers are well aware of these thermal
• processing conditions change thermal stabi- stability concerns and more. The additional concerns
lizer needs (twin screw vs. single screw for ex- involve color, odor, surface, etc., problems related to
ample) the specific polymer and materials used in the syn-
• toxicity of the additive package thesis. Catalyst residues can have major effects on
• cost, etc. these other properties and they must be handled ac-
cordingly. There are two methods: elimination and/
All of these topics are considered in detail in or quenching with additives.
Handbook of Vinyl Formulating, second edition, Hindered phenolic antioxidants are useful in ad-
Wiley-Interscience, edited by Richard F. Grossman. dressing some of these concerns. Each manufacturer
21:  Plastics Additives 491

has different standards and needs related to the ex- If crystallization is too fast, crystal size will be
act polymer and its synthesis conditions. This is why small. This is desirable for clear film but for some
there are many different thermal stabilizer systems polymers in time, there will be a growth of crystallite
in use for this large class of hydrocarbon-based size along with a change of properties.
polymers. The best sources of current information There is another meaning for nucleating agent
are patents along with analytical results. Even this that must not be confused with crystal nucleation de-
is not perfect because some additives might undergo scribed previously. In the foaming process, dissolved
chemical changes during thermal processing of the fluids in the polymer must come out of solution, form
material that they are protecting. a gas bubble and create a foam cell. In this appli-
cation, the number of nucleating agents can control
cell size. Shock nucleation is a mechanical process
21.3.4 Polyoxymethylenes that is generally independent of material nucleating
(POM Polyacetals) agent. All of this applies to the foaming process and
not crystallization.
The chemistry of the POM family of polymers and Some polymers crystallize in more than one
copolymer makes them extremely sensitive to acids, crystal type. This leads to different properties from
excessive heat, and many different types of impuri- the same polymer. For example, PP has three well
ties including many additives (colorants, fillers, etc.). known crystal forms; the alpha (α) is the usual form
Some grades are also sensitive to bases. Manufactur- with a melting point of 164°C. Special nucleating
ers of these useful engineering polymers warn pro- agents will produce the beta (β) form with a MP of
cessors and end users about these concerns. So long 150°C. This crystal form is more ductile and impact
as processors and end users observe the guidelines resistant than the alpha but it is thermodynamically
for each specific grade, there will be no need for ad- less stable, so it reverts to alpha. The third form is
ditional additives in most cases. gamma (γ) and it is formed by crystallization after
high sheer in a thin section. It is the “living hinge”
that is so important in PP items with moving parts.
21.4  Nucleating Agents Flexing immediately after molding is a factor in
some products. Other crystalline polymers have dif-
Nucleating agents are used with polymers that can ferent types of crystals that might be commercially
crystallize in order to speed cycle times. After melt- useful.
ing, it is solidification rate of the plastic into a useful
shape that controls processing and cycle time. Both
amorphous and crystalline polymers are subject to 21.5 Antioxidants
molded-in stresses that are a result of the tool geom-
etry. These are the concerns of injection molding and 21.5.1  Primary Antioxidants
extrusion experts since they are controlled largely by
tool geometry and processing conditions. Antioxidants (AOs) function in the environment
Crystalline polymers have an additional concern. and protect polymers for long times at ambient con-
When they cool, they also crystallize. The amount ditions. Several different chemical types of AO serve
of crystallization and the type of crystals formed are different polymers and different functions. Some that
controlled by thermal history, cooling rate, and addi- are in commercial use are discussed later.
tives. There are specific additives that will speed or Phenolic type AOs are very effective as thermal
slow crystal formation and they will also affect the stabilizers as well as providing long-term environ-
exact crystal that forms. mental protection. The chemistry of this class of AOs
Fast crystallization allows faster molding cycles is based on the well known food additive butylated
or clearer extruded thin film. Nucleation speeds this hydroxy toluene (BHT). BHT is an effective AO for
crystallization process. Crystallization is a complex many polymers but its low MW and poor solubility
subject because there can be a downside as well as in many polymers limits use. These limitations are
immediate economic advantage. Many different overcome by the wide range of chemical structures
types of chemicals can nucleate crystallization. The all based on BHT that are commercially available.
effect is specific for the polymer and the chemical. Cost of this class of AOs is falling as the various
Glass fibers, pigments, talc, etc. can nucleate crystal- types come off patent and production in Asia steps
lization for some polymers. up to meet demand.
492 Applied Plastics Engineering Handbook

