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The following are additional characteristics to
keep in mind:
. An-
other name commonly used for polymers based on
polymethyl methacrylate is acrylics. Acrylics are es-
ters obtained by reacting an acid such as methy-
lacrylic acid with an
alcohol. The monomer has a methyl group (CH
3
) re-
placing one hydrogen atom on an ethylene molecule
and a COOCH
3
substituent (from the acid) replacing
another hydrogen atom:
The acrylics are rigid and clear, making them useful
on machines for guards, sight glasses, and covers. An-
other major industrial use is in coatings. They are
used for clear lacquers on decorative parts, and, pig-
mented, they are used for paints. Of general interest,
most false teeth, auto light lenses, and watch crystals
are made from acrylics. They are readily injection
molded.
Fluorocarbons
Fluorocarbons are a family of polymers based on a
fluorine atom substitute. The oldest fluorocarbon,
polytetrafluoroethylene, may be more familiar under
the trade name Teflon
. It is made by polymerizing a
gas with the same chemical name. The acronym for
this polymer is PTFE. The monomer has one fluorine
atom replacing each hydrogen atom on an ethylene
molecule:
PTFE is one of the most chemically inert materials
known, so it is used for seals, tubing, and small vessels
used to handle very aggressive chemicals. The major
limitations of PTFE are that it is expensive, it is not
moldable by conventional techniques, and it has low
strength and creep resistance. It should not be used
for structural components.
The principal fabrication limitation of PTFE is
that it does not melt and flow like most thermoplas-
[CH
2
C(CH
3
)COOCH
3
]
tics (even though it is usually considered to be ther-
moplastic). Shapes and parts are compacted from
powder and sintered with techniques similar to those
used for powdered metals. A number of melt-proces-
sible grades of fluorocarbons have been developed to
circumvent this limitation.
Polytrifluorochloroethylene (PTFCE) can be in-
jection molded, and it is used for the same types of
applications as PTFE. The sacrifice for moldability is
a decrease in maximum use temperature (200C vs.
280C) and a decrease in chemical resistance, com-
pared with PTFE.
Fluorinated ethylene propylene (FEP) is a
copolymer of PTFE and hexafluoropropylene that
more closely approaches the properties of PTFE than
other fluorocarbons. Its uses are mostly in chemical
handling.
Perfluorinated alkoxy is a newer grade of injec-
tion moldable fluorocarbon that has an even higher
use temperature (260C) than PTFCE and FEP, and
better creep resistance than PTFE. The chemical re-
sistance approaches that of PTFE.
Polyvinyl fluoride is not as chemical or heat re-
sistant as PTFE, PTFCE, FEP, or PFA, but it has bet-
ter melt processibility. It can be used for molded
parts, but more frequently it is used for wire insula-
tion and for decorative and weather-resistant coat-
ings. Interior wall coverings can be made washable
and stain resistant by PVF coatings. PVF films are
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also laminated to aluminum to make house siding
and architectural panels.
Vinylidene fluoride is one of the most moldable
fluorocarbons. It is used mostly for molded parts re-
quiring chemical resistance. It is not as corrosion re-
sistant as the other fluorocarbons (except PVF), and
the maximum use temperature is only 300F (150C).
Ethylene tetrafluoroethylene is a PTFE ethylene
copolymer with excellent moldability. It has lower
density, greater toughness, and higher strength than
PTFE and FEP. The maximum use temperature,
350F (180C), however, is much lower.
Ethylene chlorotrifluoroethylene is a copolymer
similar to FEP in moldability and uses. It has better
environmental resistance and a slightly higher use
temperature, 390F (200C), than ETFE.
There are a few additional commercially avail-
able fluorocarbons, but they are essentially modified
versions of the foregoing. The modifications include
alloying, blends with other polymers, and various
reinforcements.
Summary: Ethenic Engineering Plastics
As is the situation with the commodity plastics, the
ethenic polymers are the most used. ABS, acrylics,
SAN, and the fluorocarbons easily make up more than
half of the production of engineering thermoplastics
in the United States. Some people do not consider
ABS, SAN, and acrylics to be engineering plastics, but
without a doubt these plastics are used for engineer-
ing applications. In the 1970s, a production automo-
bile (the Cord reproduction) had a body made from
ABS. PTFE is a relatively weak material, but because
of its low friction when mated with steel under heavy
loads, it is used for bearing pads to support high-rise
buildings and bridges in earthquake zones. Acrylics
are used in architectural applications for many struc-
tural items, but one of the most taxing applications is
for windshields and canopies on jet aircraft.
