EPOXY

Presented By-Biswajit Maity

M.Sc. in Polymer Science
CIPET-AHMEDABAD(INDIA)

Contents..
History
Introduction
Structure
Chemistry
Curing/hardener
What

makes epoxy resins

special

Properties
advantages

Application
Health

risks

Marketability
Industries
Conclusions
Reference

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 (

)nC

C
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-epoxycyclohexylmethyl3,4-epoxycyclohexane carboxylate). They are formed by the reaction of cycloolefins 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

c

O
C C C O

OH

O C C C O

C C

a) Diglycidyl Ether of Bisphenol A (DGEBPA)

O
C C C
C C C
O

O
N

C C C

(C

C C C
O

b) Tetraglycidylmethylenedianiline
(TGMDA)

)nC

C
C

C
C

C
C

c) Epoxidized phenolic resin

(Epoxy Novalac)

Properties with chain length (n)

Number of repeat
units (n)

Heat Distortion Temperature

(HDT) (F/C)

Physical state

105/40

Semi-solid

160/70

Solid

265/130

Solid

12

300/150

Solid

Epoxy specialty molecules

OH
O
C C C O C C O C C C O

OH
OH
OH
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

O C C
O

C
N
C
O

C
N
C
O

C C O
O

O
C C C O

O C C C

O
C C C O

High Temperature Epoxy Resins

O C C C

Epoxies HDT and structure

Resin Type
(predominate)

Heat Distortion Temp (HDT)

(F/C)

Aliphatic
(straight chain)

255-270/125-132

Aliphatic
(cyclical)

230-300/110-150

Aromatic
(cyclical)

290-350/145-175

Aromatic
(straight chain)

265-290/130-145

Curing Epoxies
Epoxies

use hardeners instead of initiators for curing

Hardeners

epoxy ring

can be almost any molecule that will react with (open) the

Epoxy Crosslink Mechanism

C C C C...
O Epoxy
H
N

C Hardener
C...
The other end can also react.

C C C C...
H N O H
Cured Polymer
C
C...

Curing

Epoxy ring
C

Epoxy ring

C (

C
)nC
O

H N
H

H N
H
Hardener molecules have two
reactive ends, so they can each
react with two epoxy molecules.

Effects of various hardeners

Hardeners

Advantages

Disadvantages

Aliphatic amines

Convenience, low cost, room

temp cure, low viscosity

Skin irritant, critical mix

ratios, blushes

Aromatic amines

Moderate heat resistance,

chemical resistance

Solids at room temp,

long and elevated cures

Polyamides

Room temp cure, flexibility,

toughness, low toxicity

High cost, high

viscosity, low HDT

Amidoamines

Toughness

Poor HDT

Dicyandiamide

Good HDT, good electrical

Long, elevated cures

Anhydrides

Heat and chem resistance

Long, elevated cures

Polysulfide

Moisture insensitive, quick set Odor, poor HDT

Catalytic

Long pot life, high HDT

Long, elevated cures,

poor moisture

Melamine/form.

Hardness, flexibility

Elevated temp cure

Urea/form.

Adhesion, stability, color

Elevated temp cure

Phenol/form.

HDT, chem resistance,

hardness

Solid, weatherability

Epoxy and Polyester Comparison

Comparisons
Active site

Polyester

Epoxy

C=C

Crosslinking reaction

Addition/free radical

O
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
Reactant toxicity

Frequent

Infrequent

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
Tough

non porous

and resistant to impact

Flexible

enough to withstand expansion without damage due to temperature

changes

Excellent
Film

adhesions on various substrates

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
Low

shrinkage on cure typically > 3%

Excellent
Versatile
No

adhesion

water, heat and chemical resistance

(formulations can be tailor made to theneeds)

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 selflevelling 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

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
Concrete
Metal

roofing, sealing, bonding

repairs weather, lightweight yet strong

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
$5

produces 30% or the worldwide market.