21.5.2  Secondary Antioxidants in artificial turf that is expected to perform for up to


a decade and more.
Secondary AOs extend the life of the more ex- HALS are used whenever high performance is de-
pensive phenolic type primary AOs. They also delay sired and the chemistry of the plastic allows. HALS
onset of color from used up phenolic type AOs. As cannot be used with halogen containing compounds,
phenolic primary AOs react with oxygen, they form such as, PVC or halogenated FR. Based on the suc-
different chemical structures that are yellow to tan in cess of HALS, other oxime-based AOs are under de-
color. These quinone type structures are not AOs and velopment. They may be less expensive than HALS
they are expensive, having formed from expensive in some cases.
primary AOs. Chemists have dealt with this problem
by developing secondary AOs that keep quinones
from forming until all the secondary AOs are con- 21.5.4 Lactones
sumed.
There are two different chemical types of sec- Lactones are similar to HALS in some of their
ondary AOs. Both have the common properties of chemistry but their nitrogen free chemistry allows
low cost relative to primary and the ability to be use in the presence of halogens. Some natural prod-
oxidized to colorless materials before the quinones ucts have lactone structures and they function as food
can form from primary AOs. Organic phosphite AOs. Lactones are becoming the AOs of choice in
and organic sulfur compounds modified to fit the some plastics as their popularity grows.
needs of specific polymers are the chemicals that
are used.
Sulfur-based secondary AOs sometimes have 21.5.5  Vitamin E
odor problem but they are very effective in rubber-
based plastics. They will react with phosphites, so Also known as, dl-α-tocopherol, vitamin E is an
mixed secondary AOs are never used. AO that is used commercially in polymers. The syn-
Phosphite type secondary AOs sometimes have thetic form of vitamin E will function as well as the
water sensitivity, so there are many different mate- natural product in polymers; most of these uses in-
rials offered for each specific polymer and end use. volve food contact or biodegradable polymers.
Some of the newer secondary AOs of this class ap-
proach or exceed primary AOs in cost, but this is jus-
tified by reduction of color and falling cost of some 21.5.6  Carbon Black
primary AOs. Carbon blacks come in many different variet-
Interaction of the sulfur and phosphorus types of ies. Some grades have AO properties especially in
chemicals can be a problem in recycling. If it is sus- high concentrations. Many grades of plastics that
pected that these two different types of chemicals are are stored or used out of doors contain high levels
present in a mixed recycling blend, additional sec- of these blacks and lesser amounts of conventional
ondary AO of one type should be added in excess to more costly AOs perform satisfactorily. In some cas-
provide long environmental life without color forma- es, the AO can be eliminated altogether.
tion. The same is true when using these systems as
thermal stabilizers.
21.5.7  Thin Films
21.5.3  Hindered Amine Light When thin films are extruded, special care must be
Stabilizers taken to avoid loss of additives by sublimation. The
high surface area and high temperatures of extrusion
Hindered amine light stabilizers (HALS) were make this a critical issue for all high surface parts
developed as photostabilizers and/or metal deactiva- exposed to high temperatures. This is the reason that
tors. It was soon determined that the oxime structure some AO molecules have very high MW to keep
functioned as an AO as well. In fact, these AOs are them from volatilizing. Other parts of the AO mol-
almost self-regenerating so they last for long times. ecule improve compatibility with the polymer that
They also serve their original functions, thus they they are designed to protect. This is why some AO
often do double and even triple duty. These addi- molecular structures look so big and complex; they
tives are responsible for high performance PP used have to be that way to function.
21:  Plastics Additives 493

