THERMOSETTING POLYMER

DEFINITION-A thermosetting polymer, resin, or plastic, often called a thermoset, is a polymer

that is irreversibly hardened by curing from a soft solid or viscous liquid prepolymer or resin.
Curing is induced by heat or suitable radiation and may be promoted by high pressure, or mixing
with a catalyst. It results in chemical reactions that create extensive cross-linking between polymer
chains to produce an infusible and insoluble polymer network.
The starting material for making thermosets is usually malleable or liquid prior to curing, and is
often designed to be molded into the final shape. It may also be used as an adhesive. Once
hardened, a thermoset cannot be melted for reshaping, in contrast to thermoplastic polymers which
are commonly produced and distributed in form of pellets, and shaped into the final product form
by melting, pressing, or injection molding.

MAKING-In general, thermoset products are made through liquid molding processes. The
polymers and other agents are fed into tanks or barrels, where they are heated to a liquid state and
mixed. Then the liquid polymers and other agents are injected into a mold cavity. As the material
cools and hardens to the configuration of the cavity, it goes through a curing process where the
polymers cross-link together. That process forms an irreversible chemical bond that prevents the
risk of melting, softening or warping when or if the finished product is subjected to high heat or
corrosive environments. This makes thermosets perfect for high-heat applications and outdoor use.

There are two primary liquid molding processes used to produce thermoset plastics:

1. REACTION INJECTION MOULDING (RIM)

2. RESIN TRANSFER MOULDING (RTM)

1. REACTION INJECTION MOULDING (RIM)

The RIM molding process begins when two liquid agents—an A-component (polyol) and B-
component (isocynate) are placed in separate tanks and heated to an elevated temperature. They
are then fed at high pressure into a mix head. Once combined, the mixed liquid flows into a mold
where the chemical reaction takes place, forming a polymer in the mold.

2. RESIN TRANSFER MOULDING (RTM)

The RTM is a closed-molding process also known as liquid molding. Resin formulations are mixed
with a hardener, or catalyst, and injected into a mold that contains dry fibers, such as fiberglass,
where the part is allowed to harden and form.
CHEMICAL PREPARATION
Curing a thermosetting resin transforms it into a plastic, or elastomer by crosslinking or chain
extension through the formation of covalent bonds between individual chains of the polymer.
Crosslink density varies depending on the monomer or prepolymer mix, and the mechanism of
crosslinking:

Acrylic resins, polyesters and vinyl esters with unsaturated sites at the ends or on the backbone are
generally linked by copolymerisation with unsaturated monomer diluents, with cure initiated by
free radicals generated from ionizing radiation or by the photolytic or thermal decomposition of a
radical initiator – the intensity of crosslinking is influenced by the degree of backbone unsaturation
in the prepolymer.

Epoxy functional resins can be homo-polymerized with anionic or cationic catalysts and heat, or
copolymerised through nucleophilic addition reactions with multifunctional crosslinking agents
which are also known as curing agents or hardeners. As reaction proceeds, larger and larger
molecules are formed and highly branched crosslinked structures develop, the rate of cure being
influenced by the physical form and functionality of epoxy resins and curing agents – elevated
temperature postcuring induces secondary crosslinking of backbone hydroxyl functionality which
condense to form ether bonds.

Polyurethanes form when isocyanate resins and prepolymers are combined with low- or high-
molecular weight polyols, with strict stochiometric ratios being essential to control nucleophilic
addition polymerisation – the degree of crosslinking and resulting physical type (elastomer or
plastic) is adjusted from the molecular weight and functionality of isocyanate resins, prepolymers,
and the exact combinations of diols, triols and polyols selected, with the rate of reaction being
strongly influenced by catalysts and inhibitors; polyureas form virtually instantaneously when
isocyanate resins are combined with long-chain amine functional polyether or polyester resins and
short-chain diamine extenders – the amine-isocyanate nucleophilic addition reaction does not
require catalysts. Polyureas also form when isocyanate resins come into contact with moisture.

Phenolic, amino and furan resins all cured by polycondensation involving the release of water and
heat, with cure initiation and polymerisation exothermic control influenced by curing temperature,
catalyst selection or loading and processing method or pressure – the degree of pre-polymerisation
and level of residual hydroxymethyl content in the resins determine the crosslink density.

Thermosetting polymer mixtures based on thermosetting resin monomers and pre-polymers can be
formulated and applied and processed in a variety of ways to create distinctive cured properties
that cannot be achieved with thermoplastic polymers or inorganic materials.
PROPERTIES

Thermosetting plastics are generally stronger than thermoplastic materials due to the three-
dimensional network of bonds (crosslinking), and are also better suited to high-temperature
applications up to the decomposition temperature since they keep their shape as strong covalent
bonds between polymer chains cannot be broken easily. The higher the crosslink density and
aromatic content of a thermoset polymer, the higher the resistance to heat degradation and
chemical attack. Mechanical strength and hardness also improve with crosslink density, although at
the expense of brittleness.They normally decompose before melting.

