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Epoxy & Phenolic Resins

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

Specific gravity 1.15-1.35


1.15-
Tensile strength, MPa 40--140
40
Tensile modulus, GPa 3-4.5
Compression strength, MPa 10--200
10
Bending strength, MPa 60--180
60
Poissons ratio 0.35--0.4
0.35
CTE, 10-6 C ~60
Cure shrinkage, % 1-5
Chemical Resistance
Ether linkages present in the cured epoxy resin can
resist most inorganic and organic acids, and inorganic
bases.
The epoxy resins cured with amines can resist most
inorganic acids and bases, but poor in resisting
organic acids.
Ester linkages can resist organic acids and the
resistance is poor in inorganic acids and bases.
Substituents present in epoxy resin or curing agents
can modify the above chemical resistance.
As in thermal resistance, the epoxy resins cured with
aromatic compounds can give better chemical
resistance than those cured with aliphatic compounds.
Applications of Epoxy Resins
Casting
Potting
Encapsulation
Tooling
Foam
Molding compound
Surface coatings
Adhesive laminates
Reinforced composites
Reinforced Products
Several types of epoxy resins have been developed for
fabricating fiber reinforced products
Fibers of glass, carbon and Kevlar are used either in the
form of strands or woven fabrics
In India, glass fiber and DGEBA based resin products
are widely used
For aerospace and other structural applications, carbon
or Kevlar fiber reinforced products are fabricated
Since epoxy resins have better chemical resistance,
storage tanks and room temperature operated chemical
reactors are fabricated with glass fiber reinforcement.
Reinforced Products
For high temperature applications phenolic based epoxy
novolac resins are used
When compared to other resin systems like polyester,
phenolics, etc., epoxy resins have better interlaminar
strength and chemical resistance
For filament winding applications, epoxy resins are
preferred
In electronic industry, especially for printed circuit
boards, epoxy resins dominate the market
For aerospace applications several epoxy resin systems
were developed world wide.
These are available mostly in the form of prepregs, adhesive
films, etc.
Composites in Military Aircraft
Aircraft Component Material Wt.
Saving
(%)
F-14 Skin on the horizontal stabiliser box B-Epoxy 19

F-11 Underwing fairings C-Epoxy -

F-15 Fin, stabiliser skins B-Epoxy 25

F-16 Skins on vertical fin box, Fin leading C-Epoxy 23


edge
F/A-18 Wing skins, Horizontal & vertical tail C-Epoxy 35
boxes, wing & tail control surfaces
AV-8B Wing skins & sub-structures, forward C-Epoxy 25
fuselage, horizontal stabiliser, ailerons
PRINTED CIRCUIT BOARDS
Epoxy + Glass
Halogen-free Fire retardants
Phenolic Resins
Thermosetting resins produced by the reaction
of phenol or substituted phenol with an
aldehyde
Advantages of phenolic resins
Superior fire resistance
Excellent high-temperature performance
Long term durability
Resistance to hydrocarbon and chlorinated solvents
Available for various fabrication processes
OH OH

CH2OH CH2OH
HCHO

CH2OH
Phenol Formaldehyde Hydroxy methyl phenol

OH OH OH

CH2OH CH2OH CH2OH CH2OH

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

Methacrylate vinyl ester 20 40


with 150 phr aluminum
trihydrate
Phenolic resins for composites
Manufacturing Resin type (solvent) Viscosity at Catalyst Cure
process 25 C (cP
(cP)) temp. C
Filament winding PF (water) 500--2000
500 Acid 65--95
65

