EPOXY RESINS
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INTRODUCTION
➢ Epoxy resin are characterized by more than one 1, 2- epoxy group per
molecule.
➢ Three-membered epoxy ring is highly reactive to many substance,
particularly by with proton donor ( eg: amine, anhydride)
➢ Such reactions allow chain extension and/or cross linking to occur
without the elimination of small molecules such as water
➢ Depending upon the non epoxy part of molecule there are wide range
of epoxy resins.
➢ Non epoxy part may be aliphatic, aromatic or it may be non-hydro
carbon and possibly polar.
➢ Commercially important epoxy resin is prepared by the reaction of
biphenol – A with epichlorohydrin
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Historical Development
➢ Commercial interest in epoxy resins was frist made apparent by the
publication of German patent 676117 by I G Farben in 1939 which
describe liquid polyepoxide.
➢ In 1943 P.Castan filed US patent covering the curing of the resins with
dibasic acids
➢ About half of epoxide resin production is used for surface coating
applications, with the rest is used for electronic applications
(particularly for printed circuit boards and encapsulation), the building
sector and miscellaneous uses.
➢ Properties of the cross-linked resins depend very greatly on the curing
system used and on the type of resin.
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MONOMERS
The monomers for general purpose epoxy resins are bis-phenol A and
epichlorohydrin.
Bis- Phenol A
Bis- phenol A is prepared by reaction of acetone and phenol.
Phenol
Acetone
Bis – Phenol A
Bis- phenol A with melting point 153o C is used for most of the
applications.
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Epichlorohydrin
➢ Starting material for the preparation of Epichlorohydrin is propylene
and chlorine. The material is a colourless liquid.
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MANUFACTURE
Manufacture of Bis-phenol A Resins
➢ Largest product epoxy resin called Digycidyl ether of bisphenol-A
(DGEBA) is manufactured by reacting bisphenol-A with epichlorohydrin
➢ Typical laboratory prepation 1 mole (228g) of bis-phenol A is dissolved in
4 moles (370g) of epichlorohydrin and the mixture heated to 105 –110o C
under an inert atmosphere.
➢ Solution is continuously stirred for 16 hrs. While 80g (2moles) of sodium
hydroxide in the form of 30% aqueous solution is added drop wise.
➢ Resulting organic layer is separated and fractionally distilled
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➢ General formula for glycidyl ether resin is represented by the structure
With n =0, the product reduces to diglycide ether and the molecular
weight is 340; with n=10, the molecular weight is about 3000.
commercial diglycide ethers mostly have a low degree of
polymersiation as they hardly ever have a molecular weight greater
than 4000.
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➢ Epoxide resins of diglycide ether type are characterized by six
parameters
➢ Resin viscosity (of liquid resin)
➢ Epoxide equivalent
➢ Hydrooxyl equivalent
➢ Average molecular weight and molecular weight distribution
➢ Melting point (of solid resin)
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Epoxide Equivalent
➢ This is the weight of the resin (in gram) containing 1 gram chemical
equivalent epoxy
➢ Determined by reacting a known quantity of resin with hydrochloric
acid and measuring unconsumed acid
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Hydroxyl Equivalent
Hydroxyl equivalent is the weight of resin containing one equivalent
weight of hydroxyl groups. It may be determined by many techniques but
normally by reacting the resin with acetyl chloride
Miscellaneous Epoxy Resins
Other glycidyl ether resins
Non – glycidyl ether resins
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Miscellaneous Glycidyl Ether Resins
Bis-phenol F- Mixture of three isomers
(a) (b) (c)
Hydrogenated bis-phenol A long chain bis-phenol
glycerol from cashew nutshell oil
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Novalak
➢ Novalak resins have also been epoxidised through their phenolic
hydroxy group
➢ This molecule has a functionality of four
➢ When cured with high temperature hardeners such as methyl “nadic”
anhydride both thermal degradation stability and heat deflection
temperatures are considerably improved
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Resin for High Heat Distortion Temperature
➢ To produce resins of high heat distortion temperature it is important to
have a high density of cross-linking.
➢ This is achieved by using anhydride hardeners such as pyromellitic
dianhydride and with the cyclic aliphatic resins.
➢ Attempts have been made to use glucidyl ether resins of higher
functionality such as the tetra functional structure
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Flame-Resistant Resins
Halogenated materials have been used. A typical example is
diglycidyl ether of tetrachlorobisphenol - A
Non-glycidyl ether epoxy resins
There are two types of Non-glycidyl ether epoxy resins
➢ Those which contain a ring structure as well as epoxide group in the
molecule – the cyclic aliphatic resins
➢ Those which have an essentially linear structure on to which are
attached epoxide groups – the aceylic aliphatic epoxide resins.
