Department of Chemical Engineering

Polymers and Plastics Engineering (0905553)

Typical Characteristics of Some Important Plastics

A) Semi-crystalline plastics
Low density polyethylene (LDPE)
This is one of the most widely used plastics. It is characterized by a density in the
range 918-935 kg/m3 and is very tough and flexible. Its major application is in
packaging film although its outstanding dielectric properties mean it is also widely
used as an electrical insulator. Others applications include domestic ware, tubing,
squeeze bottles and cold water tanks, (Tg = -95 and Tm = 115 oC).

Linear low density polyethylene (LLDPE)

This new type of polyethylene was introduced in 1977. LLDPE is produced by a low
pressure process and it has a regular structure with short chain branches. Depending
on the cooling rate from the melt, the material forms a structure in which the
molecules are linked together. Hence for any given density, LLDPE is stiffer than
LDPE and exhibits a higher yield strength and greater ductility. This new material
has taken over traditional LDPE markets.

High density polyethylene (HDPE)

This material has a density in the range 935-965 kg/m3 and is more crystalline than
LDPE. It is also slightly more expensive but as it is much stronger and stiffer it finds
numerous applications in such things as dustbins, bottle crates, general purpose fluid
containers and pipes, (Tg = -110 and Tm = 135 oC).

Cross-linked polyethylene (XLPE)

Some thermoplastic materials such as polyethylene can have their structure altered so
that the molecular chains become cross-linked and the material then behaves like a
thermoset. The action of cross-linking has a number of beneficial effects including
improved stress cracks resistance, improved creep resistance, better chemical
resistance, improved toughness and better general thermo-mechanical stability.

Polypropylene (PP)
Polypropylene is an extremely versatile plastic and is available in many grades and
also as a copolymer (ethylene/propylene). It has the lowest density of all
thermoplastics (in the order of 900 kg/m3) and this combined with strength and
excellent fatigue and chemical resistance make it attractive in many situations. These
include crates, small machine parts, car components (fans, fascia panels), chair shells,
cabinets for TV, tool handles. Polypropylene is also available in fiber form for ropes,
carpet backing and as a film for packaging, (Tg = -18 and Tm = 176 oC).

Polyamides (PA)
There are several different types of nylon (nylon 6, nylon 66, and nylon 11) but as a
family their characteristics of strength, stiffness and toughness have earned them a
reputation as engineering plastics. Typical applications for nylon include small
gears, bearings, bushes, and sprockets, housings for power tools, terminal blocks and
slide rollers. An important design consideration is that nylon absorbs moisture which
can affect its properties and dimensional stability. The density of nylon is about 1100
kg/m3, (Tg = 50 and Tm = 265 oC).

Acetals
The superior properties of acetal in terms of its strength, stiffness and toughness have
also earned it a place as an engineering plastic. It is more dense than nylon but in
many respects their properties are similar and they can be used for the same types of
light engineering application. A factor which may favour acetal in some cases is its
relatively low water absorption. The former is slightly stronger and stiffer whereas
the copolymer has improved high temperature performance. This latter feature makes
this material very attractive for hot water plumbing applications and as the body for
electric kettles. `

Polytetrafluoroethylene (PTFE)
The major advantages of this material are its excellent chemical resistance and its
extremely low coefficient of friction. Not surprisingly its major area of application is
in bearings particularly if the environment is aggressive. It is also widely used in
areas such as insulating tape, gaskets, pumps, diaphragms and of course non-stick
coatings on cooking utensils, (Tg = -20 and Tm = 327 oC).

Thermoplastic Polyesters
These linear polyesters are highly crystalline and exhibit toughness, strength, abrasion
resistance, low friction, chemical resistance and low moisture absorption.