In summary, the substitution of a functional
group on the ethylene molecules has created the low-
est-cost commodity plastics as well as some of the
plastics most used for engineering applications. The
mechanical properties range from intentionally very
weak in plasticized vinyl (PVC) to very strong in
acrylics. Chemical properties range from extremely
chemical-resistant fluorocarbons to plastics that dis-
solve in water (polyvinyl alcohol, PVAL). The most
used ethenic polymers make the lowest-cost plastic
components; other ethenic polymers are among the
most expensive plastics. This polymer family is prob-
ably the most important thermoplastic family, and
designers should become familiar with at least the
ethenic plastics that we have described.
8.4 Other Engineering Thermoplastics
Polyamides
The polyamides are polymers formed as a condensa-
tion product of an acid and an amine. They all con-
tain the characteristic amide group: . The
basic reaction involved in forming a polyamide is
There are a number of common polyamides; the
various types are usually designated as nylon 6, nylon
6
6, nylon
6
10, nylon
6
12, nylon 11, and nylon 12.
CONH
Polymer Families 201
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These suffixes refer to the number of carbon
atoms in each of the reacting substances involved in
the condensation polymerization process. They have
been maintained as an identification factor. Nylons
with a period between the numbers in the suffix are
homopolymers; nylons with a slash (/) between the
numbers are copolymers; nylon
6
12 is a copolymer of
nylons 6 and 12.
The term polyamide is the true generic name for
this class of polymers, but the term nylon has been
used for so long that it has lost its trade name status
and is now an acceptable generic name. Nylon 6 was
developed in the 1930s and was brought to promi-
nence in World War II as a replacement for silk for
parachutes. Nylons are crystalline thermoplastics
with good mechanical properties and good melt pro-
cessibilty. Nylon was one of the first engineering plas-
tics. It has sufficient mechanical properties to allow
its use in structural parts. The mechanical properties
of nylon homopolymers are among the highest of all
engineering plastics. Continuous use temperatures
can be as high as 260F (120C), but properties can
degrade with time due to oxidation. The biggest dis-
advantage of nylons as engineering materials is their
tendency to absorb moisture. Nylon 6 can absorb up
to 10% by weight [equilibrium at 20C and 100% rel-
ative humidity (RH)]. This moisture absorption
causes a lowering of tensile strength and stiffness, but
an increase in toughness. Nylons 6 and
6
6 are very
prone to moisture absorption, and nylons 11 and 12
are the most resistant of the group. The moisture ab-
sorption characteristics of the other grades are inter-
mediate. The most troublesome aspect of moisture
absorption is not the effect on strength (this can be
dealt with by design), but the size change in use and
in fabrication. A moisture absorption of 10% in a
nylon 6 part could result in a dimensional change as
high as 0.025 in./in. (0.06 cm/cm). This means that a
molded part could change size with variations in the
ambient relative humidity. For this reason, nylons are
best suited for applications in which size change in
use would not be detrimental to function. Examples
of such applications are nylon coatings on dishwasher
racks, wire covering, extruded hose, appliance
wheels, soles for footware, awnings, rope, tire rein-
forcement, textiles for clothing, and carpeting.
Nylon is widely used for gears, cams, slides, and
the like on machinery where size change in service
could affect serviceability. In these applications, man-
ufacturers data on size change must be used in de-
sign calculations on operating clearances.
New grades of nylon and new reinforcement sys-
tems are being developed to overcome some of the
limitations of the 6,
6
6, and
6
10 nylons. Aramid resins
(Nomex, Kevlarsee the Modern Plastics Encyclope-
dia for plastic trade name attributions) are polyamides
that contain an aromatic functional group in their
monomer structure:
They are produced mainly in the form of fibers and
sheet. Some aramids have high tensile strength, and
they can withstand continuous use at temperatures
as high as 500F (260C). Chopped Nomex fibers
have been used to replace asbestos as a reinforce-
ment in clutch and brake friction materials. Nomex
sheet is used for insulation on electrical devices that
see high temperatures. The aramids and other new
grades of nylon will ensure that this class of polymers
will continue to be competitive in properties with
more recently developed polymer systems. It is the
major engineering plastic in volume.