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Cyclic aliphatic resins
Compared with the diglycidyl ether resins, cyclo aliphatic resins
are characterized by
➢ Light colour
➢ Low viscosity
➢ Low rate of reaction with amine curing agents
➢ High degree of cross-linking
➢ Basically brittle resins can be made flexible by use of long-
chain aliphatic curing agents which lead to less cross-linking
➢ High dimensional stability when heated
➢ High tracking resistance and arc resistance
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Acyclic aliphatic resins
➢ Cured resins have heat distortion temperatures substantially
higher than the conventional amine-cured diglycidyl ether resins.
➢ A casting made from an epoxidised polybutadiene hardened
with maleic anhydride gave a heat distortion temperature 250o C
Nitrogen containing epoxy resin
Manufactured by glycidylization of cyanuric acid using epichlorohydrin
➢ Combination of triglycidylisocyanurate with oil-free polyesters
containing carboxyl groups leads to powder coating systems which
give films resistance to external weathering.
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GENERAL PROPERTIES
Variety of Form: Epoxy resin systems that is resin,hardeners, and
modifiers are available permitting the selection of almost any form
desired for any application, ranging from extremely low viscosities to
high melting solids.
Curing Latitude: Depending upon the selection of hardener, systems
can cure rapidly or slowly at almost any temperature from 5 to 180ºC.
Low Shrinkage: Unlike phenolic and polyester resin behaviour, the
epoxides exhibit very low shrinkage during cure.
Toughness: Cured epoxy resins are tough materials due to distance
between cross-linking points and the presence of integral aliphatic
chains. They are approximately seven times tougher than cured
phenolic resins
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Adhesion:
➢ Chemical nature of epoxies viz., the hydroxyl and ether
groups present causes outstanding adhesion to a variety
of materials.
➢ Being cross-linked, the resin will not dissolve without
decomposition but will be swollen by liquids of similar
solubility parameter to the cured resin .
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ADDITIVES
1. FILLERS
2. DILUENTS
3. FLEXIBILIZERS
4. COLORENTS AND DYES
5. RHEOLOGICAL ADDITIVES
6. THICKINING AGENTS
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Fillers
➢ Reinforcing fibers such as glass graphite and polyaramide
improve mechanical properties.
➢ Non- reinforcing fillers such as alumina powder is widely used
for thermal conductivity and electrical conductive applications.
➢ Mica is used for electrical insulation applications.
➢ Inorganic fillers such as talc, calcium carbonate and silica are
used in epoxide systems for cost reduction with some strength
enhancement.
➢ Carbon and graphite powders are used to have lubricity.
➢ Carium sulphate is used as the density controller.
➢ Use of synthetic sodium aluminium silicate in epoxy coatings
provides improved opacity over titanium dioxide
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Diluents
➢ Diluents are free-flowing liquids incorporated to reduce the
resin viscosity and simplify handling.
➢ Reactive diluents such as phenyl glycidly ether, butyl glycidyl
ether and octylene oxide are used.
➢ Non-reactive diluents include monomeric styrene, bisphenol,
hydrocarbon oils, and phthalate ester like DOP and DBP are
used.
➢ Primary benefits include viscosity and cost reduction,
extension of pot life and decrease in exotherm.
➢ Non-reactive diluents tend to degrade mechanical, electrical
and chemical resistance properties as their concentration
increases
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Flexibilizers
➢ Non-modified epoxy resins are hard and brittle. A higher
toughness and impact resistance is needed for impregnating,
casting and adhesive resins.
➢ Low molecular weight polyaminoamides and polysulphides are
used as Flexibilizers
➢ More the polysulphide the higher will be the dielectric constant
and lower the volume resistivity, but an increase in flexibility
and impact strength.
➢ Polysulphides are frequently used in casting mixes and to a
less extent in coating, laminating and adhesive applications
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Colourants and Dyes
➢ A wide variety of colourants used with epoxides.
➢ Dies are less frequently used because of the natural tendency
of clear epoxies to yellow when exposed to UV light.
➢ Encapsulation materials for electrical industries are coloured
white to brown with TiO2 or iron oxide, respectively.
➢ High performance colourants such as cadmium or
phthalocyanine pigments are used in the ship building and
aircraft industries frequently in combination with TiO2
Other Additives
➢ Rheological additives include viscosity depressants (usually
solvents, surface activators or diluents) and thixotropic agents.
➢ Hydrophobic fumedCORPORATE
silicasTRAINING
are used as thickening agents.