21.6  Flame Retardants FR systems. The phosphorus-based systems appear


to function best with oxygen containing polymers.
21.6.1  Halogen Free The char is believed to be a complex phosphorus ox-
ide based coating that blocks oxygen from coming
Halogen free flame retardant systems are highly de- into contact with monomer or other flammable ma-
sirable because they have fewer toxicity and regulatory terials. The melamine-based systems form chars that
issues than the sometimes more effective halogen sys- are based on nitrogen as well as phosphorus in the
tems. This is an active area for research, and new addi- case of melamine phosphate systems.
tives and tests are appearing with increased frequency. Nanoparticles dispersed in polymers are pre-
Some halogen free systems use phosphorus or nitrogen sumed to block or slow down the contacts between
chemistry and others are based on inorganic minerals. oxygen and fuel. This reduces burning rate and al-
lows other FR to extinguish the fire. This binary sys-
tem approach can be cost effective by reducing the
21.6.2  Inorganic Flame Retardants amounts of FR materials required. This also allows
maintenance of many physical properties that other-
The least expensive, most used, and possibly least wise would be altered by larger amounts of additives
toxic FR is aluminum trihydrate (ATH) and similar in- as often happens with the other FR systems.
organic hydrates. These materials must be used at very Some polymers have some unique chemistry that
high loadings (sometimes exceeding 60% by weight) allows the use of relatively low amounts of additives
so they function as fillers as well as FR materials. They that catalyze a molecular rearrangement that provide
function by decomposing to liberate water at tempera- some flame resistance. PC is an example. It is a poly-
tures exceeding the melt processing temperatures of mer based on para orientation of chemical bonds.
many polymers, so they are not used in many of the These para bonds can be changed to meta bonds by
high temperature thermoplastics, such as, PA, PBT, traces of sulfonic acids. Meta linkages are less flam-
polycarbonate (PC), etc. Even PP is beyond the lim- mable than the original para ones. Of course, some
its of ATH. When ATH decomposes, steam results. If other properties are changed as well. Other aromatic-
this happens during melt processing, the polymer is based polymers take advantage of this chemistry.
foamed. ATH is used in polyethylene wire and cable “Nomex” is a meta-bonded form of the better known
(W&C) formulations as well as thermoset polymers, “Kevlar.” Kevlar with para bonds has better proper-
such as, epoxy and thermoset polyesters. So long as the ties but Nomex is more flame resistant and is used by
temperature does not exceed 200°C, ATH is safe to use firefighters worldwide.
(but check first before doing large scale processing).
Magnesium hydroxide is an inorganic hydrate that
is more thermally stable than ATH. It can be used 21.6.4  Halogen Systems
in PP and similar high melting thermoplastics. Like
ATH, Mg(OH)2 must also be used at high concentra- Traditional antimony/halogen systems are still in
tions to achieve good FR performance. wide use because they are proven by years of suc-
These high concentrations of FR minerals tend to cessful applications in the electronic and electrical
increase part density and brittleness. Some polymers markets. There are many applications where thin
can react with them as well. Thermoplastic polyester sections (<1 mm) must be flame retarded to meet
like PBT cannot be used with them for this reason. UL V-0 or V-5 standards where only halogen systems
The big advantage of these inorganic materials is low are effective.
cost as well as their white or light color and the non- One of the more popular systems is decabromodi-
toxic benefits. Sometimes they are used at low con- phenyl ether (DECA) and antimony trioxide. DECA
centrations with other FR materials as cost savings has been under attack but so far, it seems to be less
additives. Sometimes they provide other benefits in toxic than several closely related bromated aromatic
certain electrical applications like ion sequestration. compounds that have been banned in Europe and
elsewhere. Some of the concern about DECA oc-
curred when decabromodiphenyl accidentally got
21.6.3  Other Halogen Free Systems into the human food chain. The similarity between
the two different chemical names (decabromodiphe-
Additives based on melamine, phosphorus, and nyl and decabromodiphenyl ether) is not easily de-
other char making materials are finding use in specific tected by those who have not studied chemistry, and
494 Applied Plastics Engineering Handbook

this may have contributed to some of the concern. On When it was determined that some colorants might
the other hand, there are real toxicity concerns about hurt the environment, they were no longer available
many brominated organic chemicals. or they were manufactured at offshore locations.
High melt processing temperatures require more Some colorants are safe under all end use conditions
thermal stability in the FR systems and this usually but can be a problem when discarded at the end of
means the more expensive bromine compounds. Re- their useful life. Other colorants might be a problem
member, the FR system must be stable at process- in fires or when incinerated.
ing conditions and decompose to extinguish the fire Due to this concern, today some dyes are used as
at temperatures slightly above the highest process- pigments by converting the soluble dyes to insoluble
ing temperature. When the thermal properties of the pigments. There can be processing problems with
polymer allows, chlorine-based compounds are used these materials because sometimes they can dissolve
with antimony oxide, because they usually decom- or melt in the polymer carrier at high temperature.
pose at lower temperatures and they are usually less When these pigment dyes come out of solution upon
expensive than their bromine counter parts. cooling, they crystallize in different sizes and/or
Halogen-based FR are special chemicals. They shapes than intended, thus altering color. This alters
are required to be relatively noncorrosive, low toxic- color and transparency leading to customer problems.
ity, and yet, liberate corrosive halogen compounds Color is a most interesting field of study. An intro-
that react with antimony oxide at fire temperatures. ductory course of several days’ length is offered by
Some of these chemicals have chemistry similar to SPE and it is useful even for plastics professionals
PVC and, thus, sometimes they require thermal sta- not directly involved with color.
bilizers to withstand thermal processing. Some of the reasons that certain colorants are
PVC and other highly halogenated polymers are more expensive than others are worth a little in-
useful in construction applications (sometimes, af- vestigation. Copper phalocyanine (CPC) blues and
ter they are upgraded with antimony oxide) such greens are relatively nontoxic colorants, but they are
as siding, windows, and electrical systems includ- manufactured overseas for the most part because the
ing commercial W&C uses. Some of these PVC process has many byproducts that are hard on the en-
type polymers are used in blends with more flam- vironment. Cadmium colors (reds, oranges, and yel-
mable polymers to make flame resistant business lows) are manufactured from cadmium compounds
machine housings with stringent FR specifications. that are highly toxic. The colorants (cadmium sulfos-
These are excellent materials that make use of sev- elenides) are nontoxic but their products of incinera-
eral properties of PVC as a blending additive. ABS, tion are toxic. All of these concerns and others apply
SBR, and similar polymers are blended with PVC for to several classes of polymer additives and modifiers
these applications. that themselves are only mildly toxic.

