Documente Academic
Documente Profesional
Documente Cultură
M. Balasubramanian
Dept. of Metallurgical & Materials Engineering
Indian Institute of Technology
Chennai - 600 036
Epoxy Resins
Epoxy group consists of a ring in
which an oxygen atom bonded with
two carbon atoms
Ring can be formed by any number of
carbon atoms but they should be
closed by an oxygen atom
Reactivity of the ring depends on the
number of carbon atoms present
Reactivity decreased with increased
number of carbon atoms in the ring
Reactivity is maximum when the rings
are three membered
a) A molecule of diglycidyl ether of bisphenol A
b) A molecule of diethylene triamine (DETA) curing agent
Advantages
Wide variety of properties, since a large
number of starting materials, curing
agents and modifiers are available
Absence of volatile matters during cure
Low shrinkage during cure
Excellent resistance to chemicals and
solvents
Excellent adhesion to a wide variety of
fillers, fibers and other substrates
Disadvantages
Relatively high cost
Long cure time
Aliphatic Epoxy Resins
Resins contain aliphatic chains, sometimes
aliphatic cyclic structures in between epoxy
groups.
Products are more flexible due to the long
aliphatic chain present between two epoxy
groups.
Not commercially important due to their flexible
nature.
These resins are used as diluents and modifiers
for aromatic high viscous epoxy resins.
Aromatic Epoxy Resins
The first commercial epoxy resins were the
reaction products of epichlorohydrin and
bisphenol A.
This reaction produces the diglycidyl ethers of
bisphenol A (DGEBA)
Most widely used among the commercial epoxy
resins.
Resins with higher molecular weight are used
as adhesives and surface coatings.
Filament winding tubes and laminates can be
made from the lower molecular weight and low
viscous resins.
Epoxy Resin Chemistry
Novolac Resins
Novolac phenolics can be epoxidised by
reacting with epichlorohydrin.
Better retention of properties at high
temperatures.
Also commercially successful, like
bisphenol A resins.
Tetraglycidyl Diamine Diphenyl
Methane
Another important resin is tetraglycidyl
diamine diphenyl methane (TGDDM).
On curing with selected curing agents can
produce products with the retention of
properties at high temperatures.
These resins are developed for making
high strength fiber prepregs, which are
required for aerospace applications.
Epoxy Vinyl Ester Resins
Basic Characteristics of Liquid Epoxy Resins
Low viscosity liquids, which readily convert to
cross-linked products by adding proper curing
agents
Low-viscosity of resin allows good wetting
Can be cured at any temperature between 5 to
150 C depending on the curing agent selected
Low shrinkage during cure
Can adhere to many surfaces and therefore are
used in many adhesive applications
Give products with good mechanical properties
when cured properly with suitable curing agents
Basic Characteristics of Liquid Epoxy Resins
Epoxy resins after cure are well known for their
excellent electrical properties.
The products made from these resins are used in
printed circuit boards.
These resins are also used for making insulators.
Proper selection of curing agent can give good
chemical resistance to the cured epoxy resin.
Most epoxy resins possess extremely high
resistance to alkalis and good to excellent
resistance to acids.
The basic properties of these resins can be modified
many ways by blending different resins, curing agents
and by the use of modifiers.
Solid Resins
Resins mainly used in coatings.
The higher molecular weight resins are
prepared with conventional drying oils.
The epoxy resin back bone imparts toughness,
scratch resistance and chemical resistance.
These coatings are used for marine
applications, corrosion prevention and for
decorative purposes.
Viscosity
Viscosity of the resins is the important parameter in processing.
When epoxy resins are made from aliphatic linear chains, these are
low viscous liquids.
The viscosity is increasing with chain length.
Aromatic based epoxy resins with three or more epoxy groups per
molecule are semi-solids or solids at room temperature.
Blending of these resins with aliphatic based diepoxy resins results in
viscous liquids at room temperature.
In general, substitution of aromatic rings decreases the viscosity,
when compared to unsubstituted aromatic epoxy resins.
The viscosity of the resin increases in proportion to the molecular
weight of the species present.
Viscosity of resin decreases with increase in temperature in the
absence of any curing reaction.
Curing Agents for Epoxy Resins
Many curing agents are commercially
available.
Broadly classified into three categories
according to their reactive functional
groups.
