Epoxy Resins

Epoxy resin is defined as a molecule containing more than one epoxide groups. The epoxide
group also termed as, oxirane or ethoxyline group, is shown below,

These resins are thermosetting polymers and are used as adhesives, high performance
coatings and potting and encapsulating materials. These resins have excellent electrical
properties, low shrinkage, good adhesion to many metals and resistance to moisture, thermal
and mechanical shock.

Viscosity, epoxide equivalent weight and molecular weight are the important properties of
epoxy resins.

Types of Epoxy Resins:

There are two main categories of epoxy resins, namely the glycidyl epoxy, and non-glycidyl
epoxy resins. The glycidyl epoxies are further classified as glycidyl-ether, glycidyl-ester and
glycidyl-amine. The non-glycidyl epoxies are either aliphatic or cycloaliphatic epoxy resins.
Glycidyl epoxies are prepared via a condensation reaction of appropriate dihydroxy
compound, dibasic acid or a diamine and epichlorohydrin. While, non-glycidyl epoxies are
formed by peroxidation of olefinic double bond.

Glycidyl-ether epoxies such as, diglycidyl ether of bisphenol-A (DGEBA) and novolac
epoxy resins are most commonly used epoxies.

Diglycidyl Ether of Bisphenol-A (DGEBA):

Diglycidyl ether of bisphenol-A (DGEBA) is a typical commercial epoxy resin and is

synthesised by reacting bisphenol-A with epichlorohydrin in presence of a basic catalyst.

structure of DGEBA

The properties of the DGEBA resins depend on the value of n, which is the number of
repeating units commonly known as degree of polymerisation The number of repeating units
depend on the stoichiometry of synthesis reaction. Typically, n ranges from 0 to 25 in many
commercial products.

Novolac Epoxy Resins:

Novolac epoxy resins are glycidyl ethers of phenolic novolac resins. Phenols are reacted in
excess, with formaldehyde in presence of acidic catalyst to produce phenolic novolac resin.
Novolac epoxy resins are synthesised by reacting phenolic novolac resin with
epichlorohydrin in presence of sodium hydroxide as a catalyst.

Structure of novolac epoxy resin

Novolac epoxy resins generally contain multiple epoxide groups. The number of epoxide
groups per molecule depends upon the number of phenolic hydroxyl groups in the starting
phenolic novolac resin, the extent to which they reacted and the degree of low molecular
species being polymerised during synthesis. The multiple epoxide groups allow these resins
to achieve high cross-link density resulting in excellent temperature, chemical and solvent
resistance. Novolac epoxy resins are widely used to formulate the moulding compounds for
microelectronics packaging because of their superior performance at elevated temperature,
excellent mouldability, and mechanical properties, superior electrical properties, and heat
and humidity resistance.

Curing of Epoxy Resins

The curing process is a chemical reaction in which the epoxide groups in epoxy resin reacts
with a curing agent (hardener) to form a highly crosslinked, three-dimensional network. In
order to convert epoxy resins into a hard, infusible, and rigid material, it is necessary to cure
the resin with hardener. Epoxy resins cure quickly and easily at practically any temperature
from 5-150oC depending on the choice of curing agent.

Curing Agents (Hardeners)

A wide variety of curing agent for epoxy resins is available depending on the process and
properties required. The commonly used curing agents for epoxies include amines,
polyamides, phenolic resins, anhydrides, isocyanates and polymercaptans. The cure kinetics
and the Tg of cured system are dependent on the molecular structure of the hardener. The
choice of resin and hardeners depends on the application, the process selected, and the
properties desired. The stoichiometry of the epoxy-hardener system also affects the
properties of the cured material. Employing different types and amounts of hardener which,
tend to control cross-link density vary the structure.

The amine and phenolic resin based curing agents, described below, are widely used for
curing of epoxy resins.

Amine based curing agents:

Amines are the most commonly used curing agents for epoxy cure. Primary
and secondary amines are highly reactive with epoxy. Tertiary amines are
generally used as catalysts, commonly known as accelerators for cure
reactions. Use of excessive amount of catalyst achieves faster curing, but
usually at the expense of working life, and thermal stability. The catalytic
activity of the catalysts affects the physical properties of the final cured
polymer.

Phenolic novolac resins:

Epoxy resins when cured with phenolic hardener, gives excellent adhesion,
strength, chemical and flame resistance. Phenolic novolac-cured epoxy
systems are mainly used for encapsulation because of their low water
absorption, excellent heat and electrical resistance. An accelerator is necessary
for the complete cure to occur. Figure 2.4 shows cure reaction of epoxy resin
with phenolic hardener.

