120 Chapter 4

• A Tg may be detected for the amorphous

phase present in a crystalline polymer.
• The amorphous phase in a crystalline poly-
mer can have profound effects on the poly-
mer's mechanical properties.

Polymer properties are significantly affected

by the degree of crystallinity. Crystallinity tends
to increase mechanical properties such as ten-
sile strength and hardness while diminishing
ductility, toughness, and elongation. The amor-
phous phase present in semicrystalline polymers,
however, can improve the toughness. Chemical
permeability and solubility generally decrease
with increasing crystallinity. Crystalline polymers
are generally optically opaque or translucent,
whereas amorphous polymers have the greatest
optical clarity.
Semicrystalline thermoplastics will gener-
ally shrink more than amprphous thermoplastics
when cooled from the injection molding tem-
perature. Over time, the crystallinity of a
semicrystalline plastic part may increase, causing
dimensional changes (shrinkage). Amorphous
polymers are typically more dimensionally
stable.
Additives
Engineering and commodity plastics, as well as
other polymeric materials such as paints and ad-
hesives, use special additives to improve their
properties and performance. Additives improve
mechanical properties, thermal processing, sur-
face characteristics, and chemical properties as
well as appearance and aesthetic properties.
Additives may be incorporated into a poly-
mer in various ways. In thermosetting polymers,
for example, most of the additives are added to
the resin though special mixing and dispersion
processes. Most thermoplastics are sold in the
form of small beads or pellets (Figure 4-21).
Pellets and beads are made using a pelletizer
machine, in which molten polymer is extruded
Figure 4-21
Typical forms of thermoplastic beads and pellets
through a plate with many small holes. As the
polymer extrudate exits the extrusion die, the
molten polymer is simultaneously quenched in a
liquid bath and cut into small pellets with a knife.
The polymer pellets are removed from the bath,
dried, and packaged for use. During the pelletiz-
ing process, various additives are typically added
to the polymer. Examples of typical polymer ad-
ditives are listed in Table 4-1.
Fully compounded resins have additives
added in the proper proportion through the en-
tire batch of resin. Alternatively, additives are
sometimes added to a plastic by dispersing poly-
mer pellets or beads that contain concentrated
additives into a base resin (virgin pellets or
beads) before molding. Polymer pellets or beads
with concentrated additives are called master-
batch resins. Color concentrates, for example,
are often added as masterbatch additions. In-
stead of purchasing large quantities of resins in
various colors, using color concentrates allows a
molder to buy large quantities of a naturally col-
ored base resin and then control the color ofvar-
ious parts by adding a color concentrate.
The strength of a polymeric material may
be improved by using fillers such as glass, car-
bon or aramid (Kevlar®) fibers. The effect of
Principles of Polymeric Materials
Figure 4-22
Effect of glass-fiber reinforcement on the properties of nylon
glass-fiber reinforcement on the properties of
a nylon thermoplastic is shown in Figure 4-22.
Mineral fillers such as talc, ~ood pulp, milled
glass, mica, calcium carbonate, and so on may
be added to reduce the cost of a polymer resin
or to increase dimensional stability and reduce
shrinkage. The toughness of polymers is typically
improved through the incorporation of impact
modifiers. High-impact polystyrene, for exam-
pIe, contains small rubber particles (e.g., styrene
butadiene rubber) that are grafted to the main
polymer chain. The rubber particles arrest crazes
and cracks-thereby increasing the toughness
and fracture resistance of the material.
Lubricants such as molybdenum disulfide,
graphite, silicone compounds, or fluoropolymers
(Teflon®) allow a polymer to be self-lubricating
for wear application such as bearings. Other lu-
bricants (or slip agents) such as fatty acid es-
ters migrate to the surface to help lubricate a
polymer during processing to prevent the poly-
121
%
mer from sticking to processing equipment or to
itself.
Plasticizers are added to thermoplastics to
improve flexibility and toughness. Polyvinyl chlo-
ride, for example, is commonly plasticized for
applications such as automotive interiors. High-
molecular-weight phthalate esters added to PVC
increase the polymer's internal free volume, pro-
viding more space within the polymer structure
for long-range motion of the polymer chains.
While improving flexibility, plasticizers reduce
the Tg, melt viscosity, and tensile strength of a
thermoplastic (Figure 4-23). The solubility and
chemistry of plasticizers in thermoplastics is im-
portant, because plasticizers can migrate to the
surface of a polymer, causing greasy films, or
may vaporize from the surface, causing the ma-
terial to become brittle. Certain phthalate esters
such as di(2-ethylhexyl) phthalate (DEHP), used
in medical devices, food packaging, and chil-
dren's toys, have come under scrutiny by some