Polyethylene terephthalate (PET)

PET has been available for many years but mainly as a fibre (e.g. Terylene). As a
moulding material it was less attractive due to processing difficulties but these were
overcome with the introduction of polybutylene terephthalte (PBT). Applications
include gears, bearings, housings, impellers, pulleys, switch parts, bumper extensions,
ect. And of course PET is now renowned for its success as a replacement for glass in
beverage bottles. PBT dose not have such a high performance specification as PET
but it is more readily moulded, (Tg = 65 and Tm = 240 oC).
Polyetheretherketone
This material, which is more commonly known as PEEK, is one of the new generation
plastics which offer the possibility of high service temperatures. It is crystalline in
nature which accounts in part for its high resistance to attack from acids, alkalis and
organic solvents. It is easily processed and may be used continuously at 200 oC where
it offers good abrasion resistance, low flammability, toughness, strength and good
fatigue resistance. Its density is 1300 kg/m3. Applications include wire coatings,
electrical connections, fans, impellers, fibres, ect.

B) Amorphous plastics
Polyvinyl Chloride (PVC)
This material is the most widely used of the amorphous plastics. It is available in two
forms – plasticised or unplasticised. Both types are characterized by good weathering
resistance, excellent electrical insulation properties, good surface properties and they
are self extinguisishing. Plasticised PVC is flexible and finds applications in wire
covering, floor tiles, toy balls, gloves and rainwear. Unplasticiesd PVC (uPVC.) is
hard, tough, strong material which is widely used in the building industry. For
example, pipes, gutters, window farmer and wall claddings are all made in this
material. The familiar credit cards are also made from uPVC, (Tg = 85 oC).

Polymethyl Methacrylate (PMMA)

This material has exceptional optical clarity and resistance to outdoor exposure. It is
resistant to alkalis, detergents, oils and dilute acids but is attacked by most solvents.
Its peculiar property of total internal reflection is include illuminated notices, lenses
and display models, (Tg = 105 oC).

Polystyrene (PS)
Polystyrene is available in a range of grades which generally vary in impact strength
from brittle to very tough. Their low cost coupled with ease of processing makes
them used for such things as model aircraft kits, vending cups, yoghurt containers,
light fittings, coils, relays, disposable syringes and casings for ballpoint pens.
Polystyrene is also available in an expanded form which is used for such things as
ceiling tiles and is excellent as a packaging material and thermal insulator, (Tg = 95
o
C).

Acrylonitrile-butadiene-styrene (ABS)
ABS materials have superior strength, stiffness and toughness properties to many
plastics and so they are often considered in the category of engineering plastics. They
compare favorably with nylon and acetal in many applications and are generally less
expensive. However, they are susceptible to chemical attack by chlorinated solvents,
esters, ketons, acids and alkalis.
Typical applications are housings for TV sets, telephones, fascia panels, hair brush
handles, luggage, helmets and linings for refrigerators.

Polycarbonates
These materials also come within the category of engineering plastics and their
outstanding feature is extreme toughness, they are transparent. Typical applications
include vandal-proof street lamp covers, baby feeding bottles, machine housings and
guards, camera parts, electrical components, safety equipment and compact discs, (Tg
= 150 oC).

Polyethersulphone
This material is one of the new high temperature plastics. It is recommended for load
bearing applications up to 180 oC. Even without flame retardants it offers low
flammability and there is little change in dimensions of electrical properties in the
temperature range 0 to -200 oC. It is easily processed on conventional moulding
equipment. Applications include aircraft heating ducts, terminal blocks, engine
manifolds, bearings, grilles, tool handles, non-stick coatings.

Modified Polyphenylene Oxide (PPO)

The word modified in this material refers to the inclusion of high impact polystyrene
to improve processability and reduce the cost of the basic PPO. This material offers a
range of properties, which make it attractive for a whole range of applications. For
example, it may be used at 100 to 150 oC where it is rigid, tough and strong with good
creep resistance and hydrolytic stability. Water absorption is very small and there is
excellent dimensional stability. Applications include business machine parts, flow
values, headlight part, engine manifolds, fascia panels, grilles, pump casings, hair
dryer housings, etc.

