Classification of plastics

Based on chemical reaction

Based on the type of chemical reaction (polymerization) that links the
molecules together, plastics are classified as either thermoplastics or
thermosets.

Classes of plastics
In addition to the broad categories of thermoplastics and thermosets, thermoplastics can
be further categorized into amorphous, (semi-)crystalline, or liquid crystal polymers
(LCPs), depending on the polymer chain conformation or morphology. The
microstructures of these plastics and the effects of heating and cooling on the
microstructures are shown in Figure 1. Other classes include elastomers, copolymers,
compounds, commodity resins, and engineering resins. Additives, fillers, and
reinforcements are other classifications that relate directly to plastics properties and
performance.

FIGURE 1. Microstructure of various plastics and effect of heating and cooling during
processing

Structures and properties of plastics

Table 1 lists a summary of the relevant structures and properties of thermoplastics
and thermosets.
TABLE 1. Structures and properties of thermoplastics and thermosets
Thermoplastics

Thermosets

Microstructure
Linear or branch molecules.
Cross-linking network with chemical bonds among
No chemical bonds among
molecules after the chemical reaction.
the molecules.
Reaction to Heat
Can be re-softened (physical
Cannot be re-softened after cross-linking without
phase change).
degradation.
General Properties
Higher impact strength.
Easier processing.
Better adaptability to
complex designs.

Greater mechanical strength.

Greater dimensional stability.
Better heat and moisture resistance.

Thermoplastics
Usefulness of thermoplastics
Thermoplastics typically have high molecular weights resulting from a
high degree of polymerization. The long molecular chain, either linear or
branched, has side chains or groups that are not attached to other
polymer molecules. As a result, thermoplastics can be repeatedly
softened (or hardened) by an increase (or decrease) in temperature.
This type of phase change without a chemical reaction permits the
recycling of thermoplastic scraps, such as the trimmed-off runners and
sprues from injection molding. An analogy is the phase change of ice
turning into water under heat, and then becoming a solid again when
cooled. Although thermoplastics are recyclable, it is very likely that a
small degree of chemical change (e.g., oxidation, thermal degradation)
takes place during processing, and therefore the properties of recycled
polymers may not be equivalent to those of the virgin polymer.

Market share distribution of thermoplastics

Thermoplastics account for more than 70 percent of all polymers produced.
Thermoplastic materials are purchased as pellets or granules. They are melted by
heat under pressure into a relatively viscous fluid and shaped into a desirable product
or form by cooling. Thermoplastics generally offer higher impact strength, easier
processing, and better adaptability to complex designs than do thermosets.
Commodity resins
Among thermoplastics, the commodity resins-for example, high-density polyethylene
(HDPE), low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS),
and polyvinyl chloride (PVC)-account for more than 90 percent of all thermoplastics.
Engineering resins
On the other hand, the engineering resins, such as acetal, acrylonitrile butadiene
styrene (ABS), nylon, and polycarbonate (PC), offer improved performance,
including higher mechanical properties, better heat resistance, higher impact
strength. Thus, they demand a higher price.

Structures and properties of thermoplastics

Table 1 lists a summary of the relevant structures and properties of amorphous
polymers and crystalline polymers.
TABLE 1. Structures and properties of amorphous and crystalline polymers
Amorphous Polymers

Crystalline Polymers

Common Materials
Acrylonitrile butadiene styrene
(ABS)
Acrylics (e.g., PAN, PMMA)
Polycarbonate (PC)
Polystyrene (PS)
Polyvinyl chloride (PVC)
Styrene acrylonitrile (SAN)

Acetals
Nylon
Polyethylene (PE)
Polypropylene (PP)
Thermoplastic Polyesters (e.g., PBT, PET)

Microstructure
Random molecular orientation in
both molten and solid phases.

Random molecular orientation in molten phase,

but densely packed crystallites occurs in solid
phase.

Reaction to Heat
Softens over a range of temperature
(no apparent melting temperature).
General Properties

Fairly distinct melting temperature.