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REINFORCEMENT
➢ Reinforcement used in epoxy systems are similar to that of
unsaturated polyester resin
CURING OF EPOXY RESIN
➢ Various forms of the epoxy resins, in their thermoplastic or
uncured state, are converted or hardened into useful
thermosets by reaction with a variety of curing agents.
1. Aliphatic and aromatic amines
2. Polyamides,
3. Anhydrides,
4. Dicyandiamide,
5. Isocyanate,
6. Polysulphides, mercaptans etc.,
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Amine Hardening System
➢ Primary and secondary amines are used as reactive curing agents
whilst the tertiary amines are used as catalyst
➢ Ethylene diamines are most widely used aliphatic amines for curing
epoxy resins
➢ Primary amino group is more reactive towards epoxy than secondary
amino groups.
➢ Primary amino-epoxy reaction results in linear polymerization while
secondary amino-epoxy reaction lead to branching and cross-linking.
Curing of epoxy resins with primary and secondary amines
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Typical amine curing agent for epoxy resin
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some characteristics of amine hardeners for use in low molecular weight glycidyl
ether resins
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Acid Hardening System
➢ Acid hardening systems provide cured resins with very high
HDT and with good physical, electrical and chemical properties.
➢ In practice acid anhydrides are preferred to acids,
➢ Three classes of anhydride : Room temperature solids, room
temperature liquids and chlorinated anhydrides. Examples
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Miscellaneous Hardener System
➢ In addition to amine, acid and anhydride hardeners many
other curing agents such as a number of amides that
contain amine groups are used. Eg- polyamides.
Comparison of Hardening Systems
➢ As a general rule that the amines are fast curing and give good
chemical resistance but most are skin sensitive.
➢ Organic anhydrides are less toxic and give cured products with
high HDT. They do not cross-link the resin at room temperature.
➢ As a general rule, with increasing aliphatic amines and their
adducts, the time and temperature of cure will improve the
properties
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Properties of epoxy resin moulding compounds
Low impact strength Medium impact High impact
Properties ASTM Unit strength strength
Mechanical
Density D.792 g/cm3 1.8 to 1.9 1.8 to 1.9 1.8 to 1.9
Flexural D.790 N/mm2 50 80 90
Impact strength (un notched) D.256 KJ/ m2 5 8 15
Notched impact strength D.256 KJ/ m2 1.5 3 15
Compressive strength D.795 N/mm2 120 to 200 140 to 180 140to 180
Tensile strength D.638 N/mm2 25 40 80
Flexural modulus of elasticity D.790 KN/mm2 12 to 15 15 to 18 18 to 25
Indentation hardness N/mm2 150 190 340
Thermal
Service temperature in air without mechanical
loading
short- term oC 180 180 180
long- term oC 130 130 130
Heat deflection Temperature oC 120 120 125
(Martens)
Coefficient of thermal expansion K-1.106 25 to 35 20 to 25 15 to 20
Thermal conductivity W/mK 0.6 0.6 0.6
Electrical
Surface resistance D 257 Ohms 12 12 12
Volume resistivity D 257 Ohms cm 1014 1014 1014
Dissipation factor at 50Hz D 150 - 0.07 0.03 0.04
1kHz - 0.1 0.03 0.05
1MHz - 0.05 0.04 0.04
Dielectric constant 50Hz D 150 - 6 6 6
1kHz - 5 5 5
1MHz - 5 5 5
Dielectric Strength D 149 KV/cm 240 210 260
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PHYSICAL PROPERTIES
Mechanical Properties
➢ Mechanical properties of cast resins depend on
Chemical structure of curing agent and epoxy resin,
Epoxy-amino stoichiometry or cross-link density of the cured
network,
Cure schedule and test temperature.
➢ TGDDM / DDS system (tetraglycidyl derivative of 4,4’ Diamino-
diphenylmethane/4.4’ diamenodiphenyl sulphur) is used in high
performance composite because of its high glass transition
temperature (Approx.250ºC) and good strength retention even after
prolonged exposure to elevated temperature
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Thermal Properties
➢ Thermal properties of epoxy resin are dependent on the degree
of cross-linking, the flexibility of the resin molecule and the
flexibility of the hardener molecule
➢ Rigid structure obtained by using cycloaliphatic resins or
hardeners such as pyromellitic dianhydride will raise the heat
distortion temperature.
➢ Tg of epoxy moulded materials is markedly affected by the
curing conditions. Example; cold cured system is 70ºC and that
of a hot-cured system 140ºC
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Electrical Properties
➢ Epoxy resin system exhibit good electrical properties over a wide range
of frequencies and temperature.
➢ Excellent insulating materials having high dielectric strength, arc and
tracking resistance.