C) Thermoplastic Rubbers
Thermoplastic elastomers (TPE), sometimes referred to as thermoplastic rubbers, are
a class of copolymers or a physical mix of polymers (usually a plastic and a rubber)
which consist of materials with both thermoplastic and elastomeric properties.
While most elastomers are thermosets, thermoplastics are in contrast relatively easy to
use in manufacturing, for example, by injection molding. Thermoplastic elastomers
show both advantages typical of rubbery materials and plastic materials.

In order to qualify as a thermoplastic elastomer, a material must have these three

essential characteristics:
1. The ability to be stretched to moderate elongations and, upon the removal of
stress, return to something close to its original shape
2. Processable as a melt at elevated temperature.
3. The absence of significant creep.

There are six types of thermoplastic rubbers currently available. These are based on:
 Olefinics (e.g. Alcryn, Santoprene)
  Polyurethanes (e.g. Elasstollan, Carprolan, Pellethane)
 Polyestres (e.g. Hytrel, Arnitel)
 Styrenics (e.g. Solprene, Cariflex)
 Polymides (e.g. Pebax, Dinyl)
 Elastomeric alloys.

D) Thermosetting Plastics
Aminos
There are two basic types of amino plastics – urea formaldehyde and melamine
formaldehyde. They are hard, rigid materials with good abrasion resistance and their
mechanical characteristics are sufficiently good for continuous use at moderate
temperatures (up to 100 oC). Urea formaldehyde is relatively inexpensive but
moisture absorption can result in poor dimensional stability. It is generally used for
bottle capes, electrical switches, plugs, utensil handles and trays. Melamine
formaldehyde has lower water absorption and improved temperature and chemical
resistance. It is typically used for tableware, laminated worktops and electrical
fittings.

Phenolics
Phenol-formaldehyde (Bakelite) is one of the oldest synthetic materials available. It is
a strong, hard, brittle material with good creep resistance and excellent electrical
properties. Unfortunately the material is only available in dark colures and it is
susceptible to attack by alkalis and oxidizing agents. Typical applications are
domestic electrical fittings, saucepan handles, fan blades, smoothing iron handles and
pump parts.

Polyurethanes
This material is available in three forms: rigid foam, flexible foam and elastomer.
They are characterized by high strength and good chemical and abrasion resistance.
The rigid foam is widely used as an insulation material, the flexible foam is an
excellent cushion material for furniture and the electrometric material is used in solid
tires and shock absorbers.

Polyesters
The main application of this material is as a matrix for glass fiber reinforcement. This
can take many forms and is probably most commonly known as a DIY type material
used for the manufacture of small boats, chemical containers, tanks and repair kits for
cars, etc.

Epoxides
Epoxy resins are more expensive than other equivalent thermosets (e.g. polyesters)
they have better toughness, less shrinkage during curing, better weatherability and
lower moisture absorption. A major area of application is in the aircraft industry
because of the combination of properties offered when they are reinforced with fibers.
They have an operating temperature range of -25 to 150 oC.

Additives and Modifiers used in Plastics

 Polymers are rarely used directly as plastics, elastomers, fibers, coatings, etc.
They do not fulfill all technological requirements and become commercially
useful only after they are admixed with certain polymer additives and/or
modifiers.
 Modern technical terminology distinguishes between additives and modifiers.
Additives are added in small proportions, usually less than 5 %; they do not
affect markedly the mechanical properties. Modifiers are used in greater
proportions; they modify mechanical properties such as the impact strength.
 Polymer additives and modifiers are to be distinguished from polymer
auxiliaries. Additives and modifiers are added to polymers after the
polymerization process, i.e., for the manufacture of plastics, whereas
auxiliaries are used for the production of polymers themselves.
 Additives and modifiers are also often subdivided according to their action
into process additives and functional additives:
o Process additives aid the processing of plastics by either stabilizing the
chemical composition of polymers or facilitating the processing itself.
o Functional additives stabilize the chemical composition against attacks by
environmental agents or improve end-use properties.

