Processing of Polymers and Composites

Lecture 20 – 02/03/2020

Dr S. Gowthaman
Indian Institute of Information Technology Design and Manufacturing Kancheepuram
Chennai - 600127
 Resins (Matrix)
Epoxy
• Very versatile resin system, allowing for a broad range of properties and
processing capabilities.
• Exhibits excellent adhesion to a variety of substrate materials.
• The most widely used resin materials and are used in many applications, from
aerospace to sporting goods.
• There are varying grades of epoxies with varying levels of performance to meet
different application needs.
• By changing the formulation, properties of epoxies can be changed; the cure
rate can be modified, the processing temperature requirement can be changed,
the cycle time can be changed, the toughness can be changed, the temperature
resistance can be improved, etc.
Epoxy
Epoxy prepolymer formed by condensation polymerization….

Epoxide group Diglycidyl ether bisphenol A Epoxide group

Curing of epoxy by adding diamines…

The amine group still has a hydrogen left on it, and can react with another epoxy group,
in the exact same manner.
As many hydrogens as the amine has, that's how many epoxy groups it can react with.
Curing of epoxy by adding diamines…
So this is what happens…

We are using diamine, so the amine group on the other end of the diamine can react with
two epoxy groups as well. So we end up with four epoxy prepolymers tied to one diamine
molecule.
Curing of epoxy by adding diamines…
The other ends of
the diepoxy prepolymers
are also attached to
other diamine molecules.
In this manner all the
diamine molecules and
all the diepoxy molecules
become tied together in
one big molecule,
a crosslinked network.

These cross-links
grow in a three-
dimensional network
and finally form a
solid epoxy resin.
Curing of epoxy by adding diamines…
• The stoichiometry of the curing reaction should be controlled for
optimum properties in the cured resin
• The epoxy prepolymers are characterized by epoxide equivalent
weight (EEW), which is the molecular weight divided by the
number of epoxide groups.
• The equivalent weight of the curing agent is the molecular weight
of the agent divided by the number of (hydrogen) sites on the
molecule capable of opening epoxy rings.
• Thus one equivalent of an epoxy prepolymer is cured by one
equivalent of a curing agent.
Curing of epoxy by adding diamines…
Curing of epoxy by adding diamines…
Epoxy
• Epoxies can be produced at room temperatures. However, by proper selection of curing agents,
the curing process can be conducted at elevated temperatures as well.
• The curing process time strongly depends on the choice of resin as well as curing agent. It can
vary between minutes to 24 hours.
• Many a times, heat is applied to accelerate the curing process. Typically, curing time decreases,
almost exponentially, with increasing temperature.
• Epoxies come in liquid, solid, and semi-solid forms.
• Liquid epoxies are used in RTM, filament winding, pultrusion, hand lay-up, and other processes with
various reinforcing fibers such as glass, carbon, aramid, boron, etc.
• Semi-solid epoxies are used in prepreg for vacuum bagging and autoclave processes.
• Solid epoxy capsules are used for bonding purposes.
• Epoxies are more costly than polyester and vinylesters and are therefore not used in cost-sensitive
markets (e.g., automotive and marine) unless specific performance is needed.
Phenolics
• Phenolics are formed by the reaction of phenol and formaldehyde
• Bakelite – phenol & formaldehyde with hydrochloric acid as curing agent

Phenolics meet aircraft requirements for low smoke and toxicity. They are used for aircraft
interiors, stow bins, and galley walls, as well as other commercial markets that require
low-cost, flame-resistant, and low smoke products.
Because of their high temperature resistance, phenolics are used in exhaust components,
missile parts, manifold spacers, and disc brakes.
Phenolic resins are used primarily in the
transport industry because they have:
• High flame resistance
• Low toxin levels
• Half the price of vinyl ester
Polyesters
• Unsaturated polyesters are obtained by the reaction of unsaturated acids like maleic,
fumaric, phthalic, and terephthalic with alcohols like ethylene glycol and propylene glycol.
• The structure of unsaturated polymer constitutes of mutually disconnected long chains of
linear polymers.
• For the curing or crosslinking process, a reactive monomer such as styrene is added in the
30 to 50 wt% range. The carbon-carbon double bonds in unsaturated polyester molecules
and styrene molecules function as the cross-linking site. Benzoyl peroxide is normally
used as initiator of curing action for polyesters.

