Outline

1. Introduction
2. Average molecular weight of polymers
3. Physical and mechanical properties of polymers
4. Technical applications of selected engineering plastics
5. Structure and classification of plastics

1. Introduction
Plastic materials can encounter mechanical stress, impact, flexure, elevated
temperatures, different environments, etc. Hence various properties are measured
and reported to give an indication of a material’s ability to perform under various
conditions. Properties are determined on standard test parts and are useful for
comparative purposes. A description of properties are as follows.
Density: The mass per unit volume of a material at 73oF (23oC).
Tensile Modulus: An indicator of the stiffness of a part. It is basically the applied
tensile stress, based on the force and cross-sectional area, divided by the observed
strain at that stress level.
Tensile Strength: The amount of force required to elongate the plastic by a
defined amount. Higher values mean the material is stronger.
Elongation at Break: The increase in length of a specimen under tension before it
breaks under controlled test conditions. Usually expressed as a percentage of the
original length. Also called ‘‘strain.’’
Flexural Modulus: The ratio of applied stress to the deflection caused in a
bending test. It is a measure of the stiffness of a material during the first part of the
bending process.
Flexural Strength: The maximum stress which can be applied to a beam in pure
bending before permanent deformation occurs.
Izod Impact Strength: The amount of impact energy that is required to cause a
test specimen to break completely. The specimen may be notched or unnotched.
Heat Deflection Temperature (HDT, also called of deflection temperature under
load, or DTUL): Gives an indication of a material’s ability to perform at higher
temperatures while supporting a load. It shows the temperature at which a test
specimen will deflect a given distance under a given load in flexure under specified
test conditions, usually at 1.82 and/or 0.42-MPa loads.
Vicat Softening Temperature: A measure of the temperature at which a plastic
starts to soften at specified test conditions according to ISO 306. It gives an
indication of a material’s ability to withstand limited short-term contact with a
heated object.
Relative Thermal Index (RTI, formerly called continuous-use temperature): The
continuous operating temperature of plastics materials used in electrical
applications, It is the maximum temperature at which the material retains at least
50% of the original value of all properties tested after the specified amount of time.
Oxygen Index: A flammability test that determines the minimum volumetric
concentration of oxygen that is necessary to maintain combustion of a specimen
after it has been ignited.
Hardness: The resistance of a material to indentation under standardized
conditions. A hard indenter or standard shape is pressed into the surface of the
material under a specified load. The resulting area of indentation or the depth of
indentation is measured and assigned a numerical value. For plastics, the most
widely used methods are Rockwell and Shore methods and Ball hardness.
Coefficient of Thermal Expansion (CTE): A measure of how much a material
will lengthen (or shorten upon cooling) based on its original length and the
temperature difference to which it is exposed. It becomes important when part
dimensions are critical or when two different materials with different CTEs are
attached to each other.
Shrinkage: The percentage of reduction in overall part dimensions during
injection molding. The shrinkage occurs during the cooling phase of the process.
Water Absorption/Moisture Absorption: The percentage weight gain of a
material after immersion in water for a specified time at a specified temperature.
Low values are preferred and are important in applications requiring good
dimensional stability. As water is absorbed, dimensions of the part tend to increase
and physical properties can deteriorate. In addition, low water absorption is very
important for most electrical properties.
Relative Permittivity (formerly called dielectric constant): A measure of the
amount of electrical energy stored in a material. It is equal to the capacitance of a
material divided by the capacitance of a dimensionally equivalent vacuum.
Important for high frequency or power applications in order to minimize power
losses. Low values indicate a good insulator. Moisture, frequency, and temperature
increases may have adverse effects.
Dissipation Factor (also called ‘‘loss tangent’’): A measure of the dielectric
characteristics of a plastic resin. Moisture, frequency, and temperature increases
may have adverse effects.
2. AVERAGE MOLECULAR WEIGHT OF POLYMERS
 3. PHYSICAL AND MECHANICAL PROPERTIES OF POLYMERS
PHYSICAL PROPERTIES

Physical properties of polymers include molecular weight, molar volume, density,

degree of polymerization, crystallinity of material, and so on.
1. Degree of Polymerization
The degree of polymerization (DP)-n in a polymer molecule is defined as the
number of repeating units in the polymer chain. For example,
-(-CH𝟐 - CH𝟐-)-n

2. Molecular Weight
The molecular weight of a polymer molecule is the product of the degree of
polymerization and the molecular weight of the repeating unit. The polymer
molecules are no identical but are a mixture of many species with different degrees
of polymerization, that is, with different molecular weights. Therefore, in the case
of polymers we talk about the average values of molecular weights That is the
Molecular Weight Averages, Number-Average Molecular Weight, Weight-
Average Molecular Weight and the Polydispersity Index or Heterogeneity Index
and can be obtained as shown above .

