EPOXY

Presented By-Biswajit Maity

M.Sc. in Polymer Science
CIPET-AHMEDABAD(INDIA)
Contents…..
• History • Application
• Introduction • Health risks
• Structure • Marketability
• Chemistry • Industries
• Curing/hardener • Conclusions
• What makes epoxy resins special • Reference
• Properties
• advantages
Epoxy Resins
• Found by C. Castan in 1930s on his search for dental use and successfully
introduced by Ciba by end 1940s in the electro industry as insulating material, as
coating and laminating material, as well as adhesive.
Epoxy Resin
• Also called "epoxy" or "polyepoxide".
• Second most widely used family of thermosets copolymer(after polyesters)
• Large portion of uses are non-reinforced (adhesives, paints, etc.)
• Circuit boards are the largest reinforced application (low conductivity, low volatiles)
• General Properties:
• High Mechanical Properties: large cohesive force
• Good Adhesive Performance: great number of polar group
• Excellent stability: without impurities(base and salt)
• Flexibility and diversity in Designing

Because of the stability and mechanical properties, epoxy resin coating owns great chemical
and physical resistance.
Epoxy Structure
Epoxy ring Epoxy ring

C C ( )n C C
O O

Polymer portion

Number of repeat units

EPOXY CHEMISTRY
Improved Epoxy Resins :
Epoxy Cresol Novolac (ECN)

• In the mid sixties, new multi functional epoxy resins of phenol novolac or cresol
novolac were introduced in the market.
• The chemistry of these resins is very similar to that of Bisphenol-A type resins.
• The main purpose of using these resins was to improve the cross linking density of
the formulation
Novolac epoxy resin
• Reaction of phenols with formaldehyde and subsequent glycidylation with
epichlorohydrin produces epoxidised novolacs, such as epoxy phenol novolacs
(EPN) and epoxy cresol novolacs (ECN).
• These are highly viscous to solid resins with typical mean epoxide functionality of
around 2 to 6.
• The high epoxide functionality of these resins forms a highly crosslinked polymer
network displaying high temperature and chemical resistance, but low flexibility.
• 100% solids hybrid novolac epoxy resin systems have been developed that contain
no solvents and no volatile or organic compounds. These hybrid novolac epoxies
have been documented to withstand up to 98%
sulfuric acid
Bisphenol A epoxy resin
• The most common and important class of epoxy resins is formed from reacting
epichlorohydrin with bisphenol A to form diglycidyl ethers of bisphenol A.
• reacting two moles of epichlorohydrin with one mole of bisphenol A to form the bisphenol
A diglycidyl ether (commonly abbreviated to DGEBA or BADGE).
• DGEBA resins are transparent colourless-to-pale-yellow liquids at room temperature,
with viscosity typically in the range of 5-15 Pa.s at 25 °C.
• since pure DGEBA shows a strong tendency to form a crystalline solid upon storage at
ambient temperature.
• which are semi-solid to hard crystalline materials at room temperature depending on the
molecular weight achieved. As the molecular weight of the resin increases,
• the epoxide content reduces and the material behaves more and more like a
thermoplastic. Very high molecular weight polycondensates (ca. 30 000 – 70 000 g/mol)
form a class known as phenoxy resins
Bisphenol F epoxy resin
• Bisphenol F may also undergo epoxidation in a similar fashion to bisphenol A.
• Compared to DGEBA, bisphenol F epoxy resins have lower viscosity and a higher
mean epoxy content per gram, which (once cured) gives them increased chemical
resistance.
Aliphatic epoxy resin
• There are two types of aliphatic epoxy resins: glycidyl epoxy resins and cycloaliphatic
epoxides.
Glycidyl epoxy resins are typically formed by the reaction of epichlorohydrin with
aliphatic alcohols or polyols to give glycidyl ethers or aliphatic carboxylic acids to give
glycidyl esters.
• This reaction is normally done in the presence of an alkali, such as sodium hydroxide, to
facilitate the dehydrochlorination of the intermediatechlorohydrin. The resulting resins
may be monofunctional (e.g. dodecanol glycidyl ether), difunctional (diglycidyl ester of
hexahydrophthalic acid), or higher functionality (e.g. trimethylolpropane triglycidyl ether).
• These resins typically display low viscosity at room temperature (10-200 mPa.s) and are
often used as reactive diluents. As such, they are employed to modify (reduce) the
viscosity of other epoxy resins. This has led to the term ‘modified epoxy resin’ to denote
those containing viscosity-lowering reactive diluents. However, they are also used without
other epoxide ingredients along with anhydride curing agents such as hexahydrophthalic
anhydride to make molded objects such as high voltage insulators. This is in fact the main
use of the diglycidyl esters.
• The cycloaliphatic epoxides contain one or more cycloaliphatic rings in the
molecule to which the oxirane ring is fused (e.g. 3,4-epoxycyclohexylmethyl-3,4-
epoxycyclohexane carboxylate). They are formed by the reaction of cyclo-olefins
with a peracid, such as peracetic acid.[4] This class also displays low viscosity at
room temperature, but offers significantly higher temperature resistance and
correspondingly better electrical properties at high temperatures to cured resins
than the glycidyl aliphatic epoxy resins.
• Another advantage is the complete absence of chlorine, since no epichlorohydrin
is used in the manufacturing process. This is particularly useful for electronic
applications such as the encapsulation of light emitting diodes. However, room
temperature
• reactivity is rather low compared to other classes of epoxy resin, and high
temperature curing using suitable accelerators is normally required.
Glycidylamine epoxy resin