21.7  Color and Colorants 21.8 Fillers


Pigments are solid materials that scatter as well as Calcium carbonate comes from natural sources
absorb light. Dyes are soluble materials that absorb such as bone, limestone, shells, or it can be made
light but do not scatter it. Thus the color from dyes synthetically. It can be pure enough to take as medi-
is often brighter, sharper, transparent, or cleaner than cine (antiacid), or it can be ground up rock with
that from pigments. many impurities (also used as antiacid). It may be
Most plastics use pigments for color in spite of the the most widely used filler. (A similar claim can
above because pigments, in general, are more ther- be made for carbon black or carbon in all its many
mally stable, more stable to exposure to light, and not forms.) Calcium carbonate is widely used in PVC as
prone to “bleeding” or exuding out of the plastic to an acid acceptor, in polypropylene as a filler, and in
discolor objects in close contact. Pigments produce many thermosets and thermoplastics as an inexpen-
opaque colors in thick sections and translucent ones sive filler.
in thinner sections. Most colors in a common series Precipitated grades as well as the pulverized ones
look better if they all have similar degrees of trans- can be surface modified. The precipitated calcium
lucency at the same thickness. Therefore, depth of carbonate that is used in polypropylene (and other
color or opacity as well as color must be matched similar thermoplastic resins) is usually surface modi-
when working with pigments in plastics. fied with stearic or isostearic acid.
21:  Plastics Additives 495

CaCO3 is an extremely important commercial ma- mining operations and machining crystalline silica
terial for a few large volume polymers; both thermo- filled plastics.
plastic and thermoset. If one grade does not work in Clay is another common material of wide ranging
your application, ask your vendor as well as other properties. Like all fillers, just because one grade or
vendors for alternatives. There will be two or three type does not perform satisfactorily does not mean
grades for most applications, but only one or two will that all grades will fail. Some time with your vendor’s
generally give superior performance. As in all addi- technical department can pay off here in finding inex-
tive situations, keep looking and asking until you get pensive filler with unique value to your application.
the results you want. Clay is becoming important in some nanocomposites
Carbon black provides a black color that protects because it can be exfoliated into nanothin platelets.
many thermoplastic polymers from the damaging ef- Talc is white and soft, so it is a valuable filler. The
fects of sunlight (UV) by absorbing the damaging flat shape of talc particles adds reinforcing value in
energy. Certain carbon blacks will function as AO addition to simply acting as a filler. Asbestos does
materials and others are used as jet black pigments. occur in some talc deposits, so the location of the talc
Still other grades function as conductive fillers for mine from where your talc supply comes could be
EMI shielding. important in some demanding applications.
Carbon blacks are made from many different raw Mica can vary in color, but this is offset by better
materials including natural gas, petroleum, coconut physical properties than talc in some filler applica-
shells, and other varied organic materials both natu- tions. There are many forms of this widely distrib-
ral and synthetic. Fibers, such as, polyacrylonitrile, uted mineral. The naturally thin sheets of mica can be
bamboo, cotton, etc. are the sources of other interest- exploited by exfoliation to the nanothickness range.
ing forms of carbon fibers and filaments. Other car- Wood and nut shell flours are natural products
bon forms are becoming available from special gas that serve as both fillers and reinforcements due to
phase chemistry yielding fullerenes and tube forms. their fiber structure. Moisture levels are a problem
These are small scale at the present time, but the fu- in many applications. These materials may become
ture might be very bright for these dark materials. much more important in the future as recycled wood
Reinforcing carbon blacks are essential ingredients products become abundant. Public concern as well
in many elastomers used in car and truck tires. as technology may get involved in some of the ap-
The structure of carbon black involves size, shape, plications, and it is becoming politically correct to
and connection of fundamental particles into high use some renewable resource in your compounding.
levels of structure that gives the reinforcement. Car- Fly ash is another product that comes from an
bon blacks have surface areas measured in tens to increasing awareness of our environment. Some ap-
many hundreds of square meters per gram. For this plications have been found in polymers for fly ash
reason, intensive mixing is often required for ul- and in time there will be more. Modern technology
timate dispersion. Degree of mixing can be judged is involving public relations and environmental is-
by viewing a thin film against a strong light. Disper- sues more and more. Whenever these issues can be
sion measurement requires a microscopic inspection turned into commercial benefit for your company or
of thin film or a pressure drop test with an extruder, organization that should be the direction of research
screen pack, and differential pressure gauge. when the cost can be justified. Quality products must
Research on carbon-based materials, such as, never be sacrificed, however. Slag is also being pro-
the fullerenes (buckey balls), single wall nanotubes cessed into filler form for plastics. Inexpensive fillers
(SWNT), and graphene (single layer of graphite) is like slag, fly ash, etc. must be carefully evaluated for
leading to many new and improved products for elec- toxicity.
tromagnetic shielding (cell phones) and advanced Wollastonite is a mineral that has enjoyed some
computer flexible folding flat screens. success as an asbestos replacement as well as finding
Silica occurs in different crystal forms and impu- niche markets on its own. The shape is elongated so
rity levels. Its low cost and widespread availability there is reinforcement as well as filler applications.
are offset by its density (2.65 g/cm3), hardness (7 on A large use is in asbestos replacement applications.
mho scale), and concern about toxicity of some but Glass spheres are a product of ground up glass
not all grades. Its wide geographic distribution makes from bottles and jars, as well as special grades that
it available in all parts of the world. So it is widely are made for specific applications. The major use
used. The crystalline form of silica causes silicosis or of this product is in reflective paints (those reflec-
white lung when inhaled in excess as occurs in some tive white stripes on black top roads are due to this
496 Applied Plastics Engineering Handbook