The physical properties (such as transition temperature, viscosity, etc.) and

mechanical properties (such as strength, stiffness, and toughness) depend on the
molecular weight of polymer. The lower the molecular weight, lower the transition
temperature, viscosity, and the mechanical properties. Due to increased
entanglement of chains with increased molecular weight, the polymer gets higher
viscosity in molten state, which makes the processing of polymer difficult.
 3. Polymer Crystallinity: Crystalline and Amorphous Polymers
The polymeric chains being very large are found in the polymer in two forms as
follows:
Lamellar crystalline form in which the chains fold and make lamellar structure
arranged in the regular manner and amorphous form in which the chains are in the
irregular manner. The lamellae are embedded in the amorphous part and can
communicate with other lamellae via tie molecules (see Fig. A1.2). Polymer may
be amorphous or semi-crystalline in nature.
The %crystallinity is given by:

𝜌c = density of the completely crystalline polymer,

𝜌a = density of the completely amorphous polymer,
𝜌s = density of the sample.

A typical range of crystallinity can be defined as amorphous (0%) to highly

crystalline (>90%). The polymers having simple structural chains as linear chains
and slow cooling rate will result in good crystallinity as expected. In slow cooling,
sufficient time is available for crystallization to take place. Polymers having high
degree of crystallinity are rigid and have high melting point, but their impact
resistance is low. However, amorphous polymers are soft and have lower melting
points. For a solvent, it is important to state that it can penetrate the amorphous
part more easily than the crystalline part.
Examples of amorphous polymers: polystyrene and poly(methyl methacrylate).
Examples of crystalline polymers: polyethylene, and PET polyester.
Spherulites: if the molten polymer is cooled down, then the crystalline lamellae
grow in radial direction from a nucleus along the three dimensions leading to a
spherical structure called spherulite. The amorphous region is in between the
crystalline lamellae (Fig. A1.3). Spherulite formation and its diameter depend on
various parameters such as the number of nucleation sites, polymer molecule
structure and rate of cooling. Due to highly ordered lamellae in the spherulite, it
shows higher density, hardness, tensile strength, and Young’s modulus. The
elasticity and impact resistance are shown, because the lamellae are connected to
amorphous regions.
MECHANICAL PROPERTIES
It is of great importance to be familiar with some basic mechanical properties of
the material before its application in any field, such as how much it can be
stretched, how much it can be bent, how hard or soft it is, how it behaves on the
application of repeated load and so on.
a) Strength:
In simple words, the strength is the stress required to break the sample. There are
several types of the strength, namely tensile (stretching of the polymer),
compressional (compressing the polymer), flexural (bending of the polymer),
torsional (twisting of the polymer), impact (hammering) and so on. The polymers
follow the following order of increasing strength: linear < branched < cross-linked
< network.
Factors Affecting the Strength of Polymers
i. Molecular Weight:
The tensile strength of the polymer rises with increase in molecular weight and
reaches the saturation level at some value of the molecular weight (Fig. A1.9). The
tensile strength is related to molecular weight by the following equation.

∞ is the tensile strength of the polymer with molecular weight of infinity. A is

some constant, and M is the molecular weight. At lower molecular weight, the
polymer chains are loosely bonded by weak van der Waals forces and the chains
can move easily, responsible for low strength, although crystallinity is present. In
case of large molecular weight polymer, the chains become large and hence are
entangled, giving strength to the polymer.
ii. Cross-linking: The cross-linking restricts the motion of the chains and
increases the strength of the polymer.
iii. Crystallinity: The crystallinity of the polymer increases strength, because in
the crystalline phase, the intermolecular bonding is more significant.
Hence, the polymer deformation can result in the higher strength leading to
oriented chains.
b) Percent Elongation to Break (Ultimate Elongation):
It is the strain in the material on its breakage, as shown in Fig. A1.10. It measures
the percentage change in the length of the material before fracture. It is a measure
of ductility. Ceramics have very low (<1%), metals have moderate (1–50%) and
thermoplastic (>100%), thermosets (<5%) value of elongation to break.
c) Young’s Modulus (Modulus of Elasticity or Tensile Modulus):
Young’s Modulus is the ratio of stress to the strain in the linearly elastic region
(Fig. A1.11). Elastic modulus is a measure of the stiffness of the material.