• Glycidylamine epoxy resins are higher functionality epoxies which are formed
when aromatic amines are reacted with epichlorohydrin.
• Important industrial grades are triglycidyl-p-aminophenol (functionality 3) and
N,N,N,N-tetraglycidyl-4,4-methylenebis benzylamine (functionality 4).
• The resins are low to medium viscosity at room temperature,
• which makes them easier to process than EPN or ECN resins.
• This coupled with high reactivity, plus high temperature resistance and
mechanical properties of the resulting cured network make them
• important materials for aerospace composite applications.
Epoxy − specific molecules
O c OH C O
C C C O C O C C C O C O C C
c n C

a) Diglycidyl Ether of Bisphenol A (DGEBPA)

O O
C C C C C C (C )nC
N C N
C C C C C C
O O C C C
C C C
b) Tetraglycidylmethylenedianiline C C C
(TGMDA) O O O
C C C
c) Epoxidized phenolic resin
(Epoxy Novalac)
Properties with chain length (n)
Number of repeat Heat Distortion Temperature Physical state
units (n) (HDT) (°F/°C)

2 105/40 Semi-solid

4 160/70 Solid

9 265/130 Solid

12 300/150 Solid
 Epoxy − specialty molecules
O OH OH OH OH O
C C C O C C O C C C O O C C C O C C O C C C N C C C O C C O C C C
C
C
Toughened Epoxy Resin C
NH2

C
C C
O C C C C O
N N
O O
C C
O O

O O
C C C O C C O C C C

O O
C C C O O C C C
High Temperature Epoxy Resins
Epoxies − HDT and structure
Resin Type Heat Distortion Temp (HDT)
(predominate) (°F/°C)
Aliphatic 255-270/125-132
(straight chain)
Aliphatic 230-300/110-150
(cyclical)
Aromatic 290-350/145-175
(cyclical)
Aromatic 265-290/130-145
(straight chain)
Curing Epoxies
• Epoxies use hardeners instead of initiators for curing
• Hardeners can be almost any molecule that will react with (open) the epoxy ring
Epoxy Crosslink Mechanism
C C C C... C C C C...
O Epoxy H N O H
H
C Cured Polymer
N H
C C...
Hardener
C...

The other end can also react.

Curing
Epoxy ring Epoxy ring

C C ( )n C C
O O
H N H N
H H
Hardener molecules have two
reactive ends, so they can each
react with two epoxy molecules.