material). In polymer applications, glass beads im- fibers (under about 2 cm) that are used in thermo-
part geometrically flat surfaces in injection-molded plastics that are intended for melt processing appli-
parts along with good color. Glass beads are used cations.
with glass fibers and thus balance reinforcement and Reinforcing fibers are used for improving the
warping. strength of composites. The vector direction(s) of the
Hollow glass and mineral spheres have all the strength improvements, the value of those improve-
advantages of solid glass spheres, plus lower den- ments, application and manufacturing techniques,
sity. The increased cost may be completely offset and special needs must be considered when selecting
by the reduced density (when volume or area pric- the fiber for the application. If very smooth surfaces
ing is used). Replacing expensive resin with hollow must result, random short fiber injection molding
spheres of lower density is often a very good trade material may not be adequate. Rocket casings must
off. Most applications are in thermosets, where be lightweight and reliable, so special fabrication
the spheres do not have to withstand high compres- techniques and fibers are used. Electrical and thermal
sive forces. Furniture manufacturers make extensive conductivity can be the reason for choosing a certain
use of hollow low-density fillers in syntactic foam construction over a less expensive one.
for legs, arms, and even tops. These materials have Glass fibers have proved themselves in many dif-
found wide use in aerospace applications as well. ficult applications. This was not always the case, but
Injection molding pressures range between about surface modification of various grades of glass fibers
10,000 and 30,000 psi, and this will crush most hol- over the past 50 years has led to a wide variety of
low spheres. In general, the lower the density, the fibers for many different applications.
lower the compressive strength of the hollow spheres; E glass is most common in thermoplastic compos-
so only low pressure fabrication can be used. ites. The E stands for glass that has superior electrical
Recycled materials of many types are coming properties, C is for glass with the best chemical resis-
onto the market. Some companies may even choose tance, and S is for highest strength glass formulation.
to make polymers specifically as compatibilizing ad- S glass is the strongest and it tends to be used in
ditives for selected types of recycled materials. The thermoset plastics where filament winding or pultru-
construction, pipe, and transportation industries are sion is used; these maximize the strength, nickel-
candidates for many of these applications. Ground coated glass is conductive, and hollow fibers with
thermosets with high filler loadings will be an impor- improved strength to weight ratios are still being
tant source of new fillers and manufacturers may be tested for cost/benefit in many composites.
required to use these products in some applications. There are still concerns about the use of glass
Recycled textile fibers can serve as reinforcements, fiber for some applications, like high temperature
which add value to composites if they can be col- fluoropolymers that might liberate hydrogen fluoride
lected in usable forms. (HF) during processing, acetal resins that are sensi-
Portland cement is inexpensive, widely avail- tive to trace amounts of impurities, polymers that are
able, and water curable. It has been tested in several processed at temperatures too high for many usual
polymers as an additive that causes the composite to surface modifiers for glass, and some durability is-
harden with time of exposure to moisture, turning a sues concerning thermosets (crazing, weathering,
thermoplastic into a more durable thermoset. etc.).
Even with all these concerns, glass fibers are the
standard against which other fibers are compared.
21.9 Reinforcements Glass fibers and indeed all rigid fibers have a tenden-
cy to introduce some warping in thermoplastic com-
21.9.1 Overview posites. This warping is related to the fiber, which is
stiff and nonshrinking, and the plastic melt which is
Reinforcing fibers for plastics are used in several initially soft but later hardens. When this occurs with
ways. They can be wrapped around polymer tubes, some degree of bonding between the fiber and the
laminated between polymer surfaces, laminated to resin, there will be molded in forces that can result
the surface, woven into complex shapes containing in warpage in the part. Some work with glass fibers
polymer as an adhesive matrix, extruded as long or that have three lobes has led to a reduction in this
short fibers into polymer composites, and blended type of warpage. Another approach to the problem is
with polymers to make carpets with fiber reinforced to mix fibers and fillers (glass spheres) to reduce the
backings. This discussion is limited to mostly short warpage.
21:  Plastics Additives 497

