Chapter 3 Polymers Thermoplastics and Additives

7.
Polymers: Structure, General Properties and Applications

7.3 Thermoplastics
• As the temperature is raised above the glass-transition temperature, or melting point
Tm, certain polymers become easier to form or mold into desired shapes.
• The increased temperature weakens the secondary bonds (through thermal vibration
of the long molecules), and the adjacent chains thus can move more easily when
subjected to external shaping forces.
2005 Pearson Education South Asia Pte Ltd

7. Polymers: Structure, General Properties and Applications
7.3 Thermoplastics
• When the polymer is cooled, it returns to its original hardness and strength; in other
words, the process is reversible.
• Polymers that exhibit this behavior are known as thermoplastics.
• Fig 7.10 shows the general terminology describing the behavior of three types of
plastics.

7.3 Thermoplastics

7.3 Thermoplastics
Effects of Temperature
• If the temperature of a thermoplastic polymer is raised above its Tg it first becomes leathery and then, with
increasing temperature, rubbery .
• Finally, at higher temperatures, it becomes a viscous fluid: its viscosity decreases with increasing temperature.
• At still higher temperatures, the response of a thermoplastic can be likened to ice cream.
• Repeated heating and cooling cause degradation, or thermal aging, of thermoplastics.

7.3 Thermoplastics
Effects of Temperature
• Fig 7.11 shows the effect of temperature on the stress–strain curve for cellulose acetate, a
thermoplastic. Note the large drop in strength and the large increase in ductility with a relatively
small increase in temperature.
• Fig 7.12 shows the effect of temperature on the impact strength of various plastics. Small changes
in temperature can have a significant effect on impact strength.

7.3 Thermoplastics

7.3 Thermoplastics

7.3 Thermoplastics
Effects of rate of deformation
• In Eq. 2.9 below, thermoplastics in general have high m values, indicating that they can undergo large uniform deformation
in tension before fracture.
• Fig 7.13(a) shows the load-elongation curve for polycarbonate, a thermoplastic. (b) High-density polyethylene tensile test
specimen, showing uniform elongation (the long, narrow region in the specimen).
  C m
(2.9)

7.3 Thermoplastics

7.3 Thermoplastics
Orientation
• When thermoplastics are deformed (say, by stretching) the long
chain molecules tend to align in the general direction of the
elongation; this process is called orientation.

7.3 Thermoplastics
Creep and Stress Relaxation
• Because of their visco-elastic behavior, thermoplastics are particularly susceptible to
creep and stress relaxation and to a larger extent than metals.
• Thermoplastics exhibit creep and stress relaxation at room temperature; most metals
do so only at elevated temperatures.

7.3 Thermoplastics
Crazing
• Some thermoplastics when subjected to tensile stresses or to bending, develop localized,
wedge-shaped, narrow regions of highly deformed material, called crazing.
• Crazing has been observed both in transparent, glassy polymers and in other types.
• A phenomenon related to crazing is stress whitening.

7.3 Thermoplastics
Crazing
• When subjected to tensile stresses (such as those caused by folding
or bending), the plastic becomes lighter in color—a phenomenon
usually attributed to the formation of microvoids in the material.

7.3 Thermoplastics
Water Absorption
• An important characteristic of some polymers, such as nylons, is their
ability to absorb water.
• Water acts as a plasticizing agent: It makes the polymer more plastic.

7.3 Thermoplastics
Thermal and Electrical Properties
• Compared to metals, plastics generally are characterized by low thermal and electrical conductivity,
low specific gravity (ranging from 0.90 to 2.2), and a high coefficient of thermal expansion.
• The electrical conductivity of some polymers can be increased by doping (introducing impurities,
such as metal powders, salts, and iodides, into the polymer.

7.3 Thermoplastics
Thermal and Electrical Properties
• Thermally conducting polymers also are being developed for applications
requiring dimensional stability and heat transfer (such as heat sinks) as well
as for reducing cycle times in molding and processing of thermoplastics.

Example 7.2 Use of electrically conducting polymers in rechargeable batteries
One of the earliest applications of conducting polymers

was in rechargeable batteries. Modern lithium
rechargeable batteries use lithium or an oxide of lithium
as the cathode and lithium carbide (Li yC6) as the anode,
separated by a conducting polymer layer. Lithium is
used because it is the lightest of all metals and has a
high electrochemical potential, so that its energy per
volume is highest.

Example 7.2 Use of electrically conducting polymers in rechargeable batteries
The polymer, usually polyethylene oxide (PEO), with a

dissolved lithium salt is placed between the cathode and
anode. During discharging, (LiyC6) is oxidized and discharges
free electrons and lithium ions. The electrons drive external
electronics, and the ions are stored in the polymer. When the
cathode is depleted, the battery must be recharged to restore
the cathode. During charging, is transferred through the
polymer electrolytes to the cathode. Lithium-ion batteries
have good capacity, can generate up to 4.5 V, and can be
placed in series to obtain higher voltages. Developments are
taking place to make battery cells in which both electrodes
are made of conducting polymers; one has been constructed
with a capacity of 3.5 V.
7.4 Thermosetting Plastics
• When the long-chain molecules in a polymer are cross-linked in a three-dimensional
arrangement, the structure in effect becomes one giant molecule with strong covalent bonds.
• These polymers are called thermosetting polymers or thermosets, because (during
polymerization) the network is completed and the shape of the part is permanently set.
• This curing (cross-linking) reaction, unlike that of thermoplastics, is irreversible.

7.5 Additives in Plastics
• In order to impart certain specific properties, polymers usually are compounded
with additives.
• These additives modify and improve certain characteristics of the polymer, such
as stiffness, strength, color, weatherability, flammability, arc resistance (for
electrical applications), and ease of subsequent processing.

• Plasticizers are added to polymers to impart flexibility and softness by lowering their
glass-transition temperature.
• Most polymers are affected adversely by ultraviolet radiation (such as from sunlight) and
by oxygen; they weaken and break the primary bonds and cause the scission (splitting) of
the long-chain molecules; the polymer then degrades and becomes stiff and brittle.

• Fillers used in plastics are generally wood flour (fine sawdust), silica flour (fine silica powder), clay, powdered mica,
talc, calcium carbonate.
• The wide variety of colors available in plastics is obtained by adding colorants — either organic (dyes) or inorganic
(pigments).
• The flammability of polymers varies considerably, depending on their composition. The flammability of polymers
can be reduced either by making them from less-flammable raw materials or by the addition of flame retardants,
such as compounds of chlorine, bromine, and phosphorus.

• The following list gives several common polymers with different burning characteristics:
1. Plastics that do not burn: fluorocarbons (Teflon)
2. Plastics that do burn but are self-extinguishing: carbonate, nylon, vinyl chloride
3. Plastics that burn and are not self-extinguishing: acetal, acrylic, acrylonitrile- butadiene-styrene, cellulose, polyester,
propylene, styrene
• Lubricants may be added to polymers to reduce friction during their subsequent processing into useful products and to
prevent parts from sticking to the molds.

Chapter 3 Polymers Thermoplastics and Additives

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7.

Polymers: Structure, General Properties and Applications

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

One of the earliest applications of conducting polymers

2005 Pearson Education South Asia Pte Ltd

The polymer, usually polyethylene oxide (PEO), with a

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

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