N N
H H H H
Effects of various hardeners
Hardeners Advantages
Aliphatic amines Convenience, low cost, room
temp cure, low viscosity
Aromatic amines Moderate heat resistance,
chemical resistance
Polyamides Room temp cure, flexibility,
toughness, low toxicity
Amidoamines Toughness
Dicyandiamide Good HDT, good electrical
Anhydrides Heat and chem resistance
Polysulfide Moisture insensitive, quick set Odor, poor HDT
Catalytic Long pot life, high HDT
Melamine/form. Hardness, flexibility
Urea/form. Adhesion, stability, color
Phenol/form. HDT, chem resistance,
hardness
Disadvantages
Skin irritant, critical mix
ratios, blushes
Solids at room temp,
long and elevated cures
High cost, high
viscosity, low HDT
Poor HDT
Long, elevated cures
Long, elevated cures
Long, elevated cures,
poor moisture
Elevated temp cure
Elevated temp cure
Solid, weatherability
Epoxy and Polyester Comparison
Comparisons Polyester Epoxy
Active site C=C C C
O
Crosslinking reaction Addition/free radical Ring opening
Crosslinking agent Initiator (peroxide) Hardener
Amount of x-link agent 1-2% of resin 1:1 with resin
Solvent/viscosity Styrene (active)/low Infrequent/high
Volatiles High Low
Inhibitors, accelerators Frequent Infrequent
Reactant toxicity Low Moderate
Cure conditions Room temp or heated Heated (some room)
Shrinkage High Low
Post cure Rare Common
Polyester and Epoxy − Properties
Property Polyester Epoxy
Adhesion Good Excellent
Shear strength Good Excellent
Fatigue resistance Moderate Excellent
Strength/stiffness Good Excellent
Creep resistance Moderate Moderate to good
Toughness Poor Poor to good
Thermal stability Moderate Good
Electrical resistance Moderate Excellent
Water absorption resist Poor to moderate Moderate
Solvent resistance Poor to moderate Good
UV resistance Poor to moderate Poor to moderate
Flammability resistance Poor to moderate Poor to moderate
Smoke Moderately dense Moderately dense
Cost Low Moderate
What makes epoxy resins special

• The aromatic structure of the resin implements a strong hydrophobic

performance far over competitive resins like polyurethanes or acrylics, which were
developed at the same time.
Corrosion resistance
Epoxy based formulations give corrosion resisting coatings or laminates .
• Absolutely non porous
• Tough and resistant to impact
• Flexible enough to withstand expansion without damage due to temperature changes
• Excellent adhesions on various substrates
• Film thickness is adaptable
• Highly resistant to chemicals, solvents, moisture andelevated temperatures
• Film-forming time is as short as possible
• Long pot life of room temperature curable systems
• Easy to apply
Other advantages of epoxy systems
• Excellent adhesion

• Low shrinkage on cure typically > 3%

• Excellent water, heat and chemical resistance

• Versatile (formulations can be tailor made to theneeds)

• No release of volatiles during curing (addition reaction)

Corrosion resistance improvement

• The performance of epoxy resins can be improved by

selecting the proper hardeners, pigments, fillers and
suitable additives
Environmentally Friendly Epoxy
Formulations
• Epoxy based coatings are reformulated into ecologically acceptable and energy
saving systems without loosing their excellent corrosion resistant performance.
• Instead of organic solvents, water was used, which was cheap, nonflammable and
non-toxic. Such epoxy coating systems, dissolved or dispersed in water have for a
long time captured a substantial share of the market as electro-deposition primer
for car bodies
Corrosion protection of crude oil tanks
• The compete absence of volatile components in combination with liquid epoxy
resins, reactive diluents and low viscose hardeners makes it possible to formulate
coatings – or reinforced with glass fibres as laminates – with high corrosion
resistance performance to protect the inside of storage tanks for crude oil and
other chemicals.
• Several tank farms in the Middle East have been successfully coated many years
ago and are still functional.
Corrosion protection of ship ballast tanks
• This highly corrosive environment requires a rugged epoxy coating, designed for
immersion service in salt water ballast tanks and fuel/sea water ballast tanks.
Engineering
• Protective coatings are therefore usually based on primers containing a linseed oil
or alkyd binder and anti-corrosion pigments such as red lead, lead chromate, zinc
chromate, potassium zinc chromate, and zinc dust.
• The completed coating system will have a dry thickness of 5 to 10 mils.
Corrosion protection in Civil Engineering
• Quartz sand filled systems enable the application as mortar or self-levelling
flooring.
• These cold curing systems are applicable even under unfavorable conditions, such
as at temperatures close to the freezing point, high humidity and even under
water.
Corrosion protection in Civil Engineering
(Powder Coating)
• Reinforced steel bars embedded into concrete can corrode because of chloride
attack, carbonation effect and humidity in a marine and coastal environment. This
takes place if the alkaline environment surrounding the bars slowly changes with
reduction of pH-value from 12.7 to under 8.4.
• The rust products of corroding steel bars occupy much more volume than that of
original steel and the expansion pushes out the concrete cover and causes cracks.
Corrosion protection in Civil
Engineering (Powder Coating
• The protection of such rebar with suitable epoxy powder coating prevents such
corrosion
Corrosion protection in Civil
Engineering
Powder Coatings
• The electrostatic application of a fine pulverized, completely solvent free, solid
epoxy resin/hardener system in the early seventies was
• a real break through in the coating industry!
• The higher molecular weight resins (1200 – 1800), based on Bisphenol-A were
predestined to be suitable for their outstanding performance in having a low
melting point and viscosity and various functionalities.
• High purity and practically no gelled particles which would deteriorate the final
quality of the coating.
Powder Coatings
• Quality metal substrates like furniture and kitchenappliances, gardening
equipment, sport goods as well as parts under the hoods of the car body are
powder coated.
• The automotive industry additionally offers significant increase potential
regarding on-line surface primer as a second layer on top of the electro-deposition
primer with excellent corrosion and stone chip resistance.
• Due to their excellent anti corrosion properties, high reactive powder systems are
mainly used to protect steel pipes transporting water, oil or gas.
Powder Coatings
• In general the performance of the powder coatings is influenced by several factors
depending on the epoxy resin types:
• Average molecular weight
• Molecular distribution
• End-group functionality VS epoxy content
• Degree of chain branching
• Compatibility with the co-reactant
• Easy homogenization in the extruder.
As for Epoxy Resin Coatings...
• Epoxy coatings were developed for heavy duty service on metal substrates and use less
energy than heat-cured powder coatings.
• Their low volatility and water clean up makes them useful for factory cast iron, cast
steel, cast aluminum applications and reduces exposure and flammability issues
associated with solvent-borne coatings.
Industrial Flooring