Hard, plastic thermosets may undergo permanent or plastic deformation under load. Elastomers,
which are soft and springy or rubbery and can be deformed and revert to their original shape on
loading release.

Conventional thermoset plastics or elastomers cannot be melted and re-shaped after they are cured.
This usually prevents recycling for the same purpose, except as filler material. New developments
involving thermoset epoxy resins which on controlled and contained heating form crosslinked
networks permit repeatedly reshaping, like silica glass by reversible covalent bond exchange
reactions on reheating above the glass transition temperature.There are also thermoset
polyurethanes shown to have transient properties and which can thus be reprocessed or recycled.

SOME OF THE PROPERTIES ARE:-

1. By heating the polymer, it turns as hard material.

2. It is available in the form of liquid at Room temperature.
3. It is a Non-Recyclable process.
4. Thermoset in the form of liquid is converted into Thermoset material in the form of solid
which is done by the action of heating and its Vice-versa is not possible.
5. Gains strength: By the action of heating, the thermoset plastic material gains strength.
6. No change in the strength of the thermosetting plastic is done by the action of cooling.
7. Shape change: During heating only, the thermoset material changes its shape.
8. Temperature: The servicing temperature of a thermoset plastic material is 300°C.
9. Structure: It exhibits a Cyclic structure.
10. It is hazardous to the environment which is more when compared to the thermoplastic and
less than the rubber.

SOME OF THE EXAMPLES OF THERMOSETTING POLYMERS

 Epoxy Resin
 Phenolic(Bakelite)
 Vinyl Ester Resin
 Cyanate Ester
 Poly Ester
USES AND APPLICATION OF THERMOSETTING POLYMER

The applications and uses for thermosetting plastics have grown substantially over the years. The
success and benefits of this type of plastic is due in large part to its favorable plastic properties.
Thermoset plastics polymers cross-link together when curing to form an irreversible chemical
bond. It is one of two organic polymer-based plastic materials, the other being thermoplastic.
However, the difference between thermoplastic vs. thermoset plastics lies in their ability to be
remelted or reshaped; thermoset plastics permanently form a rigid three-dimensional structural
network that immobilizes the molecules.

With a combination of thermal stability, performance, and chemical resistance, thermoset plastics
are extensively used in a wide variety of industries—from the manufacturing of electrical
components and durable manufactured goods to the aerospace industry, heavy duty construction
equipment, the energy sector—including oil, gas, and solar—and automotive manufacturing.
Common products and applications that are made from thermoset plastics include construction
equipment panels, electrical housings and components, insulators, cell tower tops, heat shields,
circuit breakers, agricultural feeding troughs, motor components, and disc brake pistons. In short,
thermosets and their composites can be found in all markets and sectors.

Utilizing the thermoset plastic manufacturing process, some great benefits of thermosetting
materials are their light weight and flexibility. Thermoset composites remain stable in all
environments and at many temperatures, too. Parts are dimensionally stable and structurally
sound, and can be processed at low pressures and viscosities with reinforcing composites such as
fiberglass, carbon fiber, or Kevlar to produce an incredibly strong, durable material.

USES OF THERMOSETTING POLYMERS IN AUTOMOBILE INDUSTRY

High performance plastics are playing an important role in the automotive industry these days.

The light weight of plastics makes for more fuel efficient vehicles.

It is estimated that every 10% reduction in vehicle weight results in a 5% to 7% reduction in fuel
usage. Current economic and environmental concerns make the creation of more fuel efficient cars
a top priority in the automotive industry. The use of modern materials like aluminum and carbon
fiber are helpful, but the wise allocation of plastics are making an increasing difference

Some other advantages of high performance plastics used in transport vehicles include:

 minimal corrosion, allowing for longer vehicle life

 substantial design freedom, allowing advanced creativity and innovation
 flexibility in integrating components
 safety, comfort and economy
 recyclability.
1)      Polypropylene (PP)
Polypropylene is a thermoplastic polymer used in a wide variety of applications.  A saturated
addition polymer made from the monomer propylene, it is rugged and unusually resistant to many
chemical solvents, bases and acids.

Application: automotive bumpers, chemical tanks, cable insulation, gas cans, carpet fibers.

2)      Polyurethane (PUR)

Solid Polyurethane is an elastomeric material of exceptional physical properties including
toughness, flexibility, and resistance to abrasion and temperature.  Polyurethane has a broad
hardness range, from eraser soft to bowling ball hard.  Other polyurethane characteristics include
extremely high flex-life, high load-bearing capacity and outstanding resistance to weather, ozone,
radiation, oil, gasoline and most solvents.