Nylons have tensile properties comparable to
some of the softer aluminum alloys. Types 6 and
6
6 are
the most popular grades. Together they comprise over
90% of the production in the United States. About
two-thirds of this production is of type
6
6, and one-
third of the production is nylon 6. These two grades
have the highest strength. Their impact strength is fair
in the dry condition, but when they are saturated with
water the impact properties increase substantially. The
absorbed moisture acts as a plasticizer. Manufacturers
of these materials expect that they will maintain their
popularity well into the new century, and this family of
plastics should be considered for applications in which
mechanical properties are important and moisture-
induced size changes will not affect function.
Polyacetals
Polyacetal is different from many of the other poly-
mers in that polymer molecules have a carbon-to-
oxygen bond rather than the more typical carbon-to-
carbon bond. Such a structure is called a heterochain
as opposed to a carbon chain. The basic monomer
unit is formaldehyde, and the polymer chains have
ending groups:
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Polyoxymethylene (POM) is the correct chemical
term for this polymer, but acetal is the accepted
generic term.
There are three basic types of acetals in wide
commercial use: the homopolymer (Delrin 500
), a
copolymer (with trioxane) (Celcon
), and PTFE-
filled versions (Delrin AF
, Acetron
, etc.). A num-
ber of others are manufactured, but the grade
variations remain essentially the same: There is an
unlubricated grade and a grade with PTFE added to
improve tribological properties. It is not common to
glass reinforce these polymers, and most of the usage
is in the form of one of the three variations that we
have listed. All grades are highly crystalline, with me-
chanical properties similar to those of nylons. As is
shown in Figure 85, this family of polymers is higher
in strength than most of the ethenic polymers, and
the strength is slightly lower than that obtainable with
the nylons.
The homopolymer has higher strength than the
copolymers, but the copolymers are more stable at el-
evated temperatures; maximum continuous use tem-
peratures are as high as 220F (104C), compared
with 195F (90C) for the homopolymer. One advan-
tage of acetals over nylons is their lower tendency for
moisture absorption. They still absorb moisture and
change size, but to a lesser degree. This makes acetals
more stable in service as cams, gears, and other me-
chanical devices for which size change is detrimental.
The PTFE-filled acetal has even lower moisture ab-
sorption tendencies and is even more stable in serv-
ice. The PTFE addition also allows the use of this
polymer for self-lubricating bushings and sliding de-
vices. Unlubricated nylons and acetals make poor
bearings.
A disadvantage that limits the use of acetals is
high shrinkage in injection molding. It is difficult to
mold unfilled grades to accurate part dimensions.
Glass filling and foaming often are required to mini-
mize molding shrink.
Thus, there are advantages and disadvantages of
acetals, but, in general, they are one of the most im-
portant engineering plastics and one of the most fre-
quently used in machine design and in structural
components of consumer items.
Cellulosics
Cellulose is a natural substance that makes up a sig-
nificant portion of all plant life. The cellulose mole-
cule (monomer) is quite complex, and bonding is
obtained by oxygen linkages to form a polymer:
Most polymers are made from petroleum or
natural gas feedstocks. The raw material for the
manufacture of cellulosics is cotton linters or wood
pulp.