d) Toughness:
The toughness of a material is given by the area under a stress–strain curve (Fig.
A1.12).
The toughness measures the energy absorbed by the material before it breaks.
A typical stress–strain curve is shown in Fig. A1.13, which compares the stress–
strain behavior of different types of materials. The rigid materials possess high
Young’s modulus (such as brittle polymers), and ductile polymers also possess
similar elastic modulus, but with higher fracture toughness. However, elastomers
have low values of Young’s modulus and are rubbery in nature.
The yield strength of the plastic polymer is the corresponding stress where the
elastic region (linear portion of the curve) ends (Fig. A1.14). The tensile strength is
the stress corresponding to the fracture of the polymer. The tensile strength may be
higher or lower than the yield strength (Fig. A1.14).
The mechanical properties of the polymer are strongly affected by the temperature.
A typical plot of stress versus strain is shown in Fig. A1.15. From the plot, it is
clear that with increase in the temperature, the elastic modulus and tensile strength
are decreased, but the ductility is enhanced.
e) Viscoelasticity:
There are two types of deformations: elastic and viscous. Consider the constant
stress level applied to a material as shown in the Fig. A1.16.
In the elastic deformation (Fig. A1.17), the strain is generated at the moment the
constant load (or stress) is applied, and this strain is maintained until the stress is
not released. On removal of the stress, the material recovers its original dimensions
completely, that is the deformation is reversible (Fig. A1.17), that is:
𝜎 = E𝜀
where E is the elastic modulus, 𝜎 is applied stress, and 𝜖 is the strain developed.
However, in viscous deformation (Fig. A1.18), the strain generated is not
instantaneous and it is time dependent. The strain keeps on increasing with time on
application of the constant load, that is, the recovery process is delayed. When the
load is removed, the material does not return to its original dimensions completely,
that is, this deformation is irreversible (Fig. A1.18).

where
𝛾 = viscosity, and
d𝜖/dt = strain rate

Usually, polymers show a combined behavior of elastic and plastic deformation

(Fig. A1.19) depending on the temperature and strain rate. At low temperature and
high strain rate, elastic behavior is observed, and at high temperature but low strain
rate, the viscous behavior is observed. The combined behavior of viscosity and
elasticity is observed at intermediate temperature and strain rate values. This
behavior is termed as viscoelasticity, and the polymer is termed as viscoelastic.
f) Viscoelastic Relaxation Modulus.
At a given temperature, when the polymer is strained to a given value, then the
stress required to maintain this strain is found to decrease with time. This is called
stress relaxation (Fig. A1.20).
The stress required to maintain the constant strain value is decreased with time,
because the molecules of polymer get relaxed with time, and to maintain the level
of strain, somewhat lower value of stress is sufficient (Fig. A1.20).
 4. TECHNICAL APPLICATIONS OF SELECTED ENGINEERING PLASTICS
Plastics clearly constitute an important component of the range of materials used in modern
society. Almost all aspects of daily life involve plastics or rubber in some form or the other.
These include clothing and footwear, together with products for use in food and public health
applications. Over 40 million tonnes of plastics were converted into textile fibre (mainly nylon,
polyester and acrylics) worldwide for use in apparel manufacture. Polycotton clothing contains
high levels of PET plastic; high-performance clothing is almost exclusively plastics—polyesters,
fluoropolymers and nylons. Fleece clothing is 100 per cent plastic (PET) and can be made from
recycled PET. Most footwear also relies heavily on plastics; the footbed and outsoles are made
from polyurethane or other elastomeric material while the uppers might be made of vinyl or
other synthetic polymer.
Plastics also deliver many public health benefits. They facilitate clean drinking water supplies
and enable medical devices ranging through surgical equipment, drips, aseptic medical
packaging and blister packs for pills. They provide packaging that reduces food wastage, for
instance in the use of modified atmosphere packaging (Mullan 2002) that prolongs the life of
meat and vegetables.
Owing to their light weight, plastics reduce transportation costs and, therefore, atmospheric
carbon dioxide emissions. Public and private transportation vehicles can now contain up to 20
per cent plastics typically as parcel shelves, door liners, steering wheels, electrics and
electronics, and recent aircraft such as the Boeing Dreamliner is designed from up to 50 per cent
plastics. Plastics can also be used to improve the performance and reduce the costs of building
materials; examples of this include lightweight fixings, window and door frames, fixtures and
insulation materials. Plastics also save energy in a variety of other applications and enhance the
quality of many recreational activities, World Cup standard footballs and other equipment such
as tennis, squash racquets and golf clubs use nylons, polyether ether ketones, PP and polymeric
rubber compounds.
Plastics deliver unparalleled design versatility over a wide range of operating temperatures. They
have a high strength-to-weight ratio, stiffness and toughness, ductility, corrosion resistance, bio-
inertness, high thermal/electrical insulation, non-toxicity and outstanding durability at a
relatively low lifetime cost compared with competing materials; hence plastics are very resource
efficient. As reported by PlasticsEurope (2008), plastics can be made from any feedstock
containing carbon and hydrogen. Currently, fossil fuels are the preferred feedstock, but plastics
are also made from renewable resources such as sugar and corn. Around 4 per cent of global oil
and gas production is used as the raw material for plastics production and a similar amount is
used as energy in the process. However, plastics by their very nature store carbon, and this
energy is retained by reusing and recycling plastics.
The Plastics Pyramid
With so many industrial plastics to choose from, materials are commonly organized into a
pyramid to demonstrate the differences between different families of amorphous and crystalline
plastics. At the bottom, you find commodity plastics such as acrylic, ABS, polypropylene,
HDPE, and PVC. Commodity plastics are cost-effective, and depending on the material, can
offer good chemical resistance and machinability (although not all plastics in this category
exhibit these qualities).
Moving up a level in the pyramid, you find engineering plastics such as nylon, acetal, UHMW-
PE, and polycarbonate. While again, materials at this level vary in characteristics, this family of
materials can be suited for general structural or bearing and wear applications, featuring
moderate temperature resistance and strength.
For more specialized and demanding applications, the top two tiers of the pyramid house high-
performance plastics and imidized plastics. High-performance plastics such as PEEK, PPS, and
PTFE can withstand high service temperatures while exhibiting excellent chemical resistance.
Imidized plastics, once considered suited only for aerospace applications, are becoming more
widely specified for thermal insulators, high-performance bearings, electrical connectors, and
ablative structures. Imidized plastics include polyamide-imide (PAI), polybenzimidazole (PBI),
and polyimide (PI), which feature the highest temperature resistance and load bearing
capabilities, among other features.