Application: flexible foam seating, foam insulation panels, elastomeric wheels and tires, automotive
suspension bushings, cushions, electrical potting compounds, hard plastic parts.

3)      Poly-Vinyl-Chloride (PVC)

PVC has good flexibility, is flame retardant, and has good thermal stability, a high gloss, and low
(to no) lead content.   Polyvinyl chloride molding compounds can be extruded, injection molded,
compression molded, calendered, and blow molded to form a huge variety of products, either rigid
or flexible depending on the amount and type of plasticizers used.

Application: automobile instruments panels, sheathing of electrical cables, pipes, doors.

4)      ABS

Acrylonitrile Butadiene Styrene is a copolymer made by polymerizing styrene and acrylonitrile in

the presence of polybutadiene. The styrene gives the plastic a shiny, impervious surface. The
butadiene, a rubbery substance, provides resilience even at low temperatures. A variety of
modifications can be made to improve impact resistance, toughness, and heat resistance.

Application: automotive body parts, dashboards, wheel covers.

5)      Polyamide (PA, Nylon 6/6, Nylon 6)

Nylon 6/6 is a general-purpose nylon that can be both molded and extruded. Nylon 6/6 has good
mechanical properties and wear resistance.  It is frequently used when a low cost, high mechanical
strength, rigid and stable material is required.  Nylon is highly water absorbent and will swell in
watery environments.

Application: gears, bushes, cams, bearings, weather proof coatings.

6)      Polystyrene (PS)
Naturally clear, polystyrene exhibits excellent chemical and electrical resistance.  Special high gloss
and high impact grades are widely available.  This easy to manufacture plastic has poor resistance
to UV light.

Application: equipment housings, buttons, car fittings, display bases.

7)      Polyethylene (PE)

Polyethylene has high impact resistant, low density, and exhibits good toughness. It can be used in a
wide variety of thermoplastics processing methods and is particularly useful where moisture
resistance and low cost are required.

Application: car bodies (glass reinforced), electrical insulation.

8)      POM (POLYOXYMETHYLENE)

POM has excellent stiffness, rigidity, and yield strength.  These properties are stable in low
temperatures.  POM also is highly chemical and fuel resistant.

Application: interior and exterior trims, fuel systems, small gears.

9)      Polycarbonate (PC)

Amorphous polycarbonate polymer offers a unique combination of stiffness, hardness and
toughness. It exhibits excellent weathering, creep, impact, optical, electrical and thermal
properties.  Because of its extraordinary impact strength, it is the material for car bumpers,
helmets of all kinds and bullet-proof glass substitutes.

Application: bumpers, headlamp lenses.

10)   ACRYLIC (PMMA)

A transparent thermoplastic, PMMA is often used as a lightweight or shatter-resistant alternative
to glass.  It’s cheaper than PC but is also more prone to scratching and shattering.

Application: windows, displays, screens.

11)   PBT (POLYBUTELENE TEREPHTHALATE)

The thermoplastic PBT is used as an insulator in the electrical and electronics industries.  It is
highly chemical and heat resistant.  Flame-retardant grades are available.

Application: door handles, bumpers, carburetor components.

12)   Polyethylene Teraphthalate (PET)

PET is mostly used to create synthetic fibers and plastic bottles.  You may recognize it on clothing
labels under the name “polyester.”

Application: wiper arm and gear housings, headlamp retainer, engine cover, connector housings.

13)   ASA (acrylonitrile styrene acrylate)

Similar to ABS, ASA has great toughness and rigidity, good chemical resistance and thermal
stability, outstanding resistance to weather, aging and yellowing, and high gloss.  Be careful not to
burn this material.  It will cause a toxic smoke.

Application: housings, profiles, interior parts and outdoor applications.

RUBBER & CERAMICS
The crystallinity of ceramic materials ranges from highly oriented to semi-crystalline, vitrified, and
often completely amorphous (e.g., glasses). Most often, fired ceramics are either vitrified or semi-
vitrified as is the case with earthenware, stoneware, and porcelain. Varying crystallinity and
electron composition in the ionic and covalent bonds cause most ceramic materials to be good
thermal and electrical insulators (extensively researched in ceramic engineering). With such a large
range of possible options for the composition/structure of a ceramic (e.g. nearly all of the elements,
nearly all types of bonding, and all levels of crystallinity), the breadth of the subject is vast, and
identifiable attributes (e.g. hardness, toughness, electrical conductivity, etc.) are difficult to specify
for the group as a whole. General properties such as high melting temperature, high hardness, poor
conductivity, high moduli of elasticity, chemical resistance and low ductility are the norm,with
known exceptions to each of these rules (e.g. piezoelectric ceramics, glass transition temperature,
superconductive ceramics, etc.). Many composites, such as fiberglass and carbon fiber, while
containing ceramic materials, are not considered to be part of the ceramic family