An experimental low melting glass fiber will soft- Special applications in body armor justify the current
en at the processing temperature of the engineering price of $45–85/kg.
plastic like polyether ether ketone (PEEK). Then, as Stainless steel is an excellent conductor of elec-
the resin cools, the glass will move a bit to accommo- tricity. Very fine diameter SS fibers can be added to
date the shrinkage of the matrix resin. In theory, this many polymer composites without loss of mechani-
will provide strength enhancement without molded- cal strength or toughness. This has led to their use in
in stresses normally found with conventional fiber injection moldable electrically conductive RFI/EMI
glass reinforcements. shielding applications.
The latest new development in glass fiber innova- Cotton and cellulose fibers like sisal have good
tion is a commingled glass and polymer fiber. This high temperature properties (equal to or even above
morphology allowing close contact of the two mate- nylon). Some cotton fibers are as long as 4 in. Water
rials is offered in hopes of improving the wetting of removal is a problem in the use of natural fibers, but
the glass more completely. benefits including renewable resource may offset the
Graphite or carbon fibers are very high modulus difficulties. Polymer-coated cotton fabric is widely
materials that are conductive (electrical and ther- used in many different applications. Some excellent
mal) and withstand flexing within their elastic limits work on recycled wood and natural fiber composites
very well. The surface is inert so it is difficult to for use in construction is being done at the USDA
modify. As a result, the full value of these materi- Forest Products Laboratory in Madison, WI.
als is seldom realized in many applications unless Wood flour (sawdust) is used in PE or PVC to
the fibers are placed individually to maximize their make the popular grades of plastic lumber that com-
value. An immense amount of work has been done petes with pressure treated wood. Plastic lumber is
on this surface modification problem by some excel- maintenance free and colorable, giving it a big ad-
lent scientists, but progress has been slow. Current vantage over lumber in several specific applications
interest in fullerenes and microtubes (SWNT) may like outdoor decking.
help in this area. Woven and nonwoven synthetics are finding use in
The very high flexural modulus and the light many niche markets; some of which are quite large.
weight make carbon fibers the material of choice for Kevlar is growing so fast that it is mentioned by it-
many aerospace parts and high tech sports equip- self, but there are many other materials just looking
ment. With just a slight improvement in surface ad- for problems that they alone can solve. For example,
hesion, the use could skyrocket. So far this problem PTFE fibers have been used in low friction acetal
has not been solved, but many small improvements resin and PTFE covered glass is used in domed sta-
are upgrading the value of carbon fibers constantly. diums.
Kevlar is a high temperature polymeric fiber that Mineral fibers are coming onto the market place
is tough. Surface bonding is a concern but less than every so often. They tend to be brittle but inexpen-
in the case of carbon fibers because Kevlar is more sive. Some must be checked for toxicity (asbestos
flexible. Price will drop as supply is increased and type). As new applications arise, the user of these
more manufacturers come into the business. Many of (and other) fibers must remain alert to new develop-
the applications that might have gone to carbon will ments in toxicity concerns.
go to Kevlar because it can be modified to meet end
use requirements easier than carbon fibers.
Polyethylene can be spun in the gel form (5% 21.10  Impact Modifiers and Impact
UHMWPE in decahydronapthalene) to a very high Modification
strength fiber on the basis of the free-breaking length.
(Free-breaking length is the height to which a fiber One theory holds that failure begins at a flaw.
can be lifted before breaking under its own mass.) If flaws are kept below a certain critical flaw size,
The best UHMWPE fibers have a free-breaking failure will be prevented. This is seldom possible,
length value of 336 km compared with Kevlar of so rubber particles are used to dissipate the point of
193 km, carbon of 171 km, and steel with a value of the crack so that the crack can no longer propagate
37 km. This measure of strength to weight is truly through the brittle matrix resin. According to this
impressive for polyethylene. The low melting point view of why plastics fail in impact or stress situa-
(145°C) and the difficulty of modifying the surface to tions, rubber particles must be placed in the path of
make it reactive with coupling agents are serious lim- the crack to prevent failure. The questions to be an-
itations that are yielding slowly to research efforts. swered concern the amount of rubber and the size of
498 Applied Plastics Engineering Handbook