• Low costs aspect

• Applicability
• UV resistance
Vinyl Ester
• Vinyl ester is produced by the esterification of an epoxy prepolymer with acrylic
or methacrylic acids.
• For the curing or crosslinking process, a reactive monomer such as styrene is added in the
35 to 40 wt% range. Benzoyl peroxide is normally used as initiator of curing action for
vinyl ester.
• They offer good chemical and corrosion resistance and are used for FRP pipes and tanks
in the chemical industry.
• They are cheaper than epoxies and are used in the automotive and other high-volume
applications where cost is critical in making material selection.
• The properties are in-between of epoxy and polyester.

• Better mechanical properties [than Polyester]

• Resistance to water
• Resistance to other chemicals
• Lower shrinkage [than polyester]
Cyanate Ester
• Cyanate esters are formed via the reaction of bisphenol esters and cyanic acid
• Good balance of mechanical properties and toughness
• High-temperature thermosetting resin - they can achieve high Glass-Transition
temperatures up to 250°C.
Bismaleimide and Polyimide
• BMI and polyimide are used for high-temperature applications in aircrafts, missiles, and
circuit boards.
• The glass transition temperature (Tg) of BMIs is in the range of 300 to 350°C, these
values are much higher than for epoxies and polyesters.
• The lack of use of BMIs and polyimides is attributed to their processing difficulty. They
emit volatiles and moisture during curing.
• Other drawbacks of these resins include the fact that their toughness values are lower
than epoxies and cyanate esters, and they have a higher moisture absorption ability.
Polyurethane
• Formed using isocynate and polyol through Reaction
Injection Moulding process
• Polyurethane is currently used for automotive applications
such as bumper beams, hoods, body panels, etc. Unfilled
polyurethane is used for various applications, including truck
wheels, seat and furniture cushions, mattress foam, etc.
• Polyurethane offers excellent wear, tear, and chemical
resistance, good toughness, and high resilience.
Thermoset
Resin
Properties
Thermoplastics
Polyethylene
• Consumer goods- Toys, food storage containers, buckets
• Medial Applications- much of the packaging for medical instruments is polyethylene and some implants (hips) are
made from UHMWPE
• Packaging-Film wrap, plastic bags, industrial and household chemical containers, milk jugs, cereal box liners, etc.
• Construction-Wire and cable insulation, water pipes (PEX)
Polypropylene
• Consumer goods - Food storage containers, weather resistant clothing, indoor–outdoor carpeting. Polypropylene is
usually used for food storage containers so that they don’t warp and lose their shape in the microwave or in the
dishwasher.
• Medial Applications- Syringes, storage containers for needles, surgical disposable fabrics
• Automotive- Instrument panels, fender liners, and brake/coolant reservoirs. Polypropylene is usually reinforced with
glass fibers in mass-produced automotive and structural applications.
• Packaging-Notably anything with a living hinge is usually made from PP like tic-tac container lids and shampoo bottle
lids, food storage containers, water bottles, pill bottle lids, etc.

Highly Resistant to Fatigue - hence the living hinge. Bend

it back and forth, it doesn't begin to break like other
plastics (try bending a piece of PVC back and forth, you'll
see it discolour and become brittle quite quickly)
Polyamide (Nylon)

• Example – Nylon 6,6 obtained by condensation reaction of hexamethylene

diamine and adipic acid
• Nylons are used for making intake manifolds, housings, gears, bearings,
bushings, sprockets, etc.
• Glass-filled and carbon-filled nylons in pellet form are available for injection
molding purposes.
• Nylons absorb moisture, which affects the properties and dimensional
stability of the part.
• Impact resistance of long glass-filled nylon is higher than conventional
engineering materials such as aluminim and magnesium
Poly-ether-ether-ketone (PEEK)

• Poly-ether-ether-ketone (PEEK) has high mechanical properties and high use

temperature.
• The glass transition temperature (Tg) of PEEK is ~150°C and melting temperature is
~350°C.
• It is reinforced with glass or carbon fibers and used in some high-performance
applications.
• Carbon-reinforced PEEK composites (APC-2) have already demostrated their
usefulness in fuselage, satellite parts, and other aerospace structures; they can be
used continuously at 250°C.
• It has better water resistance than epoxy and the toughness offered by PEEK is 50 to
100 times higher than that of epoxies.
• The drawback of PEEK-based composites is that the materials cost is very high
Polyphenylene Sulfide (PPS)
• PPS is an engineering thermoplastic and provides high operating temperatures
• Has reasonable mechanical properties. It is reinforced with glass or carbon fibers and used in
some high-performance applications.
• Maintains strength and high rigidity over wide temperature ranges
• Can be used continuously at 225°C.
• The Tg of PPS is 85°C and melting temperature is ~285°C.
• Excellent chemical resistance and is inherently flame retardant.
• PPS-based composites are used for applications where great strength and chemical resistance are
required at elevated temperature. (Example- Automotive under-the-hood applications)