Advanced ceramics materials are incorporated into automotive designs when demanding conditions
require a material that is robust and reliable. The thermal and electrical properties of ceramic
materials allow them to be used in a variety of sensors, mechanical seals, ceramic bearings, and
valves. Ceramics are more cost-efficient than metal and more durable than plastic, and can be
found throughout the automotive industry, as advances in car manufacturing require higher
complexity in automotive components. Elan Technology’s proprietary ceramic materials like the
96% Alumina ceramic and Yttria (3%) Stabilized Zirconia retain their form in mechanical
applications while maintaining heat and chemical resistance. Yttria Stabilized Zirconia, for
instance, is a high strength ceramic ideal for pump components like fuel injectors and high
durability mechanical seals in engines. When high temperature environments call for high
durability materials, advanced ceramic engineering technology provides all the necessary
components for peak engine performance and extended component lifespans.

Ceramic sensors are also used in the development of advanced monitoring systems. For example,
ceramic tire pressure monitoring systems warn occupants if there is any sudden loss of tire pressure
or if one of the tires is improperly pressurized. Ceramic coated zirconia oxygen sensors monitor
combustion efficiency, allowing the driver to maintain peak engine performance

The automobile manufacturing industry is one of the largest users of rubber products. Tires,
dashboards, and floor mats are just a few examples of products and applications that are based on
rubber material. Rubber compounding can be a mixture of different types of polymers and
additives. There is always a high possibility of impurities contained in the composition of a rubber
from and during the compounding and the manufacturing process. As the result, material
characterization of compounding rubbers (qualitatively and quantitively) is one of the analytical
challenges in many rubber manufacturing and polymer makers laboratories.

In response to these analytical challenges, the Frontier Multi-Shot Pyrolyzer’s “method map” was
developed (more information on the “method map” can be found here). The first step when
developing the method map using the Frontier Multi-Shot Pyrolyzer is to perform an Evolved Gas
Analysis (EGA). This technique provides a clear picture of the sample’s composition by identifying
its thermal zones. The EGA thermogram is then used to determine the next step in the evolution of
the analytical method map using the Multi-Shot Pyrolyzer which may include thermal desorption,
pyrolysis, reactive pyrolysis, or heart cutting.
Uses of Rubber in the Automotive Industry

One of the most commonly used materials across various industries, rubber possesses many distinct
features that make it very purposive, especially in the car manufacturing industry. Given that
vehicles are exposed to varying temperatures and different chemicals, it is essential to pick a
material that can withstand harsh environments.

From small-scale gaskets and seals to tyres and rubber matting products, the following features
make rubber a very useful component in the auto industry.

RUBBER’S SALLIENTS CHARACTERICTS

Extremely flexible and durable, rubber’s unique features render it ideal for many applications. While
different types of rubber have their own distinct features, they all have the following beneficial
characteristics in common:

 Abrasion resistance
 Chemical and grease resistance
 Excellent resistance to petroleum and oil
 Hot and cold temperature sustainability
 High tear strength
 Ozone resistance

RUBBER PRODUCTS USED IN CARS

The following car components are made from rubber:

TYRES
Tyres are known for their ability to withstand extreme temperatures. They can also retain their
shape while carrying heavy loads. Since tyres are made up of almost 50% of different kinds of
finely produced rubber materials, this makes them highly suitable for vehicular use.

With premium tyres, you can look forward to:

 Tyres that last 15,000 to 20,000 miles under normal conditions

 Good grip – whether in wet or dry conditions
 Noticeably lower noise levels

RUBBER PAD ON PEDALS

Demonstrating an excellent anti-slip design, rubber pads on vehicle pedals are the key to safer foot
control. You know your rubber pads are made of high quality rubber when they deliver reliable
and extended driving benefits.

O-RINGS, GROMMENTS and SEALS

O-rings, grommets and seals are rubber mouldings that are commonly found in a car’s engine.

 O-rings - mechanical gaskets that are used as seal to prevent the escape of air and fluid
 Grommets - reinforcement materials that protect a hole from damage while safeguarding
hoses and other cables that pass through
 Seals - any rubber component that is used to prevent leaks, vibrations and noise, they
usually come in two types: crankshaft seals and radiator seals

BUSHINGS
Serving as anti-vibration mountings, car bushings provide cushioning that reduces the friction
between the metal components of a vehicle. Two of the most common types include A-arm bushings
and sway bar bushings.

RUBBER MATS
Commonly used as a vehicle flooring alternative, rubber mats are a great way to protect your car’s
interior from spills and stains, while preventing the accumulation of dirt and grime. They can also
withstand severe weather conditions.

While carpet is also a popular alternative, a good comparison between the two suggests that rubber
mats are more advantageous when it comes to protecting your vehicle’s interior.