The most commonly used cellulose polymers are
cellulose acetate (CA), cellulose acetate butyrate
(CAB), and cellulose acetate propionate (CAP). The
cellulose nitrates are now seldom used because of
their flammability. Cellulose acetate is a thermoplas-
tic often used for films and fibers. It is an ester re-
sulting from the reaction of cellulose with acetic
acid. Cellulose acetate propionate and cellulose ac-
etate butyrate are mixed esters with improved physi-
cal and mechanical properties over the cellulose
acetates. They are thermoplastics with good molding
characteristics and thus find wide application in in-
jection molded and vacuum formed domestic arti-
cles. The familiar roadside signs with fluorescent
Polymer Families 203
Figure 85
Approximate tensile yield
strength of nylon and acetal
homopolymers
M08_BUDI8426_09_SE_C08.QXD 11/13/08 9:36 AM Page 203
lights inside usually are thermoformed from cellu-
lose acetate butyrate. One of the most commonly
encountered cellulosics is cellulose produced by
the viscous process. The familiar name for the end
product of this process is rayon. Another common
cellulosic is cellophane, which is also a product of
the viscous cellulose regeneration process. In gen-
eral, cellulosics are low-cost thermoplastic poly-
mers with good moldability, desirable colorability,
and weatherability. Their application is more often
found in domestic goods than in machine and in-
dustrial applications. A good consumer application
is cigarette filters. They are made from cellulose
triacetate.
Most photographic film is made with a cellulose
acetate support. Other film applications include
safety goggles, sunglasses, screwdriver handles, and
ski goggles. This material is selected for goggle appli-
cations because it has good mechanical properties, it
is not brittle, and cellulosics have excellent resistance
to sunlight. Many plasticspossibly, most plastics
cannot withstand sunlight. Ultraviolet radiation
causes the chemical breakdown of molecular bonds
in many plastics, and undesirable things can happen
with repeated exposure. Polyethylenes get brittle,
many elastomers craze, plasticized vinyls lose their
plasticizer, and rigid vinyls can form a powdery sur-
face. Essentially, most plastics are not well suited to
outdoor use. This is one of the outstanding properties
of the cellulosics. They can withstand UV from sun-
light without substantial loss of mechanical proper-
ties, color, or transparency.
Thermoplastic Polyesters
Thermoplastic polyesters have been used for about
40 years, predominately in films for packaging and
in fibers. Everyone is familiar with polyester cloth-
ing and polyester auto tire reinforcement. These
are thermoplastic polyesters, usually polyethylene
terephthalate (PET):
PET has been used for plastic liter-size beverage bot-
tles and for engineering plastic applications such as
auto parts, gears, and cams. PETG is a glycol-modified
PET that is used for similar applications.
The other basic type of thermoplastic polyester
that is used for similar engineering applications is
polybutylene terephthalate (PBT):
PBT has good injection molding characteristics and
mechanical properties similar to nylons. It has a use
temperature above that of most nylons, and it does
not have the moisture absorption problems of nylon.
Glass-reinforced PBT has a stiffness similar to that of
thermosetting resins, while maintaining good tough-
ness. As a class of materials, thermoplastic polyesters
have performance characteristics that make them
likely candidates for structural applications in appli-
ances, automobiles, and consumer products.
About 45% of the production of PET goes into
films for photography and packaging, and in fibers
for clothing, tire reinforcement, and the like. A simi-
lar percentage of the U.S. production is used in blown
beverage bottles. Thus, the major usage of this poly-
mer is for nonstructural applications. About 10% of
the production is in grades that are made to be in-
jection moldable, and these grades are used for all
sorts of mechanical parts. It is common practice to
reinforce thermoplastic molding grades of PET and
PBT with 15% to 50% glass or minerals. The rein-
forced grades of PBT and PET are similar in me-
chanical properties to nylons, and they are used for
the same types of applications. Both PET and PBT
are crystalline and somewhat notch sensitive. Me-
chanical parts made from the engineering grades of
these materials should have generous radii on reen-
trant corners.
PET and PBT are closely related polymers in use
properties with only subtle differences. PET is
slightly stronger and lower in cost. Some grades of
PBT have processing advantages over PET grades. In
any case, the grades that are used for engineering ap-
plications have properties similar to those of nylons,
and those properties make PET and PBT competitive
with nylons, but these families of resins do not have
the moisture absorption problems that are indige-
nous to nylons. PBT is widely used in blends: Mixed
with PET, it is marketed as a family of Valox
resins;
mixed with polycarbonate, it forms Xenoy
; mixed
with polyphenylene ether, it forms Gemax
resins.
Other blends are available, but as a family of plastics,
the thermoplastic polyesters are made up of two basic
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polymer systems: PET and PBT. There are many
grades of each of these polymers for films, bottles, and
molding resins. Both polymer systems produce engi-
neering grades with excellent properties for general
use in automotive, electrical, and appliance applica-
tions. In general, polyesters have higher strengths and
use temperatures than commodity plastics like PE
and PP, and they compete with nylons and acetals in
mechanical properties.