Antistatic Agents
Most polymers, because they are poor conductors of current, build up a charge of
static electricity. Antistatic agents attract moisture from the air to the plastic surface,
improving its surface conductivity and reducing the likelihood of a spark or a
discharge.

Coupling Agents
Coupling agents are added to improve the bonding of the plastics to inorganic filler
materials, such as glass fibers. A variety of silanes and titanates are used for this
purpose.

Blowing Agents

Foamed plastics are blends of polymers with gases. The gases may be air, N2, CO2,
fluorinated hydrocarbons, etc.

Fillers
Some fillers, such as short fibres or flakes of inorganic materials, improve the
mechanical properties of a plastic. Others, called extenders, permit a large volume of
a plastic to be produced with relatively little actual resin. Calcium carbonate, silica
and clay are frequently used extenders.

Flame Retardants
Most polymers, because they are organic materials, are flammable. Additives that
contain chlorine, bromine, phosphorous or metallic salts reduce the likelihood that
combustion will occur or spread.

Lubricants
Lubricants such as wax or calcium stearate reduce the viscosity of the molten plastic
and improve forming characteristics.

Colorants

Colorants are subdivided into dyes (soluble in polymer matrix) and pigments
(insoluble). Textile fibers are dyed mainly with dyes, while pigments are preferred
for plastics because they have a higher light fastness and are more stable against
migration than dyes.

Plasticizers
Plasticizers are low molecular weight materials which alter the properties and forming
characteristics of the plastic. An improved example is the production of flexible
grades of polyvinyl chloride by the use of plasticizers.

Reinforcement
The strength and stiffness of polymers are improved by adding fibers of glass, carbon,
etc.

Stabilizers
Stabilizers prevent deterioration of the polymer due to environmental factors.
Antioxidants are added to ABS, polyethylene and polystyrene. Heat stabilizers are
required in processing polyvinyl chloride. Stabilizers also prevent deterioration due
to ultra-violet radiation.

Selection of plastics
There are more than 40 different types of plastics materials (not including elastomers)
in use today and for each of these there can be up to 50 different formulations or
grades with subtle differences in properties. In addition, many basic homopolymers
can be blended or mixed with other materials such as stabilizing fillers and
 reinforcements. This leaves the designer with what appears to be an impossible task of
selecting the most suitable material from a list of thousands.
The previous section has given an indication of the range of plastics available to the
design engineer. The important question then arises How do we decide which plastic,
if any, is best for a particular application? Material selection is not as difficult as it
might appear but it dose require an awareness of the general behavior of plastics as a
group, as well as a familiarity with the special characteristics of individual plastics.

The first and most important steps in the design process are to define clearly the
purpose and function of the proposed product and to identify the service environment.
Then one has to assess the suitability of a range of candidate materials. The following
are generally regarded as the most important characteristics requiring consideration
for most engineering components:

1. Mechanical properties – strength, stiffness, specific strength and stiffness, fatigue

and toughness, and the influence of high or low temperatures on these properties.
2. Corrosion susceptibility and degradation.
3. Wear resistance and frictional properties.
4. Special properties, for example , thermal, electrical, optical and magnetic
properties, damping capacity, ect;
5. Moulding and/or other methods of fabrication.
6. Total costs attributable to the selected material and manufacturing route.

The following table shows some of the properties for polymers available in the
market:

Material Density Specific Thermal Coeff. Of Thermal Glass Max.