Billion industry in North America

Hexion (Shell Development Company)

Dow Chemical Company
Huntsman Corporations 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

Supreme Silicones

Contact Person Mr. Dalip Kumar (CEO)

Contact Person : Omkar Waikar

Address

Mobile
Phone
E-mail

No. 1209, Shankar Building,

Gali No.11, Sadar Bazar
New Delhi, Delhi - 110 006,
India
+(91)-9810355592 /
9910007842/9910007832
+(91)-(11)-23673462 /
23616830 / 23558239 /
23618457
sdc_luxmi@yahoo.co.in

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 :
No 316 QingHeLiTing, AnDong Road, TunXi
district, HuangShan city, AnHui P.R.,CN

City :
huangshan

Country/Region :
China (Mainland)

Telephone:
86-559-2335676

Office Address: 30/F, Yanqiao Building ,

No.89 Yanling Road , Tian He District , China

Tel:0086-20-62213889 Fax: 0086-2062213898

Email: gt@sscigz.com , gt3@sscigz.com ,

gt4@sscigz.com

MSN: ssci@hotmail.com , ssci3@hotmail.com

, ssic4@hotmail.com

 SHREEJI

PHARMA INTERNATIONAL

Contact Person

India Office
Mr. Nilesh

Address

Sheth / Mr. Tushar Kavade

311, ATLANTIS

HEIGHTS,
SARABHAI MAIN ROAD,
VADIWADI, Vadodara - 390 007
Gujarat, INDIA.
Tele:0091-265-2313036

Mobile:8866002331 / 8758805202

City
State
Country
Pin Code

Email:info@shreejipharma.com,inquiry@shreejipharma.com

Phone

Skype Id :Nilesh.sheth70

Fax

Email Address

:
:
:
:
:
:
:
:

Mr. Vinod Sapla

A-701, Parasnath Darshan
Complex, Kirol - Kurla Road,
Vidyavihar, Ghatkopar (west).
Mumbai
Maharashtra
India
400086
+91-22-22918490
+91-22-25128442
sales@amglobal.in

Global Polytech

Conpro Chemicals Private Limited

Shanti Niketan, Opposite Mahindra Global Gallery, Ghodbandar Road, Ovala Naka, Ovala,
Thane - 400615, Maharashtra, Indiawww.indiamart.com/globalpolytech ,
Contact no-08377809504

E- 8, Site- 4, Industrial Area ,

Sahibabad - 201010, Uttar Pradesh, Indiawww.conprochemicals.com
Contact no-08376808245

Stanvac-superon Group

S. M. Adhesives

Plot No. 552, Sector 37, Pace City II ,

Gurgaon - 122001, Haryana, Indiawww.stainlesssteelwiresindia.com
Contact no-08377801164

Shop No. 4, Ganga Bhuvan, SRPS Road, Opposite Chetna Apartment,

Bhandup West ,
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 ,

Gurgaon - 122001, Haryana, Indiawww.indiamart.com/drtechmart
Contact no- 09953359946

C/5 /4, Road No. 8, Hojiwala Industrial Estate, SSUML, Sachin,

Surat - 394230, Gujarat, Indiawww.magikgroup.in
Contact no-09953353143

Clean Coats Pvt. Ltd.

Shankar Dyes & Chemicals

No. 101, Metro House, B- Block, Metro Estate, No. 178 CST Road,
Behind Mercedes Benz Showroom,
Mumbai - 400098, Maharashtra, Indiawww.indiamart.com/cleancoats
Contact no-08377801668

No. 1209, Shankar Building, Gali No. 11, Sadar Bazar ,

New Delhi - 110 006, Delhi, Indiawww.shankardyes.com
Contact no-08447498163

MPR Technique

Grauer & Weil (I) Ltd

No. 6, Thirumalai Nagar 200 Feet Road, Kolathur,

Chennai - 600099, Tamil Nadu, Indiawww.epoxyfloor.co.in
Contact no-08447564070

Akurli Road, Kandivli East ,

Mumbai - 400101, Maharashtra, Indiawww.grauerandweil.com
Contact no-08586970105

Roto Polymers And Chemicals

Perma Construction Aids Private Limited

63, Reddipalayam Road, Mugappair West ,

Chennai - 600037, Tamil Nadu, Indiawww.rotexepoxy.com
Contact no-08373904240

No. 611/612, Nirmal Corporate Center, Mulund West ,

Mumbai - 400080, Maharashtra, Indiawww.permaindia.in
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