THERMOSETS

INTRODUCTION:
Thermoset, or thermosetting plastics are synthetic materials that undergo a chemical
change when they are treated, creating a three-dimensional network. After they are
heated and formed, these molecules cannot be re-molten and reformed.
For thermosets, the main distinguishing element of these materials is the process of
interaction between chains of polymers, which is called cross-linking. The thermo
implies that the cross-linking proceeds through the influence of heat energy input.
Thermoset, or thermosetting, plastics are synthetic materials that strengthen during
being heated, but cannot be successfully remolded or reheated after their initial heat-
forming. This is in contrast to thermoplastics, which soften when heated and harden and
strengthen after cooling. Thermoplastics can be heated, shaped and cooled as often as
necessary without causing a chemical change, while thermosetting plastics will burn
when heated after the initial molding. Additionally, thermoplastics tend to be easier to
mold than thermosetting plastics, which also take a longer time to produce (due to the
time it takes to cure the heated material).
Thermosetting plastics, however, have a number of advantages. Unlike thermoplastics,
they retain their strength and shape even when heated. This makes thermosetting
plastics well-suited to the production of permanent components and large, solid shapes.
Additionally, these components have excellent strength attributes (although they are
brittle), and will not become weaker when the temperature increases. The vulcanization
of rubber is an example of a thermosetting process: before heating with sulfur, the
polyisoprene is a tacky, slightly runny material; after vulcanization, the product is rigid
and non-tacky.
Thermoset plastic products are typically produced by heating liquid or powder within a
mold, allowing the material to cure into its hardened form. These products can be
removed from the mold even without allowing it to cool. The reaction used to produce
thermosetting plastic products is not always the result of heating, and is sometimes
performed by chemical interaction between specialized materials. Typical types of
thermosetting plastics are epoxies, polyesters, silicones and phenolics. Vulcanized
rubber is also an excellent example of a thermosetting plastic; anyone who has ever
driven an automobile can attest to the properties of a superheated tire it burns but does
not mold into a new shape.
HISTORICAL MILESTONE OF THERMOSETS:
Goodyears discovery of the vulcanization of natural rubber in 1839 could be construed
as the first successful commercial venture based on thermosetting polymers. The
plastics industry dates the beginning of thermosetting plastics to the development of
phenolics by Leo Baekeland in 1909. In this instance, Baekeland not only produced the
first synthetic cross-linked polymer, but as importantly, he discovered the molding
process that enabled him to produce homogenous useful articles of commerce. The
Bakelite product line dominated plastics technology for years until the advent of alkyds
in 1926 and the aminos in 1928.
PROCESSES:
Thermoset plastic products are typically produced by heating liquid or powder within a
mold, allowing the material to cure into its hardened form. These products can be
removed from the mold even without allowing it to cool. The reaction used to produce
thermosetting plastic products is not always the result of heating, and is sometimes
performed by chemical interaction between specialized materials. Typical types of
thermosetting plastics are epoxies, polyesters, silicones and phenolics.
Thermoset plastic industrial laminates are identified in process by three stages: A, B
and C.
A-stage refers to the key raw materials described earlier - reinforcing substrates and
resin binders.
B-stage refers to the product produced when reinforcing substrates and resin binders
are brought together but not fully cured. The reinforcing substrate is unwound from a
large master roll and dipped into a bath of liquefied resin binder. The reinforcing
substrate becomes either saturated, as is the case with absorbent papers and cotton
cloths, or coated, as is the case with glass and graphite cloths. Once the wet resin
binder is joined with the reinforcing substrate in this method, it is slowly drawn through a
long conveyorized oven where the liquefied resin binder is dried (see sketch
below). The result leaves dry semi-cured resin bind in and/or on the reinforcing
substrate. Once joined and dried in this fashion, the product is referred to as B-stage or
prepreg, and the process described is called B-staging, prepreging or treating.
C-stage refers to sheet, rod, tube, angle or other in their "cured stage".
Sheets - B-stage is sheeted into plies then laid on top of each other into predetermined
stacks that will render a given thickness. These stacks are placed into the hydraulic
laminating press between two flat surfaces and pressure is applied. While under
pressure, heat is introduced to begin the bake cycle. The resin in the B-stage product is
re-activated by the heat to a sticky state which moves slowly, filling and bonding the
layers together until it eventually hardens and cures. Once plies bond to each other and
cure, they are referred to as C-stage laminate sheet and the process described is called
laminating or pressing.
Rods - The B-stage is convolutely wrapped under tension onto itself, much like a roll of
paper towels is wound. Once the B-stage is rolled to form a rod, it is placed into a
laminating press which has upper and lower half round mold cavities. When the two
half round molds close and meet each other, a full round is formed. The size of the
mold cavity determines the diameter of the finished rod. Once pressure is applied, the
layers are pressed together filling all voids. Similar pressures and heat cycles
employed for making sheet are used. When the layers bond to each other and cure,
they are referred to as C-stage laminate rod or rolled and molded rod.
Tubes - Rolling tubes is nearly identical to rolling rods with the exception that a steel rod
called a mandrel is employed to size and form the inside diameter of the tube. B-stage
rolled tubes are usually placed into an oven chamber as opposed to a press. Tube
bake cycles compare to those of sheet and rod. Once cured, the center mandrel is
extracted. The final cured product is referred to as C-stage laminate tube or rolled tube.
Angles - This process is nearly identical to that of sheets except the mold cavities are
"V" shaped rather than flat surfaces. The final cured product is referred to as C-stage
laminate angle or molded angle.
Other shapes - Once cured, the end product is referred to as C-stage.

Specific methods of molding thermosets are:

Reactive injection molding (used for objects such as milk bottle crates)
Extrusion molding (used for making pipes, threads of fabric and insulation for
electrical cables)
Compression molding (used to shape SMC and BMC thermosetting plastics)
Spin casting (used for producing fishing lures and jigs, gaming
miniatures, figurines, emblems as well as production and replacement parts)
CATEGORIES OF THERMOSETS:
The broad classification of plastics applies to thermosets as well as thermoplastics.
General purpose thermosets are characterized by average mechanical properties, lower
resistance to temperature, higher coeffecients of expansion, and low cost/commodity-
like production and sales.
Engineering thermosets have higher mechanical properties and temperature resistance
and they are perceived to be more durable. They are more expensive and have a
moderate production volume.
Specialty thermosets are useful because of one or more highly specific and unusual
property that offsets any lack of other good properties. They are usually very
expensive and are produced in relatively small quantites.
EXAMPLES OF THERMOSPLASTICS:

NAME PROPERTIES PRINCIPAL USES

EPOXY RESIN Good electrical insulator, hard, Casting and

brittle unless reinforced, resists encapsulation, adhesives,
chemicals well bonding of other materials

MELAMINE Stiff, hard, strong, resists some Laminates for work

FORMALDEHYDE chemicals and stains surfaces, electrical
insulation, tableware

POLYESTER RESIN Stiff, hard, brittle unless laminated, Casting and

good electrical insulator, resists encapsulation, bonding of
chemicals well other materials

UREA Stiff, hard, strong, brittle, good Electrical fittings, handles,

FORMALDEHYDE electrical insulator and control knobs,
adhesives