Polycarbonates
A polycarbonate is really a polyester because it is an
ester of carbonic acid and an aromatic bisphenol:
The polycarbonates are amorphous linear poly-
esters with excellent moldability and impact strength.
The combination of impact strength, temperature re-
sistance, and transparency makes them suitable for
the same types of applications as acrylics: guards,
sight glasses, and the like. Their cost usually is higher
than that of acrylics, so they are used only where the
higher impact strength is needed. Polycarbonate is
widely used for helmets and face shields. For struc-
tural applications, it is similar in properties to the
nylons and acetals. The tensile properties of polycar-
bonates are similar to those of nylons and acetals, but
the impact strength can be as much as 10 times
greater. Thus, polycarbonates are replacing materials
such as ABS and nylon for automotive parts such as
dashboards, window cranks, small gears, and similar
mechanical components.
Polycarbonate is an important engineering ther-
moplastic for industrial applications as well as for
consumer goods such as power tool housings, tele-
phones, cellular phones, and sporting goods.
Each manufacturer of polycarbonate has at least
a dozen grades. Some are specially formulated for
electrical applications, some are designed for clear
applications, and others are designed for mechanical
applications. Grades are available with glass or other
reinforcement, and some grades are lubricated with
PTFE or similar materials for tribological applica-
tions. Probably the most familiar application of poly-
carbonates is for clear sheets (Lexan
and others)
and lenses for automotive lights. Polycarbonate com-
petes with acrylics (PMMA) for safety-glass applica-
tions. It is more expensive than acrylics, but it can
have up to 16 times the impact strength. A similar sit-
uation exists with clear styrenes: Polycarbonates cost
more, but they are used because of their increased
toughness. The molding grades of polycarbonate
have similar toughness, with strengths comparable to
acetals, nylons, and polyesters. These plastics are also
candidates for use outdoors because of their good re-
sistance to UV light. Windows and similar clear pan-
els can tolerate outdoor exposure without degradation
in clarity or loss of properties. As molding resins, PC
parts have good stability and make accurate molded
parts. Principal applications are for automotive trim,
lenses and dashboard components, electrical connec-
tors, and the like, and for all sorts of appliance parts.
Clear impact-resistant sheet is the most familiar ap-
plication. It is almost a standard material for con-
struction hard hats, football helmets, and similar
applications where moldability, toughness, and good
appearance are required. The thickness or section
size of polycarbonate parts can affect the apparent
toughness of polycarbonate. When thicknesses are
greater than about 0.10 in. (2.5 mm), polycarbonate
may behave in a brittle manner. Other factors such as
residual stress, notches, or annealing may also reduce
the toughness of polycarbonate. Polycarbonates are
susceptible to environmental stress cracking in cer-
tain solvents, and they can craze (develop fine
cracks) under sustained load if creep stress limits
are exceeded. These factors should be considered in
design.
Polyimides
The polyimides came into commercial use as engi-
neering plastics in the 1970s. They have very complex
structures characterized by chain stiffening due to the
presence of ring structures in the mer:
The presence of the imide group in the mer structure
makes a polyimide. The different types of polyimides
depend on the reacting species. The thermoplastic
Polymer Families 205
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types have a linear structure, and the thermosetting
types have a cross-linked structure. The usual method
for making polyimides is by reacting aromatic di-
amines and dianhydrides. The common feature of
this family of polymers is resistance to elevated tem-
perature. Some of the materials have continuous use
temperatures in the range of 500 to 600F (260 to
315C). They maintain stability and decent mechani-
cal properties at these temperatures, and adequate
data are tabulated on elevated temperature proper-
ties to allow the prediction of service at these high
temperatures.