Rubber Toughening of Epoxy Resins

The usefulness of epoxy resins in many engineering applications is often limited by their
brittle nature and poor thermal conductivity. The term toughness is a measure of material's
resistance to failure i.e. the total amount of energy required to cause failure.

There are several approaches to enhance the toughness of epoxy resins which includes: (i)
chemical modification of the epoxy backbone to make it more flexible structure, (ii)
increasing the molecular weight of epoxy, (iii) lowering the cross-link density of matrix, (iv)
incorporation of dispersed toughener phase in the cured polymer matrix, and (v)
incorporation of inorganic fillers into the neat resin.

Amongst these approaches, toughening via dispersed toughener (flexibiliser) phase has been
shown to be most effective. The flexibilisers can be reactive or non-reactive rubber.

Toughening Agents
Various types of thermoplastic polymers as well as reactive rubbers are employed to
enhance toughness of epoxy resin. Thermoplastic polymers, such as polyetherimide,
polysulphone, polyethersulphone, and polycarbonate have been studied to modify epoxy
resins. These studies show significant improvement in the toughness of epoxy resins.

The reactive rubbers used for toughening epoxy resins include, liquid acrylonitrile-
butadiene copolymers with various terminal groups, polysiloxanes, polyepichlorohydrin,
and polyurethanes.

Although liquid acrylonitrile-butadiene copolymers with carboxyl- (CTBN) and amine-

(ATBN) terminated groups have been widely used for epoxy toughening, the relatively high
glass transition temperature of the copolymer limits their low-temperature applications. In
addition, these copolymers also increase the CTE value of the moulding compound. Also
the presence of unsaturated structure of butadiene system is prone to thermal instability and
thus unsuitable for long term use at higher temperatures.

Polysiloxanes have excellent thermal stability, moisture resistance, good electrical

properties, low stress and lower Tg values. However polysiloxanes are not compatible with
epoxy resins. Addition of compatibilisers such as, methylphenylsiloxane enhances the
compatibility but at the same time raises the Tg of polysiloxane modifier restricting its low
temperature applications.
A BASIC GUIDE ON DIFFERENT TYPES OF
EPOXIES
There are many different uses for epoxy coatings, and nearly as many choices for
the type of epoxy that will best do the job. Included here is a quick guide that
differentiates between some common forms of epoxy and when to use each. If you
have additional questions, come see us at Maxwell Supply in Tulsa.

Polyamide Epoxies
The molecular make-up of these epoxies helps to reduce the vapor pressure of the
resin. Because of this, polyamide epoxies are great for use in primers, which can
create improved flexibility, adhesion, wetting characteristics, and corrosion
resistance. These epoxies stand up well to moisture, weather and alkali, but break
down when exposed to chalk and acid.

Polyamine Epoxies
Within the broader category of polyamine epoxies are several smaller sub-categories
that offer different chemical resistance properties to epoxy coatings. All polyamine
epoxies share similar abilities to improve film hardness, abrasion resistance, and
chemical resistance. They’re often utilized when corrosion from microbiological
factors is a concern. When compared to polyamides, these epoxies offer more
toughness, more brittle and more chemically resistant, but not as flexible or resistant
to most types of corrosion.

Phenolic Epoxies
These epoxies aren’t utilized for many applications. You’d likely only need them to
create a coating chemically resistant containers like cans and drums. They’re
created by heat-curing epoxy resin with a phenolic resin.
Novolac Epoxies
Acid is used as a catalyst to create a reaction between phenol and formaldehyde.
The resulting product of this reaction is used to create the base for novolac epoxies.
These are used when high resistance to both chemicals and heat is required. While
they typically fully cure at high heats, specific formulas can be used to allow novolac
epoxies to cure at room temperature.

Before applying epoxies on your next project, come see us at Maxwell Supply in
Tulsa. We’ll help point you in the right direction.
The term epoxy has been widely adapted for many uses beyond its original use
for fiber-reinforced polymer composites. Today, epoxy adhesives are sold in
local hardware stores, and epoxy resin is used as the binder in countertops or
coatings for floors. The myriad uses for epoxy continue to expand, and
variants of epoxies are constantly being developed to fit the industries and
products they are used in. Here are some things that epoxy resin is used in:

 General-purpose adhesives
 Binder in cement and mortars
 Rigid foams
 Nonskid coatings
 Solidifying sandy surfaces in oil drilling
 Industrial coatings
 Potting and encapsulating media
 Fiber-reinforced plastics

In the realm of fiber-reinforced polymers, or plastics, epoxy is used as the

resin matrix to efficiently hold the fiber in place. It is compatible with all
common reinforcing fibers including fiberglass, carbon fiber, aramid, and
basalt.

