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 DesigningBecause of the stability and mechanical properties, epoxy resin coating owns great chemical and physical resistance.

Epoxy Structure

C C

Epoxy ring

OC C

O

()n

Polymer portion

Epoxy ring

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

CCCO

CCCO

NC C C

O

C C CO

N C

C

C

C

CO

C

C

C

C

CO

C

C

C

CO

C

a) Diglycidyl Ether of Bisphenol A (DGEBPA)

b) Tetraglycidylmethylenedianiline(TGMDA)

c) Epoxidized phenolic resin(Epoxy Novalac)

CO CO

C

C

C

OCCCO

OH

COCCCO c

c n

( )n

Properties with chain length (n)

Number of repeat units (n)

Heat Distortion Temperature (HDT) (°F/°C)

Physical state

2 105/40 Semi-solid

4 160/70 Solid

9 265/130 Solid

12 300/150 Solid

Epoxy − specialty molecules

OO

CCOCCOCCCOH

C O C C COH

O C C O C C COH

NCCCNH2

C C COH

O C C O C C CO

Toughened Epoxy Resin

O

CC

ON

C

O

OCCCOC

C C CO

OC

O

CC

ON

C

O

OC C C O C

CCCO

O CC

High Temperature Epoxy Resins

Epoxies − HDT and structureResin 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 can be almost any molecule that will react with (open) the epoxy ring

Epoxy Crosslink Mechanism

HHN

C

C...

C

O

C C...

N

C

C...

C C C...

O

C C

H H

Hardener

Epoxy

The other end can also react.

Cured Polymer

Curing

C C

Epoxy ring

OC

O

()n

Epoxy ring

N

N

HH

HH

N

N

HH

HH

C

Hardener molecules have tworeactive ends, so they can eachreact with two epoxy molecules.

Effects of various hardenersHardeners 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 ComparisonComparisons Polyester Epoxy

Active site C=C

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

OC C

Polyester and Epoxy − PropertiesProperty 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 CivilEngineering (Powder Coating• The protection of such rebar with suitable epoxy powder coating prevents such corrosion

Corrosion protection in CivilEngineering

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 ApplicationsIndustrial 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)

Address

No. 1209, Shankar Building,Gali No.11, Sadar BazarNew Delhi, Delhi - 110 006, India

Mobile+(91)-9810355592 / 9910007842/9910007832

Phone+(91)-(11)-23673462 / 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 411046India.

Tele : +91 20 2410 8067Mobile : +91 9822281671Email : business@supremesilicones.comEmail : 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: 0086-20-62213898

• Email: gt@sscigz.com , gt3@sscigz.com , gt4@sscigz.com

•  

• MSN: ssci@hotmail.com , ssci3@hotmail.com , ssic4@hotmail.com

• SHREEJI PHARMA INTERNATIONAL

•

India Office

• Mr. Nilesh Sheth / Mr. Tushar Kavade

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

•

Mobile:8866002331 / 8758805202

•

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

•

Skype Id :Nilesh.sheth70

Contact Person:

Mr. Vinod Sapla

Address :

A-701, Parasnath Darshan Complex, Kirol - Kurla Road, Vidyavihar, Ghatkopar (west).

City :

Mumbai

State :

Maharashtra

Country :

India

Pin Code :

400086

Phone :

+91-22-22918490

Fax :

+91-22-25128442

Email Address :

sales@amglobal.in

Mobile :

+91-9321003115

Web Site :

http://www.am-global.com

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

Stanvac-superon Group Plot No. 552, Sector 37, Pace City II , Gurgaon - 122001, Haryana, Indiawww.stainlesssteelwiresindia.comContact no-08377801164

D & R Tech Mart Pvt. Ltd. GF - 8, Guru Nanak Market, Opposite D.A.V. School, Sector- 17 , Gurgaon - 122001, Haryana, Indiawww.indiamart.com/drtechmartContact no- 09953359946

Clean Coats Pvt. Ltd. No. 101, Metro House, B- Block, Metro Estate, No. 178 CST Road, Behind Mercedes Benz Showroom, Mumbai - 400098, Maharashtra, Indiawww.indiamart.com/cleancoatsContact no-08377801668

MPR Technique No. 6, Thirumalai Nagar 200 Feet Road, Kolathur, Chennai - 600099, Tamil Nadu, Indiawww.epoxyfloor.co.inContact no-08447564070

Roto Polymers And Chemicals 63, Reddipalayam Road, Mugappair West , Chennai - 600037, Tamil Nadu, Indiawww.rotexepoxy.comContact no-08373904240

Conpro Chemicals Private Limited E- 8, Site- 4, Industrial Area , Sahibabad - 201010, Uttar Pradesh, Indiawww.conprochemicals.comContact no-08376808245

S. M. Adhesives Shop No. 4, Ganga Bhuvan, SRPS Road, Opposite Chetna Apartment, Bhandup West , Mumbai - 400001, Maharashtra, Indiawww.smadhesives.netContact no-08447509908

Marble Magik Corporation C/5 /4, Road No. 8, Hojiwala Industrial Estate, SSUML, Sachin, Surat - 394230, Gujarat, Indiawww.magikgroup.inContact no-09953353143

Shankar Dyes & Chemicals No. 1209, Shankar Building, Gali No. 11, Sadar Bazar , New Delhi - 110 006, Delhi, Indiawww.shankardyes.comContact no-08447498163

Grauer & Weil (I) Ltd Akurli Road, Kandivli East , Mumbai - 400101, Maharashtra, Indiawww.grauerandweil.comContact no-08586970105

Perma Construction Aids Private Limited No. 611/612, Nirmal Corporate Center, Mulund West , Mumbai - 400080, Maharashtra, Indiawww.permaindia.inContact 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