Plastics Pyramid
ENGINEERING PLASTICS
Engineering plastics and high performance plastics are our main business in the field of
Engineering. Engineering plastics have a whole array of benefits to offer, and in many cases can
effectively replace metals or ceramics. Moreover, engineered plastic components often provide
the only alternative when it comes to the implementation of unusual technical applications -
which makes them a true pacemaker for innovation in every key of industry.
Engineering plastic are thermoplastic polymers, possess better mechanical and/or thermal
properties than the more widely used standard plastics such as polystyrene, PVC and
Polyethylene. They are a group of plastic materials that have better mechanical and/or thermal
properties than the more widely used commodity plastics (such as polystyrene, PVC,
polypropylene and polyethylene).
Being more expensive than standard plastics, engineering plastics are produced in lower
quantities and tend to be used for smaller objects or low-volume applications (such as
mechanical parts), rather than for bulk and high-volume ends (like containers and packaging).
Engineering plastics have a higher heat resistance than standard plastics and are continuously
usable at temperatures up to about 150°C.
The term usually refers to thermoplastic materials rather than thermosetting ones. Examples of
engineering plastics include polyamides (PA, nylons), used for skis and ski boots;
polycarbonates (PC), used in motorcycle helmets and optical discs; and poly(methyl
methacrylate) (PMMA, major brand names acrylic glass and plexiglass), used e.g. for taillights
and protective shields. The currently most-consumed engineering plastic is acrylonitrile
butadiene styrene (ABS), used for e.g. car bumpers, dashboard trim and Legos.
Engineering plastics have gradually replaced traditional engineering materials such as metal,
glass or ceramics in many applications. Besides equalling or surpassing them in weight/strength
and other properties, engineering plastics are much easier to manufacture, especially in
complicated shapes. All different product types together, worldwide more than 22 million tonnes
of engineering plastics were consumed in 2020
In comparison to widely used commodity plastics for packaging as PE, PP, PVC, engineering
plastics are chosen in case of higher requirements in mechanical strength or thermal resistance,
but are not as sophisticated and expensive as high temperature plastics.
Material blends and modifications permit product characteristics to be optimised across a broad
range to suit different applications. Engineering plastics consequently cover a wide spectrum of
different properties.

Engineering plastics can be used permanently at temperatures between 100°C and 150°C. In
general, this product group is also referred to as technical thermoplastics.
Engineering plastics offer:
a. Good mechanical characteristics
b. Excellent machinability and dimensional stability
c. Good chemical resistance
d. Good wear resistance
Below are sum of the applications of these polymers
 5. STRUCTURE AND CLASSIFICATION OF SELECTED POLYMERIC
MATERIALS
The different plastics material groups are presented over the following pages together with a
description of their typical properties, identifying characteristics, structure and so on.
Characteristic application examples for the relevant materials are also listed.