➢ Resins are somewhat polar and this is reflected in the comparatively
high dielectric constant and power factor for an insulating material.
CHEMICAL PROPERTIES
Resistance to chemicals
➢ Resistant to weak acids, weak alkalis, alcohols, petroleum, benzene,
oils, fats, solvents
➢ Limited resistant to hot water
➢ Not attacked by strong acids, strong alkalis, ammonia, acetone, esters,
ketones.
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Resistance to weathering
➢ Epoxy resin system serves as excellent moisture barriers exhibiting
low water absorption and resistance to most of the fungi growth.
➢ Absorb only a tiny parts of UV component of sunlight
Resistance to High Energy Radiation
➢ Epoxy moulded materials are like PF and UP moulded materials, very
resistant to radiation.
Flammability
➢ Use of tetrachlorobisphenol A or tetrabromobisphenol A as hardener
imparts to the product a high flame retardancy
Toxicological Assessment
➢ In appropriate handling of epoxy reactive resins and reactive materials
such as acid anhydrides, polyamides and accelerators can cause skin
irritation. In contract the cured moulded materials are non-toxic
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PROCESSING OF EPOXY RESINS
1. Casting of epoxy resins
2. Glass fiber reinforced moulding
3. Epoxy Laminates
4. Powder coating
5. Epoxy Prepregs
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Casting of epoxy resins
➢ Though the volatile content is very small in epoxy resin system,
degassing is necessary when making high performance electrical
mouldings.
➢ All additives used in the formulations must be dry. It is preferable to stir
additives and resin under vacuum.
➢ Casting resin prepared at the given mixing temperature is poured into
the mould which has been pre-warmed to the curing temperature. Items
to be encapsulated must also be pre-dried.
➢ Moulds may be of steel, light alloy or epoxy cast resin.
➢ High curing temperatures and highly reactive resin systems shorten
the occupation time of moulds but which lead to poorer mechanical
and electrical properties in the finished products
➢ Advantages of epoxy casting resins such as good mechanical and
electrical properties, low shrinkage and the lack of disruptive by-
products during processing contribute towards their wide use.
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Glass fiber reinforced moulding
➢ Fiber reinforced articles are manufactured by hand lay up or filament
winding process.
➢ Curing time for mouldings manufactured by hand lay up is between 6
and 24 hours at room temperature.
➢ Wound containers and tubes cure in an oven in 15 minutes to 3 hours.
➢ Techniques are similar to those used for unsaturated polyester reactive
resins.
Epoxy Laminates
➢ Resin, curing agent and accelerator are dissolved in acetone.
➢ Webs to be impregnated (usually glass fiber fabrics) are drawn through
the impregnating bath.
➢ In the drying tunnel the solvent vaporizes and a pre-reaction of resin
starts. The prepregs are dried and wound up.
➢ Later cut-to-size pieces are pressed in a multi-platen press at pressures
of 40 bar and temperature of 170 oC
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Powder coating
➢ Epoxy powder is sprayed electrostatically on the pre-heated parts; it
melts and cure in 15 to 30 seconds.
➢ Welds and damaged parts are protected with an epoxy putty (curing
time 3 hours at 20o C).
➢ Coatings of 50 - 300 micron protect against corrosion.
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Epoxy Resin moulding Compounds
➢ EP moulding compounds can be processed by compression,
transfer and injection moulding.
➢ Excellent flowability allows the manufacture of complicated
moulded items at low injection pressures.
➢ Moulded items produced from these moulding compounds are
having the following properties
Low processing shrinkage,
High dimensional stability,
No tendency to stress crack formation,
Good adhesion on all materials,
Mouldings with many inserts can be manufactured.
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Epoxy Prepregs
➢ Glass fibre prepregs with epoxide resins have been available for the
manufacture of reinforced EP moulded items.
➢ Glass content lies between 37 and 60%
➢ Shelf life of these prepregs is six months at -18 °C and 10 days at
room temperature.
➢ Prepregs pressed at temperatures between 120 and 160 °C and
pressures of 0.7 to 7.0 bar
➢ EP prepregs reinforced with carbon fiber are also available
commercially.
Secondary Processing
➢ Secondary processing of epoxy resin such as cutting joining and
surface finishing are similar to that of unsaturated polyester resin.
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AVAILABILITY
➢ Epoxy reactive resins are available in great variety as casting,
impregnating, paint and coating resins.
➢ Epoxy reactive resins are available in solid and liquid (unthinned and
thinned with solvent) forms as well as glass fiber prepregs
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TYPICAL APPLICATIONS
Coating Applications
➢ Coating application consume more than fifty percent of epoxy resin
production.