Transparent
Poor chemical resistance
Low volumetric shrinkage in
molding
Generally low strength
Generally high melt viscosity
Lower heat content

Translucent or opaque
Excellent chemical resistance
High volumetric shrinkage in molding
Generally high strength
Generally low melt viscosity
Higher heat content (with heat of
crystallization)

Amorphous polymers
Molten polymer molecules in an unstressed state are randomly oriented and entangled
with other molecules. Amorphous materials retain this type of entangled and disordered
molecular configuration regardless of their states, as shown in Microstructure of various
plastics and effect of heating and cooling during processing.
Response to temperature
When the temperature of melt decreases, amorphous polymers start becoming rubbery.
When the temperature is further reduced to below the glass transition temperature, the
amorphous polymers turn into glassy materials. Amorphous polymers possess a wide
softening range (with no distinct melting temperature), moderate heat resistance, good
impact resistance, and low shrinkage.
Differential shrinkage in thickness direction
The molecules tend to be uncoiled and stretched in the flow direction as the cavity is
filled. Those molecules that are quenched by contact with the cold mold wall will be
frozen, stretched out in the flow direction. Molecules toward the interior of the part are
insulated from the mold wall by the frozen layer. These will have time enough to recoil
as they cool more slowly. That is, the molecules on the surface will be oriented and will
shrink less; molecules in the interior will be less oriented and will shrink more. The
differential shrinkage in the thickness direction results in flow-induced residual stresses
in molded plastics.
Similar linear shrinkages
Families of amorphous plastics can often be substituted one for another, in the same
injection cavities, since their linear shrinkages are in the same range. Therefore, styrene
can be substituted for ABS; acrylics can be molded in the same cavities as
polycarbonates. The properties will be different for the substitution, but the dimensions
will usually be close enough to be within specified tolerances.

(Semi-)crystalline polymers
Crystalline materials are polymer chains that do not have bulky pendant groups, chain
branches, or cross-links. They may accommodate themselves in a well-ordered regular
lattice (polymer crystallite) when the molten polymers are cooled below the melting
temperature, as shown in Microstructure of various plastics and effect of heating and
cooling during processing.

Controlling the degree of crystallinity

The crystallization process stops when the materials are cooled below the glass transition
temperature. Since it is difficult to achieve 100 percent crystallization under normal
processing conditions, any crystallizable polymers are typically semi-crystalline,
possessing both amorphous and crystalline phases. The degree of crystallinity depends on
both the chemical structure of the polymer and the processing conditions. Fast-cooling
pvT for semi-crystalline materials discusses how a fast cooling rate, which occurs during
molding, affects the material's transition to the crystalline phase. (Semi-)crystalline
polymers have a distinct melting point, good chemical and heat resistance, good lubricity,
low moisture absorption, and high shrinkage.
High linear shrinkage
The significantly higher linear shrinkage of the semi-crystalline polymers precludes them
being molded in the same cavities that are used for amorphous plastics: most dimensions
will be significantly different and will most likely miss tolerances enough not to be
functional in the same application.

Liquid crystal polymers

Liquid crystal polymers (LCPs) exhibit ordered molecular arrangements in both the melt
and solid states, as shown in Microstructure of various plastics and effect of heating and
cooling during processing. These materials are characterized by their stiff, rod-like
molecules that form the parallel arrays or domains. LCPs offer a number of processing
and performance advantages including low melt viscosity, low mold shrinkage, chemical
resistance, stiffness, creep resistance, and overall dimensional stability.

Thermosets
How they differ from thermoplastics
Cross-linking is a chemical process in which chemical bonds form among
molecules of thermosetting materials, resulting in an interconnected
network, as shown in Microstructure of various plastics and effect of heating
and cooling during processing. This cross-linking process is the principal
difference between thermoplastics and thermosets. Thermosets inherently
possess greater mechanical strength, higher service temperature limits, and
greater dimensional stability than thermoplastics. Many thermosets are
engineering resins and, because of the cross-linking, thermosets possess
an amorphous structure.

Cross-linking (reaction)
Prior to molding, the chain-like structure of thermosets is similar to thermoplastics.
During processing, thermosets polymerize (react or cure) with the activation of heat

and/or a chemical means into a cross-linked microstructure. Once the reaction is

completed, the polymer chains are bonded (cross-linked) together to form a threedimensional network. These cross bonds among molecules prohibit the slippage of
individual molecular chains. Consequently, a thermoset becomes an infusible and
insoluble solid and cannot be re-softened and reprocessed through the application of heat,
without degrading some linkages. The best analogy to thermosets is that of a hard-boiled
egg; the yolk has turned from a liquid to a solid and cannot be converted back to a liquid.

Processing thermosets
Thermosets are usually purchased as liquid monomer-polymer mixtures or as a partially
polymerized molding compound. Starting from this uncured condition, they can be
formed to the final shape in the cavity by polymerization (activated either by heat or by
chemical mixing) with or without pressure. Thermosets are generally filled or reinforced
with materials, such as minerals, talc, or glass fibers to impart specific properties, such as
shrinkage control, chemical and shock resistance, electrical and thermal insulation, and/or
to reduce cost.