Unfortunately, the stable aromatic structure of
these materials creates processing problems. The
thermoplastic grades of polyimide require very high
molding temperatures that often tax the capabilities
of conventional plastic molding machines. Some of
the polyimides are direct formed to shape at about
800F (426C), with techniques similar to those used
in powder metallurgy. Powder is compacted and sub-
sequently sintered into a shape under pressure in a
mold. Sometimes, vacuum sintering is used. The pow-
der particles do not melt; the particles develop suffi-
cient plasticity to fill voids, and the particles coalesce
to form a full, dense part or standard shape. One
commonly used polyimide, Vespel
, is offered in di-
rect formed standard shapes that can be machined to
the desired part shape. Individual parts can be direct
formed if there is sufficient part volume to justify the
compaction tooling.
In addition to good mechanical properties at el-
evated temperatures, polyimides have excellent me-
chanical properties. Tensile strength can be higher
than 15 ksi (103 MPa); compression strength can be
higher than 30 ksi (206 MPa). One reason for the
thermal stability of polyimides is their low coeffi-
cient of thermal expansion (as low as in./
in. F). This property makes polyimides candidates
for precision parts that must function at high
temperatures.
Polyimides are available in molding pellets, in
direct formed shapes for machining, in direct
formed parts, in films, as resins for adhesives, and as
a matrix for advanced composites. Two popular ad-
ditives to the molding grades are graphite and
PTFE. These materials are added to grades destined
for tribological applications. These lubricious fillers
provide the capability for using these materials as
self-lubricating bearings. Other applications are for
structural parts that must maintain good mechanical
strength at temperatures that destroy many other
plastics. Films (Kapton
, is a liq-
uid crystal. Chemically, liquid crystals have an inter-
mediate in their structure, hydroxybenzoic acid
(HBA), that promotes the liquid crystal state. The
following is the mer structure of one type of liquid
polymer:
There are other possible mer structures. It is the mor-
phology of the polymer that makes it a liquid crystal.
Aligned polymer chains form in the melt, and these
aligned chains are maintained into the solid condi-
tion. One manufacturer of these resins uses the term
self-reinforced plastics to describe this family of poly-
mers, thus suggesting that the polymer chains that
form in the melt are analogous to the fiber reinforce-
ment used in polymer composites.
The properties of liquid crystal polymers (LCPs)
depend on the specific mer formed by the reacting
species. However, as a family of materials, the char-
acteristics that set them apart from other polymer
systems are high strength and high-temperature capa-
bility, without the molding and processing problems
that are characteristic of many other high-temperature
Polymer Families 209
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thermoplastics. They have good injection molding
characteristics; they do not require long curing times
in the mold before ejection, and they have good di-
mensional stability; the mechanical properties can
be higher than those for nylon, and glass reinforce-
ment gives them tensile strengths in excess of 20 ksi
(140 MPa). The tensile modulus can be in excess of
20 million psi (138 GPa), with good fracture toughness.
The competitive materials are engineering plastics such
as PEEK, PPO, and some of the more advanced types
of commodity plastics, such as polyesters.
The cost of LCPs in 2008 is in the range of $5 to
$8/lb ($10 to $16/kg). Such pricing puts this material in
a favorable position compared with high-performance
engineering plastics such as the polyimides, polypheny-
lene sulfides, and the like. The LCPs are relatively low
in cost, with premium properties.
Applications of these materials are common in the
electronic and electrical area. The LCPs have good sta-
bility, are easily molded, have low flammability, have
good electrical properties at elevated temperature, and
have very low coefficients of thermal expansion, which
allows for stability in service. Obviously, this mix of
properties coupled with excellent strength makes LCPs
candidates for many mechanical parts that require
something more than is offered by a commodity plastic.
New applications are proliferating, and new LCP types
are being developed to further reduce costs. Eventu-
ally, these plastics may replace many of the glass-filled
plastics that are used when high strengths are required.
This is a desirable goal, because glass reinforcement
produces tool wear in all phases of processing.
Polyphenylene Oxide
The acronym PPO ( polyphenylene oxide) has been
registered as a trademark Noryl
. Many of
the other rubbers discussed are copolymers or ter-
polymers. CSM is made by treating polymerized
220 Chapter 8
Figure 88
Large roof covered with EPDM rubber
M08_BUDI8426_09_SE_C08.QXD 11/13/08 9:37 AM Page 220
Polymer Families 221
polyethylene with gaseous chlorine and sulfur dioxide
to chemically add chlorine and sulfur to the mer:
Fillers such as carbon black and sulfur are not neces-
sary to achieve strength in vulcanization. This rubber
has outstanding resistance to weathering, heat, and
abrasion. It is used for tank liners and in many chem-
ical plant applications such as pond liners. It is also
used for high-voltage electrical insulation. It is con-
sidered to be a high-performance elastomer rather
than a general-purpose rubber.