PRF (water/alcohol) 500--2000


500 Formaldehyde 25--65
25

Hand lay-
lay-up PF (water) 500--2000
500 Acid 25--80
25

Pultrusion PF (water) 2000--10000


2000 Base 165--245
165

PRF (water/alcohol) 2000--10000


2000 Formaldehyde 165--245
165

Sheet moulding & PF (water) 1000--2000


1000 Base 150--175
150
Bulk moulding
Solution PF (water/alcohol) 300--1000
300 Base--neutral
Base 120--175
120

Hot melt PF (water) 50000--100000


50000 Base--neutral
Base 120--175
120

Honeycomb PF (water/alcohol) 500--1000


500 Base--neutral
Base 120--175
120

PRF Phenol resorcinol formaldehyde


Phenolic Prepregs
Impregnation with resin having viscosity
from 300-1000 cP
The reinforcement is passed through a
resin containing bath and then into a
heated tower
Solvent & water removed, cured to B-
stage
Prepregs are cured under heat (120-
175 C) and pressure (345-3450 kPa)
Phenolic Prepregs
Conventional application of these
prepregs are in ballistic components
Used in helmets, land vehicles & military
aircraft
Carbon-carbon composites can be
prepared
Current applications include rocket motors,
aerospace engine components, aircraft
brakes, racing car brakes
Phenolic Honeycomb
Phenolic prepregs are used as face
sheets on Nomex honeycomb to construct
sandwich panels
Panels have high strength-to-weight ratio
Panels are used in cargo liners, walls,
galleys, ceilings, floors
Used in Californias Bay Area Rapid
Transit subway cars
Phenolic Pultrusion
Phenolic resole resins are used to manufacture
pultruded composites
Fiber volume fraction is higher
Mechanical properties are comparable
Phenolic gratings are manufactured for offshore oil
platforms
Can withstand direct flame contact without major structural
damage
It has low thermal conductivity and strength of steel grating
at a lighter weight
Walk ways, ducting for tunnels/mass transit,
automotive, aircraft and marine structures are other
potential applications
Phenolic Filament Winding
Filament winding of phenolics has been well established
Phenol-formaldehyde with an acid catalyst and resorcinol
resins with paraformaldehyde catalysts are currently used
Processing requirements
Resin viscosity of 500-2000 cP
Pot life must be greater than 30 min
Gel time at 80 C must be 90-150 s
Cure temperature must be 65-95 C
Currently being used for ventilation ducting in mining &
tunnelling
Offshore oil platform water piping systems
For protection of damaged utility and transmission poles
Repaired phenolic wrapped poles perform better than new
ones
Phenolic Sheet Molding Compounds
Resin requirements are
High solids (75%)
Low viscosity (1500 cP)
Minimal levels of monomers and solvents
Quantum Composites has commercialised phenolic
SMC products for specific aircraft and military
applications
Kaiser Compositek is producing air scoops in inner fan
duct for aircraft engine structures
A chopped carbon fiber/phenolic SMC product was
used to manufacture the base and cover of the IBM
Think pad
Better thermal resistance & low shrinkage value
Phenolics for Hand Lay-up
Resin requirements
Viscosity 500-2000 cP
Pot life 10-60 min
Cure temperature 60-80 C
Waterborne phenolic resole resins with sulfonic
acid and phosphate ester catalysts are used
Phenolic laminates are more porous
This shortcoming is addressed using phenolic
based surface coat
Phenolics for Hand Lay-up
Hand lay-up phenolic composites have been
used in mass transit in Europe since 1988
Most of the underground railways in UK, France
and Scandinavian countries switched to
phenolic composites
Large panels (1.8 by 5.4 m) for constructing
homes are manufactured
Phenolic panels eliminate the possibility of
termite damage and provide better fire safety
and easier construction
Mass Transit
Underground / Metro:
London Underground- Northern & Jubilee lines
Madrid Underground
Bilbao, Rome, Rotterdam & Dublin Metros
Overground
Channel Tunnel - Eurostar
Gardemoen Express, Norway
High Speed Talgo, Spain
Hong Kong Shuttle,
Heathrow Express,
Scottish Regional Railways
West Coast & Cross Country route, UK
Off-shore
Fire and blast resistant panel systems, modules
and temporary safe refuges
Syntactic foam insulation and protective
coatings
Low pressure and pressure rated pipe systems.
Pultruded profiles and grid flooring.
Pipes, ducts and man-safe escape corridors.
Pre-insulated process pipe.
Steel faced, phenolic foam insulated panels.
Filament wound beams
Marine
Public rooms on cruise ships.
Phenolic panelling will not contribute to the fire load
and gives off almost no smoke or fumes on fire.
Lining panels and window masks complying with
the High Speed Craft Code of Practice on
Scandinavian, Spanish and British built high-
speed fast ferries.
Lining panels and overhead lockers in
commercial vessels approved by US Coastguard.
The exceptional fire performance of phenolics
made them a natural choice for confined spaces
with limited exit
Construction
Piping for Gas and Liquid Transport
Phenolic piping has been used for many years for methane drainage in mines.
The lightweight phenolic product is easier to fit than traditional steel pipe and
suffers less corrosion in this damp and aggressive environment.
Cladding for New Build and Building Refurbishment
Phenolic composite cladding and phenolic composite faced insulated panels.
Coloured composite cladding is available in a wide range of colours and
textures.
Suited to schools, hospitals, transport termini and municipal housing projects.
Phenolic Composites as Tunnel Linings
Phenolic linings have already been installed in the Clyde and Glasgow tunnels.
Air Conditioning and Ducting
Cellobond J2027L is approved by Factory Mutual for the manufacture of
ducting.
Cable Trays
Because of its exceptional fire and flame resistance Phenolic pultruded cable
trays can restrict the spread of fire that starts in the cable system, and in
addition protect cables from external fire sources.
DURAGRID Phenolic Grating is accepted for use in locations and
applications allowed in the US Coast Guard Policy File Memorandum
2.98 for fire retardant FRP (GRP) grating meeting structural fire integrity.
Manufactured by Strongwell
Water Pump Housing
The housing of the waterpump is made
from Vyncolit X7010, an engineering
moldable phenolic composite offering
high mechanical strength and creep
resistance.
It is able to withstand the severe side load
caused by the belt tension and the
comprehensive load generated by bolting
directly (without metal inserts!) to the
engine block.
Conclusion
Recent years, technology improvement in
phenolic resins has taken place
Low emission resins, latent acids for desired
pot life/cure temperature and modifiers for
higher strength are available
Application of phenolic composites
continues to increase where fire safety is
a primary requirement
Comparison of thermosetting laminating resins
Property Epoxy Polyester Phenolic
Cure mechanism Polymerisation of resin Catalytic Condensation
plus hardener copolymerization of polymerization of resin
resin and vinyl aided by catalysts
monomer
Typical temperature for 25-150 25-100 25-170
cure, C
Typical cure time, min 60-180 10-60 60-180
Shelf stability of liquid Excellent Fair Poor
resin
Shrinkage of resin Low High High
system during cure
Adhesion to metal Excellent Fair Fair
substrates
Adhesion to wood Good Good Fair
Adhesion to concrete Excellent Fair Poor
Electrical properties of Excellent Excellent Good (poor arc
cured laminate resistance)
Physical properties of Excellent Excellent Excellent (better heat
cured laminate resistance)
Cost Moderate Low low
References
1. Mallick, P.K. (2008) Fiber-reinforced
Composites, 3rd Edition, CRC Press,
Boca Raton.
2. Balasubramanian, M. (2013) Composite
Materials and Processing, CRC Press,
Boca Raton.
3. ASM Handbook. 2001. Vol. 21.
Composites, Materials Park, OH, USA:
ASM International.
mbala@iitm.ac.in