the particles. Apparently, there are some flaws that compatibilizers. This is because all of them have two
require many small rubber particles and there are different phases with the exception of the vulcanized
some flaws that require fewer but larger rubber par- or thermoset elastomers. At least one of the phases
ticles. For each polymer matrix, there is an optimum must be compatible with a known polymer in order
size or sizes of particles. These rubber particles do for these materials to be commercially useful. If the
not have to be spherical, but they frequently are. The other phase is compatible with a different commer-
rubber phase is not compatible with the plastic phase cial polymer, then you have a compatibilizer that is
and this can lead to uneven distribution of the elas- also an impact modifier. Because of the similarity of
tomer in the resin matrix. There are several ways to technology and growing interest in both impact mod-
overcome this fundamental problem. ification and compatibilization, there will be more
The rubber phase can be in a copolymer that has materials appearing every year for the next decade
blocks of elastomer and blocks of matrix polymer. or longer.
This will make the elastomer compatible with the
continuous polymer phase. Many polymers of the
A─B, A─B─A, A─B─C, etc. exist. 21.11 Miscellaneous
The rubber phase can be grafted to the polymer
phase. The rubber toughened nylons are a spectacu- 21.11.1  Coupling Agents
lar example of this technology. A variation consists
of polymers grafted to elastomers to provide a three Coupling agents chemically bond dissimilar ma-
dimensional interface. The rubber phase can be en- terials together even in challenging environments.
capsulated inside of a particle rich in the matrix resin. When plastic composites are made with inorganic
Sometimes, the rubber particles are mixed with reinforcements, wood fibers, or other fillers, these
the plastic without special compatibilizers due to materials tend to separate from the plastic and make
an unusual affinity between the two phases; one of the composite weak if they are not compatible with
which is crosslinked and the other is not. Some ther- the plastic. Coupling agents increase the time that
moset systems are formulated in this fashion. it takes for dissimilar materials to fail in service.
The aforementioned discussion assumed that a The improvements are measured in orders of magni-
propagating flaw was the cause of failure. It would be tude. Many of our modern high performance plastics
better if the flaw never existed. Many modern impact would not exist without coupling agents. There are
modifiers are designed to prevent the formation of some special cases where polymeric coupling agents
the flaw. The approach here is to prevent the polymer can react with metal oxides, amines, or with them-
phase from yielding by extending the elastic range of selves to form cross-linked composite structures that
the polymer by control of monomers. have commercial value as well as great scientific in-
The previous discussion points the need for dif- terest. The best coupling agents for many polymers
ferent types of impact modifiers. Some are used to are based on silane chemistry. Some other materials
prevent flaws, and some minimize the effects of are claimed to act as coupling agents. These products
these flaws even though they do not prevent flaws. must be carefully checked for durability (especially
Some impact modifiers modify the effects of flaws in wet or humid environments) because they do give
that are caused by other additives. There are many some short-term property and even processing im-
materials to serve these many different functions. provements, but they may not last as well as true du-
rable coupling agents.
• Thermoplastic elastomers
• Random copolymers 21.11.2  Surface Modifiers
• Vulcanized or thermoset elastomers
• Polymers grafted to elastomers Surface modifiers change the physical chemistry
of mineral and fiber surfaces. Hydrophilic surfaces,
• Elastomers grafted to polymers
as commonly found with many mineral fillers, can be
• Block polymers made hydrophobic by surface modification. Mineral
• Plasticizers and glass fibers can be treated so that the polymers
they reinforce will wet their surfaces. Surface modi-
In addition to serving as impact modifiers, fiers are chemically bound to one surface and physi-
many of the above materials can also function as cally attracted to another surface or material. They
21:  Plastics Additives 499