Polysulfide Rubber
There are a great number of polysulfide rubber
formulations, but their general characteristic is a
heterochain of a carbon-based group and sulfur
atoms:
The carbon-based functional group can change,
as can the number of sulfur atoms. Polysulfides are
technical elastomers usually used for special appli-
cations. The noteworthy characteristics of polysul-
fide rubbers are their solvent and oil resistance,
impermeability to gases and moisture, and weather
and aging resistance. They do not have the tensile
strength, resilience, and tear resistance of natural
rubber or SBR. They can be made into two-compo-
nent systems that cross-link after mixing and into
systems that cure by oxidation in air or moisture.
These latter characteristics make polysulfides suit-
able for caulking compounds, sealants, puttying
agents, and castable shapes. Polysulfide rubber is
widely used to seal boat windshields and bed deck
hardware.
Silicones
Silicones are inorganic polymers. Instead of the nor-
mal carbon atom backbone, this family of materials
has a structure characterized by siliconoxygen
bonds. The repeating structure is similar to that of sil-
icate minerals. (Sand is SiO
2
.) In fact, it is the silicon-
to-oxygen bonding that gives this family of materials
its superior thermal stability. The backbone
tends to be linear, and varying properties are
achieved by varying the nature of the organic side
chains that are bonded to silicon atoms. A silicone
structure is illustrated here:
Silicones are commercially produced as liquids
and greases (for lubrication), as elastomers, and as
rigid solids. The elastomer grades are available as
one-component systems that cure by hydrolysis of
functional groups from moisture in the air (these
are called RTV resins, for room temperature vul-
canizing) or as two-component systems that cure
when the components are mixed. Some grades of
elastomers are heat cured as in vulcanizing. Poly-
mer composites with silicones as the matrix mate-
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the rigid types. Elastomer composites usually are
laminates of varying durometer silicone rubbers
with woven reinforcements such as cotton cloth. A
significant use of these laminates is for printing
press blankets and for heat-resistant rubber di-
aphragms. Silicones are extremely important in the
printing industry because in the lower durometers
they have a unique ability to transfer ink to other
materials; nothing sticks to them. Silicone caulks
are widely available, and they are used for countless
sealing applications, they cure by reaction with
moisture in the air.
Polyurethane
The unique feature of polyurethanes is that they can
behave as elastomers (rubbers), as rigid hard ther-
mosets, or as injection moldable thermoplastics. A
castable elastomer can be designed to suit a particu-
lar application by varying the reacting substances.
Simple metal molds can be used, and polymerization
is accomplished by heating to approximately 500F
(260C). An elastomer-covered roll, for example, can
be made by pouring the urethane resins into a tube
around the roll core, baking, and then grinding to
final diameter. Sheets and blocks are made by
Si O
M08_BUDI8426_09_SE_C08.QXD 11/13/08 9:37 AM Page 221
pouring the resin into temporary low-cost metal
forms. Hardnesses of from 30A (Shore) to 95A can
be made. All these hardnesses have elastomeric
properties, and they can be used for die springs,
forming dies, wear pads, and the like. The injection
moldable urethanes are used for ski boots and sports
equipment. The abrasion resistance of polyurethane
elastomers is a function of its durometer. Low Shore
A hardness elastomers have low abrasion resistance,
as do the rigid polyurethanes with hardnesses on the
Shore D scale. A hardness in the range of 90 to 95
Shore A usually produces the best abrasion resist-
ance. Figure 89 is an example of a cast silicone
shape.
Special-Purpose Elastomers
In addition to the elastomers described here in detail,
several special-purpose rubbers have characteristics
that warrant mention.
Polyacrylic rubber (ABR) can resist hot oils and
solvents and is used for spark plug insulation and
transmission seals where these conditions exist.