(kg/m3) Heat (kJ/kg Conductivity Thermal Diffusivity Transition Operating
K) (W/m/K) Expansion (m2/s) x Tg (oC) Temp. (oC)
(μm/m/oC) 10-7
ABS 1040 1.3 0.25 90 1.7 115 70
Acetal (H) 1420 1.5 0.2 80 0.7 -85 85
Acetal (C) 1410 1.5 0.2 95 0.72 -85 90
Acrylic 1180 1.5 0.2 70 1.09 105 50
Cellulose 1280 1.6 0.15 100 1.04 - 60
CAB 1190 1.6 0.14 100 1.27 - 60
Epoxy 1200 0.8 0.23 70 - - 130
PPO 1060 - 0.22 60 - - 120
Nylon 66 1140 1.7 0.24 90 1.01 56 90
PEEK 1300 - - 48 - 143 204
PET 1360 1.0 0.2 90 - 75 110
Phenolic 1700 - 0.5 18 - - 185
Polyamide 1400 - 0.25 36 - 260 210
Polycarbonate 1150 1.2 0.2 65 1.47 149 125
Polyester 1200 1.2 0.2 100 - - -
Polyetherimide 1270 - 0.22 56 - 200 170
Polyethersulphone 1370 - 1.18 55 - 230 180
Ployimide 1420 - - 45 - 400 260
Polyphenylene sulfide 1340 - - 49 - 85 150
Polypropylene 905 2.0 0.2 100 0.65 -10 100
Polysulphone 1240 1.3 - 56 - 180 170
Polrstyrene 1050 1.3 0.15 80 0.6 100 50
Polythene (LD) 920 2.2 0.24 200 1.17 -120 50
Polythene (HD) 950 2.2 0.25 120 1.57 -120 55
PTFE 2100 1.0 0.25 140 0.7 -113 250
PVC (rigid) 1400 0.9 0.16 70 1.16 80 50
PVC (flexible) 1300 1.5 0.14 140 0.7 80 50
SAN 1080 1.3 0.17 70 0.81 115 60
Polystyrene foam 32 - 0.032 - - - -

The following table shows the chemical structure of some repeating units:
Polymer Engineering Abbreviations
Thermoplastics
PMMA: Polymethylmethacrylate (Acrylic)
ABS: Acrylonitrile-butadiene-styrene
CA: Cellulose Acetate
CN: Cellulose Nitrate
CAB: Cellulose Acetate Butyrate
SAN: Styrene-acrylonitrile
PTFE: Polytetrafluoroethylene
PVdF: Polyvinylidene Fluoride
PVF: Polyvinylfluoride
PA: Polyamide (Nylon)
POM: Polyoxymethylene (Acetal)
PC: Polycarbonate
PET: Polyethylene-terephthalate (Polyester)
PBT: Polybutylene-terephthalate ( " )
PPO: Polyphenylene Oxide
MPPO: Modified Polyphenylene Oxide
PPS: Polyphenylene Sulphide
PP: Polypropylene
PS: Polystyrene
SB: (HIPS) Styrene Butadiene (High impact PS)
PVC: Polyvinyl Chloride
uPVC: Unplasticised PVC
PVA: Polyvinyl Acetate
LDPE: Low Density Polyethylene
HDPE: High Density Polyethylene
EVA: Ethylene Vinyl Acetate
PEEK: Polyetherether-keytone
PEK: Polyether-keytone
PSU: Polysulphone
PES: Polyethersulphone
PI: Polyimide
PEI: Polyetherimide

Thermosets
AK: Alkyds
EP: Epoxies
PF: Phenolics
UP: Unsaturated Polyesters
UF: Urea Formaldehyde (Amino)
MF: Melamine Formaldehyde (Amino)
PUR: Polyurethanes
SI: Silicones
PI: Polyimides

Elastomers
TR: Thermoplastic Rubber
NR: Natural Rubber
SBR: Styrene Butadiene Rubber
BR: Butadiene Rubber
EPM: Ethylene-propylene Co-polymer
EPDM: Ethylene-propylene-diene Terpolymer
CR: Chloroprene Rubber
BU: Butyl Rubber
NBR: Acrylonitrile Butadiene Rubber