unite dissimilar materials with physical and chemical as many as three hundred or more simple chemicals
bonds, where the physical bond is not permanent and and polymers that have been used commercially over
the chemical bond is. Again, silanes are very effec- the past decades.
tive in these applications, but so are some titanates, Acrylic polymers are used in outdoor applications
and chemicals like stearic acid. of rigid PVC formulations. Other ABS and SBR
polymers are used in less demanding applications.
The workhorse for flexible PVC is DOP (dioctyl
21.11.3  Wetting Agents phthalate, bis-2-ethylhexyl phthalate, and several
other names). Questions about toxicity have been
Wetting agents have a physical attraction for both raised and addressed, but some concerns still exist.
surfaces involved. Wetting agents have no permanent This has led to DNP (dinonyl phthalate), citric acid
chemical bond to the surfaces that they wet. Therefore, esters, and many other substitutes. Many of these
wetting agents are easily extracted from composites are more expensive and less effective than DOP, but
by means of solvents and, consequently, they are not safety concerns keeps them on the market, especially
permanent. They cannot survive in water or high hu- in toy applications.
midity because they are extracted or the water comes Some FR grades of flexible PVC use phosphorus-
between the wetting agent and the hydrophilic surface, based plasticizers. There are special plasticizers for
thus destroying the temporary bond. Many titanates nonskid vinyl floor tile. These applications illustrate
and organic surfactants (both ionic and nonionic) are many of the specialized needs of PVC that require
examples of additives that function in this application. specialty plasticizers.

21.11.4 Biocides 21.11.6  Mold Release Agents


Most synthetic polymers are of little or no food Some mold release agents are sprayed directly
value to bacteria, mold, mildew, etc. The exceptions onto the tool steel of the mold. These include among
appear to be polymers that contain nitrogen like ny- others some silicone and some fluorocarbon-based
lon or polymers that contain plasticizers that are ap- materials. Other mold release agents are coated or
petizing to the microbes involved. sprayed onto the surface of the molding powder.
Additives used for biological defense cover the This is done in batch blenders just before pack out
spectrum from ones with odors that offend rodents to avoid passage through an extruder. Most release
to toxic materials that kill mold and mildew. There agents that are melt blended with polymer can be ap-
is a wide range available but there are still reports plied in this alternative fashion.
of squirrels electrocuted while biting through power Mold release agents function by coming to the
lines. surface between plastic and tool. Some like certain
Plasticizers for PVC are a special problem that fluoropolymers do not mix or dissolve well in the
must be carefully considered when making formula- polymer, but they do have a good affinity for the
tions for shower curtains and other applications that die or mold surface. Other mold release agents dis-
involve good growth conditions for mildew and fun- solve in hot polymer but come out of solution during
gus. There are many additives to consider for each the extrusion or molding process.
application and the user has a wide field from which Mold release agents may have more than one func-
to select. Quaternary ammonium salts prevent bac- tion. Some stay on the plastic surface and lubricate
terial attack. A very old and well known biological the plastic. Others bring other additives with them as
control agent is coming back into popularity. they go the shape or part surface. This is useful for
Silver salts are well known to inhibit many kinds surface active additives, such as, biocides and some
of biological species. This technology is currently UV stabilizers.
the material of choice for many plastics. Sometimes mold release agents function too well
and interfere with printing, gluing, and painting.
Changing from a calcium salt of a fatty acid to bar-
21.11.5 Plasticizers ium or zinc salt can make all the difference. A good
metal deactivator, such as, calcium stearate is a mold
Plasticizers are a high volume class of additive release agent, but it might hurt printability of the part
mainly used in just one polymer, PVC. There may be surface in some systems.
500 Applied Plastics Engineering Handbook

When mold release agents dissolve in the melt, often improve surface appearance. Traces of PA 6
they can reduce melt viscosity and function as a pro- will make PA 6, 6 a bit easier to process and a bit of
cessing aid. Many processing aids also function as recycled PET will reduce the cost of some polyesters
mold release agents. like PBT. Many of the major additives discussed in
Since the class of chemicals that function as mold this article are important enough to have books writ-
release agents is broad (salts, amides, polymers, ten about their use. Some of the books that this au-
etc.), many individual members can have more than thor uses are noted subsequently.
one function. Function varies with polymer type as
well as chemistry of the mold release agent. Polymer Modifiers and Additives, by John R. Lutz
and Richard F. Grossman. Marcel Dekker, Inc.
2000 ISBN 0824799496.
21.11.7 Others Coloring of Plastics Fundamentals second edition
There are dozens of other additives that are used by Robert A. Charvat. Wiley-Interscience 2003
occasionally. Along with these additives comes spe- ISBN 0471139068.
cial processing techniques like grafting an additive Plastics Additives third edition by R. Gächter
to a polymer to keep it immobile. Small amounts of and H. Muller. Hanser Publishers 1990 ISBN
polymers like polymethylmethacrylate (PMMA) will 3466156801.