Waterproofing
Industrial Applications
• Waterproofing – roofing, sealing, bonding
• Concrete repairs – weather, lightweight yet strong
• Metal protection – corrosion resistant

Before

After repair
Industrial Applications
Industrial flooring
• rubber carpet: playgrounds, water parks, bathrooms chemical
resistant and hard-wearing
• non-slip flooring: stadiums, gyms, industry
Health risks
Primary risk associated with epoxy use is often related to the hardener component
• Amine hardeners –corrosive, toxic and/or carcinogenic or mutagenic.
• Aromatic amines -health hazard (most are known or suspected carcinogens) their
use is now restricted to specific industrial applications.
• safer aliphatic or cycloaliphatic amines are commonly employed.
• Liquid epoxy resins in their uncured state-irritant to the eyes and skin, as well as
toxic to aquatic organisms.
• Solid epoxy resins are generally safer than liquid epoxy resins.
• Exposure to epoxy resins can, over time, induce an allergic reaction.
“Marketability” of the Epoxy Coatings
Industry
• Epoxy coatings are chemically resistant to water, saltwater, organics, and acid
• Also resistant to mechanical damage (scratches)
• Also does not deform at high temperatures, due to its thermoset polymer nature
• Thanks to this wide variety of desirable properties and applications, epoxy coating are
marketed in industrials, commercial, and residential sectors
Demand and Applications for Epoxy
The Industry of Epoxy Resins
• China produces 30% or the worldwide market.
• $5 Billion industry in North America
• Hexion (Shell Development Company)
• Dow Chemical Company
• Huntsman Corporation’s Advanced Materials

• Some current applications are on “under-the-hood” automotive components,

floor coatings, underground tanks/pipes/cables, electrical connectors, circuit
boards, adhesives, structural support additive in high stress areas like wind
turbines and aerospace frames
Marketability
Marketability
SHANKAR DYES & CHEMICALS
Contact Person Mr. Dalip Kumar (CEO)
No. 1209, Shankar Building,
Gali No.11, Sadar Bazar
Address
New Delhi, Delhi - 110 006,
India
+(91)-9810355592 /
Mobile
9910007842/9910007832
+(91)-(11)-23673462 /
Phone 23616830 / 23558239 /
23618457
E-mail sdc_luxmi@yahoo.co.in
Supreme Silicones
Contact Person : Omkar Waikar
A − 704, Nancy Lake Homs, Satara Road,
Opp. Bharati Vidyapeeth, Katraj,
Pune, Maharashtra 411046
India.
Tele : +91 20 2410 8067
Mobile : +91 9822281671
Email : business@supremesilicones.com
Email : omkar@supremesilicones.com
HuangShan KBR Chemical CO.,LTD
Manufacturer[China (Mainland)]

