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
o
any temperature from 5-150 C 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.