Amine curing agents
Acid anhydride curing agents
Acid curing agents
Aliphatic Amines
Primary aliphatic amines are the first curing agents to
gain acceptance in epoxy industry
These amines cure glycidyl ethers at room temperature
The end product properties depend on the linear chain
length of the curing agent
With increasing chain length, the flexibility in the end product is
increased
Ethylene diamine and 1,3 diaminopropane give brittle
products with DGEBA
Diethylene triamine (DETA), triethylene tetramine
(TETA), Tetra ethylene pentamine (TEPA), and
Dicyandiamide (DICY) are the commercially used curing
agents
Aliphatic Amine Hardeners
Dicyandiamide (DICY)
Solid at room temperature and reacts with
epoxy above 120 C
Suitable for increasing the life of resin
mixture at room temperature and for
curing at high temperatures
This curing agent is mainly used in
prepreg formulation for aerospace
applications
Aromatic Amine Curing Agents
Overtake all amine type curing agents
Some of the more commonly used aromatic
diamines
m-phenylene diamine (MPDA)
4,4'-methylene dianiline (MDA)
diamine diphenyl sulfone (DDS)
These amines can be used as sole curing agents
Generally, a mixture of these amines are employed
in commercial practice
These amines react very slowly at room
temperature and need heating for fast and
complete cure
Aromatic Amine Curing Agents
Products cured with aromatic amines
have good chemical resistance to alkalies
and solvents
Superior to aliphatic amine cured products
in mechanical properties
Solids at room temperature
Dissolved in resin at high temperature
Medium temperature cure
Aromatic amines
Curing of Epoxy Resins
Epoxy resins are available in a wide range of
molecular structures, suitable for curing with a
large variety of curing agents to make products
with the required properties.
During the curing of these resins, physical and
chemical changes are taking place.
Physical changes are occurring due to chemical
reaction
Viscosity
Temperature due to exothermic nature of curing
Gel effect
Reaction of epoxy group with DETA molecule
Network structure of epoxy
Exotherm
In the case of curing of DGEBA with aliphatic
amines, the exotherm occurs before gelation
Initially all the primary amine hydrogens are
reacted with epoxy groups to form long chains
The primary amine groups produce secondary
amine groups on reaction with epoxy group
Secondary amine groups can react with epoxy
at high temperature only
Secondary amine reaction brings cross-linking
between chains at slow rate and cause gelation
Viscosity During Cure
Initially the viscosity of resin decreases
The viscosity reaches to a minimum level at the
peak exotherm, and then it increases rapidly
with cross-linking of chains
After glassy state practically no reaction takes
place
Post-curing at higher temperature has to be
done
Post-curing increases the heat distortion
temperature of the cured product
Gelation
When all the chains have at least one cross-link,
the gelation occurs
The chains cannot be mobile
All the processing operations should be
completed before the onset of gelation
It is also necessary to remove voids before the
onset of gelation
Generally, a dwell is employed at minimum viscosity
level to allow the bubbles present in the system to
come to the surface
Properties of the Cured Epoxy Resins
The physical and chemical resistance of cured epoxy
resins depends on the extent of cure.
It is very difficult to determine the extent of cure and it is
also not possible to achieve 100% cure due to solid
phase reactions at the end of the cure.
Brittle product is the result of high cross-link density.
Cross-link density is defined as the number of cross-links per
unit chain length.
The distance between cross-links is dictated by the
structure of epoxy resin and curing agent.
Thus, it is possible to modify the properties of cured
epoxy resins by selecting proper resin-curing agent
system.
Typical Properties of Cast Epoxy Resin
CH2OH CH2OH
HCHO
CH2OH
Phenol Formaldehyde Hydroxy methyl phenol
OH OH OH
OH OH
CH2OH CH2OH
CH2OCH2 CH2 CH2
CH2 CH2
nH2O
O
CH2
OH
CH2 CH2 CH2
CH2
CH2
Phenol formaldehyde
Resin Chemistry
Catalyst and phenol to formaldehyde (P/F) ratio
determine the type of resin
Acid catalyst & P/F molar ratio greater than 1
are Novolacs
Novolac powders with hexamethylene tetramine are
commonly used in molding compounds
Alkaline catalyst & P/F molar ratio less than 1
are Resoles
Resole resins are commonly used in fiber reinforced
composites
Phenolic Composites
Low flame spread
Low smoke generations
Low smoke toxicity
Excellent chemical resistance
Relatively inexpensive
Meet the Federal Aviation fire specifications
Walls, ceilings and floors of aircraft interiors
Non-aerospace applications include mass
transit, construction, marine, mine ducting and
offshore structures
Flame spread index and smoke density
comparison of thermosetting resins
(ASTM E 84 tunnel test)
Resin Flame spread Smoke
index density
Phenolic 10 10
Halogenated polyester 15 600-800
Halogenated vinyl ester 45 600-800
Hand lay-
lay-up PF (water) 500--2000
500 Acid 25--80
25