➢ Epoxy’s chemical resistance, toughness and durability and good
adhesion are the prime features for this arena.
➢ Used as coatings in appliance and automotive primers, industrial
maintenance paints, and corrosive protection coatings for marine
products
➢ Two component, water based epoxy emulsion paints are being used
in architectural applications.
➢ Traditional coal-tar epoxies and zinc-rich wash coat primers are used
for maintenance and marine products protection coatings.
➢ UV curable epoxy coatings have been developed for environmental
protection of printed circuit boards
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Casting and Encapsulation Applications
➢ High resistivity and relatively low dissipation factor, and high
mechanical properties, allow for widespread use of epoxies in electrical
and electronic applications as a insulators.
➢ Encapsulation and coating of transistors, switches, coils, insulators,
and integrated circuits, outdoors transformers, switching gears etc.,
are some of the routine usages of epoxy resins.
➢ Tools like Patterns, jigs, metal shaping moulds and vacuum forming
moulds are frequently made from epoxy castings
➢ Deep diving submersible pump from acrylic and epoxy resins will
provide diving capability to depths of 6500 feet
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Adhesives and Bonding Sealants
➢ Since from the early stage of introduction of epoxy resins, they have
been a dominant force in adhesives and bonding.
➢ Volatile-free curing and minimal shrinkage combined with excellent
lap-shear strength make epoxies the premier adhesive.
➢ Epoxy adhesive systems successfully bonded to and filled enamel
dentin and cementum in the dental field.
➢ Automotive industry have promoted the replacement of welding
riveting and other traditional metal joining processes with epoxy
adhesive bonding
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Laminates and Composites
➢ Glass, graphite and polyaramid reinforced epoxy composites continue
to find major use in industries such as space, printed circuitry, tanks
and pressure vessels and pipes.
➢ Epoxide resin laminates are of particular importance in the aircraft
industry. It has been stated that the Boeing 757 and 767 aircraft use 1.8
tons of carbon fibre/epoxide resin composite for structural purposes
per aeroplane.
➢ Epoxy resin also been used with Aramid fibres for filament wound
rocket motors and pressure vessels.
➢ Epoxy/carbon fibre composite also being used in large quantities in
aircraft helicopter blades.
➢ Epoxide resins reinforced with carbon and aramid fibres have been
used in small boats with a 40% saving in weight over traditional
polyester/glass fibre composite.
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➢ Aramide/epoxy composites also being used as helmets for military
purposes to replace steel.
➢ One fourth of the epoxy resin production is being used in the
application of printed circuit boards.
➢ A violin is constructed with the composite replacing traditional woods.
Cost and fabrication time were substantially reduced.
Surface Coating
➢ Largest end use of epoxide resins is surface coating.
➢ Industrial chemically resistant flooring remains a major use of epoxy
resins.
➢ Some decorative `pour-a-floor’ systems are still popular because of the
ease of application and excellent adhesion to glass, quartz, marble
chips and other attractive inclusion materials.
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Aerospace application
Boeing’s 787 Dreamliner aircraft is being built using over 50%
(by weight) composite materials, mainly using carbon fiber.
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Major Carbon Fibre Reinforcement Plastic (CFRP) Applications in A - 380
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Launch Vehicles / Missile
1. Nozzles – Divergent / Convergent
• Silica – Phenolic
• Carbon – Phenolic
• Carbon – Carbon
2. Heat Shield / Nose Cone
• Carbon Fibre Epoxy
• Silica – Epoxy
• Carbon – Carbon Nozzle Assembly War-Head Assembly
3. Radomes
• Silica-Silica Composite
• Glass Phenolic
4. Re-Entry Vehicle Heat Shield
• Ceramic Tiles
5. Gas Bottles
• Graphite Fibre - Epoxy
• Kevlar Fibre - Epoxy
6. Inter Stage Rings
• Graphite Fibre - Epoxy
7. Motor Case
• Kevlar – Epoxy
• Glass - Epoxy Radomes Silica – Tile Billet
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Epoxy in Spacecrafts
1. Antennas
• Carbon - Epoxy
• Graphite Fibre – Epoxy
2. Structures
• Carbon - Epoxy
• Graphite – Epoxy
3. Gas Bottles
• Graphite Fibre - Epoxy
• Kevlar – Epoxy
4. Solar Panels
• Carbon Fibre – Epoxy
5. Inserts
• Silica - Epoxy
• Carbon Fibre – Epoxy
Solar Panel
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Filament winding on a four axes, three spindle winder using
carbon/fiberglass fibers for CNG tanks for buses and cars.
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