Common Products for Fiber Reinforced Epoxy

Products commonly manufactured with epoxy, listed by manufacturing
process, are:

Filament Winding

 Pressure vessels
 Pipes
 Rocket housings
 Recreational equipment

Pultrusion

 Insulator rods
 Arrow shafts

Compression Molding

 Aircraft parts
 Skis and snowboards
 Skateboards
  Circuit boards

Prepreg and autoclave

 Aerospace components
 Bicycle frames
 Hockey sticks

Vacuum Infusion

 Boats
 Wind turbine blades

The same epoxy resin likely can't be used for each of these processes. Epoxies
are fine-tuned for the desired application and manufacturing process. For
example, protrusion and compression molding epoxy resins are heat-
activated, while an infusion resin might be an ambient cure and have a lower
viscosity.

When compared to other traditional thermoset or thermoplastic resins, epoxy

resins have distinct advantages, including:

 Low shrinkage during cure

 Excellent moisture resistance
 Excellent chemical resistance
 Good electrical properties
 Increased mechanical and fatigue strength
 Impact resistant
 No VOCs (volatile organic compounds)
 Long shelf life

Chemistry
Epoxies are thermosetting polymer resins where the resin molecule contains
one or more epoxide groups. The chemistry can be adjusted to perfect the
molecular weight or viscosity as required by the end-use. There are two
primary types of epoxies: glycidyl epoxy and non-glycidyl. Glycidyl epoxy
resins can be further defined as either glycidyl-amine, glycidyl ester, or
glycidyl ether. Non-glycidyl epoxy resins are either aliphatic or cyclo-aliphatic
resins.

One of the most common glycidyl epoxy resins is created using Bisphenol A
(BPA) and is synthesized in a reaction with epichlorohydrin. The other
frequently used type of epoxy is known as novolac based epoxy resin.

Epoxy resins are cured with the addition of a curing agent, commonly called a
hardener. Perhaps the most common type of curing agent is amine-based.
Unlike in polyester or vinyl ester resins, where the resin is catalyzed with a
small (1-3%) addition of a catalyst, epoxy resins usually require the addition of
the curing agent at a much higher ratio of resin to hardener, often 1:1 or 2:1.
Epoxy resin can be "toughened" with the addition of thermoplastic polymers.

Prepregs
Epoxy resins can be altered and impregnated into the fiber and be in what is
called a B-stage. This is how prepregs are created.

With epoxy prepregs, the resin is tacky, but not cured. This allows layers of
prepreg materials to be cut, stacked, and placed in a mold. Then, with the
addition of heat and pressure, the prepreg can be consolidated and cured.
Epoxy prepregs and the epoxy B-stage film must be kept at a low temperature
to prevent premature curing, which is why companies using prepregs must
invest in refrigeration or freezer units to keep the material cool.
Epoxies in Building and
Construction
Epoxy resins are used in the manufacture of adhesives, plastics, paints, coatings,
primers and sealers, flooring and other products and materials that are used in building
and construction applications. Epoxies are thermoset plastics made by the reaction of
two or more industrial chemical compounds.

Epoxy resins are used in a wide array of consumer and industrial applications because
of their toughness, strong adhesion, chemical resistance and other specialized
properties.

How Are Epoxies Used in Residential, Commercial,

and Industrial Construction?
 Most adhesives known as “structural “or “engineering” adhesives are epoxies.
These high-performance adhesives are used to make laminated woods for decks,
walls, roofs and other building applications, as well as in other products that
require strong bonds to a variety of substrates, for example to concrete or wood.
Epoxies can stick to wood, metal, glass, stone and some plastics, and are more
heat- and chemical-resistant than most glues.

 Epoxy resins also help to provide durable, high-gloss outdoor coatings, as well as
sealers for concrete floors and other heavy-duty protective coatings used in
industrial settings.

 Epoxy resins are used

for high performance and decorative flooring, such as terrazzo flooring, chip flooring,
and colored aggregate flooring. These types of flooring are available in a wide
range of colors and decorative patterns that are created by adding contrasting
vinyl chips or colored quartz aggregate to the top epoxy layer. Epoxy flooring can
also be augmented with paint chips, or other additives like polymer grit, that
provide an anti-skid texture to a floor.

 New technologies are enabling development of sustainable architectural surfaces

and countertops made from a composite blend of epoxies, recycled glass, and other
commonly discarded post-consumer materials. Using this technology, surfaces
and countertops can be composed of up to 90 percent recycled materials and help
builders attain LEED credits for their construction products.

 Water-based epoxy paints dry quickly, providing a tough, protective coating. Their
low volatility and clean-up with water make them useful for factory cast iron, cast
steel, and cast aluminum applications, with far less risk from exposure or
flammability than alternatives based on organic solvents.