Fluoroelastomers (FPM) such as Viton
, which
is a copolymer of vinylidene fluoride and hexafluoro-
propylene, have excellent solvent and chemical re-
sistance and can be used at continuous service
temperatures as high as 400F (204C). FPM is ex-
pensive and is not as resilient as most rubbers. Thus,
it is used only where its temperature or chemical re-
sistance is necessary.
Epichlorohydrin rubber (ECO) has excellent fuel
and oil resistance and can be used at very low tem-
peratures. It is suitable for use in snow handling
equipment and recreational vehicles.
Polynorbornene (PNB) is a very soft rubber used
for vibration absorption and dampening. Because of
its ability to absorb energy and dissipate concentrated
forces, it is used for body armor. PNB typically is not
used above 70C and is nonresistant to oils, hydrocar-
bons, or ozone.
Thermoplastic Elastomers (TPEs)
Conventional rubbers such a EPDM, nitrile, and
polybutadiene are cross-linked or vulcanized during
molding or fabrication. Such rubbers are often
fabricated into components by compression mold-
ing. Additionally, some rubbers such as silicones,
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M08_BUDI8426_09_SE_C08.QXD 11/13/08 9:37 AM Page 224
225
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M08_BUDI8426_09_SE_C08.QXD 11/13/08 9:37 AM Page 225
226 Chapter 8
to further aid in selection. In selecting an elastomer
for a high-production application, much more de-
tailed information should be obtained from suppliers
and handbooks. The principal properties to be scruti-
nized are physical and mechanical properties and en-
vironmental resistance. If a special combination of
any of these properties is required, special blends can
be obtained if production quantities are sufficient.
If machine design situations require only occa-
sional selection of an elastomer, most needs can be
met by weighing the relative merits of only a few rub-
bers. Most O rings are made from buna N rubber, as
are many gaskets for oil sumps and the like. Neo-
prene is a good general-purpose rubber that can tol-
erate some oil exposure; it is also flame retardant.
EPDM is a similar general-purpose, low-cost rubber,
but it has better heat resistance than neoprene. Cast
polyurethanes are extremely useful in machine de-
sign applications. They have better abrasion and tear
resistance than almost all other rubbers, as well as the
phenomenal advantage that they can be cast to shape
in simple molds with no special tools other than a cur-
ing oven. They are extremely useful for roll coverings,
testing seals, part fixtures, and similar machine appli-
cations. The silicones have similar castability, but
they have higher heat resistance and lower tear and
abrasion resistance. For extreme corrosion environ-
ments, the fluoroelastomer, Viton-type materials
often can be justified.
If cost is not a factor, the average designer can be
effective with a knowledge of a relatively small num-
ber of elastomers. Parts that are to be made in signif-
icant quantities will require a more thorough search
for the most cost-effective and serviceable elastomer.
Summary
This chapter is intentionally encyclopedic. It should
serve as the reference for the engineer or designer
looking up various plastics when, for example, poly-
sulfone is recommended for a particular part. That
section can be reread, and the designer can be reac-
quainted with that plastic or elastomer. The other
purpose for stressing chemical formulations is that a
user cannot have a good appreciation of differences
between various plastics without knowing how their
mers differ. Use characteristics do not adequately
describe polymers. Effective use of plastics requires
a basic understanding of polymerization, whether
plastics are thermosetting or thermoplastic, and
some idea of the structure and unique characteris-
tics of each plastic. It is not necessary to memorize
the structure of each plastic that we have discussed,
but it is important to have an understanding of poly-
mer families and basic types. The ethenic polymers,
cellulosics, epoxides, amides, acetals, polyesters,
silicones, and phenolics have chemical similarities
within the family, but the families have funda-
mental differences in chemical composition and
use characteristics.
As will be pointed out in the subsequent chapters,
we can effectively use plastics in engineering design if
we understand relatively few polymer systems and if
we develop a feel for the characteristics of a dozen or
so specific polymers. Thus, this chapter should serve as
a reference on polymer chemistry and as a guide for
the selection of polymers and elastomers.
Some of the important concepts covered in this
chapter are the following:
PVC, PS, PP, and PE are used for all sorts of con-
sumer items; they often are used for recyclable
items, but they have reasonable mechanical prop-
erties and can be used for structural applications
if they are used properly.