• Street Address : • Office Address: 30/F, Yanqiao Building ,

No 316 QingHeLiTing, AnDong Road, TunXi No.89 Yanling Road , Tian He District , China
district, HuangShan city, AnHui P.R.,CN
• Tel:0086-20-62213889 Fax: 0086-20-
• City : 62213898
huangshan
• Email: gt@sscigz.com , gt3@sscigz.com ,
• Country/Region : gt4@sscigz.com
China (Mainland)
•
• Telephone:
86-559-2335676 • MSN: ssci@hotmail.com , ssci3@hotmail.com
, ssic4@hotmail.com
• SHREEJI PHARMA INTERNATIONAL Contact Person : Mr. Vinod Sapla
• A-701, Parasnath Darshan
India Office Address : Complex, Kirol - Kurla Road,
• Mr. Nilesh Sheth / Mr. Tushar Kavade Vidyavihar, Ghatkopar (west).
City : Mumbai
• 311, ATLANTIS HEIGHTS,
SARABHAI MAIN ROAD, State : Maharashtra
VADIWADI, Vadodara - 390 007
Gujarat, INDIA. Country : India
Tele:0091-265-2313036
Pin Code : 400086
•
Mobile:8866002331 / 8758805202 Phone : +91-22-22918490
• Fax : +91-22-25128442
Email:info@shreejipharma.com,inquiry@shreejip
harma.com Email Address : sales@amglobal.in

• Mobile : +91-9321003115
Skype Id :Nilesh.sheth70 Web Site : http://www.am-global.com
Global Polytech Conpro Chemicals Private Limited
Shanti Niketan, Opposite Mahindra Global Gallery, Ghodbandar Road, Ovala Naka, Ovala, E- 8, Site- 4, Industrial Area ,
Thane - 400615, Maharashtra, Indiawww.indiamart.com/globalpolytech , Sahibabad - 201010, Uttar Pradesh, Indiawww.conprochemicals.com
Contact no-08377809504 Contact no-08376808245

Stanvac-superon Group S. M. Adhesives

Plot No. 552, Sector 37, Pace City II , Shop No. 4, Ganga Bhuvan, SRPS Road, Opposite Chetna Apartment,
Gurgaon - 122001, Haryana, Indiawww.stainlesssteelwiresindia.com Bhandup West ,
Contact no-08377801164 Mumbai - 400001, Maharashtra, Indiawww.smadhesives.net
Contact no-08447509908

D & R Tech Mart Pvt. Ltd. Marble Magik Corporation

GF - 8, Guru Nanak Market, Opposite D.A.V. School, Sector- 17 , C/5 /4, Road No. 8, Hojiwala Industrial Estate, SSUML, Sachin,
Gurgaon - 122001, Haryana, Indiawww.indiamart.com/drtechmart Surat - 394230, Gujarat, Indiawww.magikgroup.in
Contact no- 09953359946 Contact no-09953353143

Clean Coats Pvt. Ltd. Shankar Dyes & Chemicals

No. 101, Metro House, B- Block, Metro Estate, No. 178 CST Road, No. 1209, Shankar Building, Gali No. 11, Sadar Bazar ,
Behind Mercedes Benz Showroom, New Delhi - 110 006, Delhi, Indiawww.shankardyes.com
Mumbai - 400098, Maharashtra, Indiawww.indiamart.com/cleancoats Contact no-08447498163
Contact no-08377801668

MPR Technique Grauer & Weil (I) Ltd

No. 6, Thirumalai Nagar 200 Feet Road, Kolathur, Akurli Road, Kandivli East ,
Chennai - 600099, Tamil Nadu, Indiawww.epoxyfloor.co.in Mumbai - 400101, Maharashtra, Indiawww.grauerandweil.com
Contact no-08447564070 Contact no-08586970105

Roto Polymers And Chemicals Perma Construction Aids Private Limited

63, Reddipalayam Road, Mugappair West , No. 611/612, Nirmal Corporate Center, Mulund West ,
Chennai - 600037, Tamil Nadu, Indiawww.rotexepoxy.com Mumbai - 400080, Maharashtra, Indiawww.permaindia.in
Contact no-08373904240 Contact no-08373904199
Conclusion
• Epoxy Resin Coatings' Performance:
• Properties-Adhesion,Shear strength,Fatigue
resistance,Strength/stiffness,Creep resistance, Thermal
stability,Electrical resistance, Solvent resistance
• Producing☺☺
• Cost-Moderate

 As a result, epoxy resin coatings has been widely used in

many different conditions.
Reference:
• http://en.wikipedia.org/wiki/Epoxy_resin

• http://en.wikipedia.org/wiki/Coating

• http://www.epoxy.com/633.aspx

• http://www.hitechcivilindia.com/pronserv.htm

• http://www.sika.in/construct_project.htm

• http://jycl.tede.cn/2008/05/120995758970581.html

• http://www.knovel.com/web/portal/knovel_content