140225 composites expo 2014

DOW EPOXY BUILDING BLOCKS=

UNLIMITED POSSIBILITIES FOR THE COMPOSITE INDUSTRY

THE DOW CHEMICAL COMPANY IS A GLOBALLY LEADING SUPPLIER OFINDUSTRIAL RAW MATERIALS FOR MANY APPLICATIONS. OVER THE LASTDECADES DOW HAS ESTABLISHED ITSELF AS A MAJOR GLOBAL PRODUCER

TOF HIGH QUALITY EPOXY PRODUCTS. THE CHEMISTRY OF SOME BUILDINGBLOCKS WILL BE EXPLAINED AND THEIR RELATION TOWARDS PRODUCTPROPERTIES SUCH AS MECHANICAL STRENGTH AND TEMPERATURERESISTANCE (E.G. GLASS-TRANSITION TEMPERATURE)..

Composite-Expo - 20147th International Specialized Exhibitionon composite materials and technologiesMoscow, RussiaToine Dinnissen, February 25th 2014

Outline

The Dow Chemical CompanyThe Dow Chemical Company• Epoxy business & Commitment,

Epoxy Compositespo y Co pos es• Bisphenol-A Epoxy Resins• Curing Agents

l P t lif / hi h fl ibilit– long Pot-life / high flexibility– high temperature resistance

• Bisphenol-F Epoxy Resin• Epoxy Novolac Resins• Curing

– Gelation– Gelation– Crosslink Density– Glass Transition

Toine Dinnissen, February 25th 2014

• New development Novolac

The Dow Chemical Company

• Founded in 1897 by Herbert H. Dow in Midland, Michigan• Supplies broad range of products / services in about 160 countries• More than 5,000 products manufactured at 188 sites in 35 countries• Employs 52,000 employees worldwide

A l l f $57 billi (2013 +1%)• Annual sales of $57 billion (2013 = +1%)• $1.7B in R&D investment (2012)

Our MissionTo passionately innovate what is essential to human progress by providing sustainable solutions to our customers

2010 – Dow becomes a Worldwide Partner and the “Official Chemistry Company” of the Olympic Games


of the Olympic Games

Dow Epoxy

•The world’s largest producer of epoxy resins & intermediates.• Broad product mix & strong global presence.• Eight manufacturing facilities in:Eight manufacturing facilities in:

• Asia Pacific – China, Korea• Europe – Germany, Italy• Latin America – BrazilLatin America Brazil• North America – USA

• Backward integration into feed-stocks that allows consistent,reliable product supplyreliable product supply.

• Almost 60 years of industry service• Strong commitment to product technology & solution innovation

Strong re investment in the business• Strong re-investment in the business• Continuously improving our business to:

• maintain reliable partner for our clients

• create shareholder value


• create shareholder value

Epoxy Products in Composites

Features:• Excellent adhesion to many (difficult) substrates• Low shrinkage upon cure• Excellent Chemical Resistance• Excellent Mechanical Properties• Good Heat ResistanceGood Heat Resistance• …

Often used to produce light weight composite parts that can replace metal articles.e g FRP pipes automotive parts storage tanks wind mill blades e.g. FRP pipes, automotive parts, storage tanks, wind-mill blades, ….

Toine Dinnissen, February 25th 2014 ™ Trademark of The Dow Chemical Company

Mechanical Properties ComparisonBlack Steel Stainless Steel Hastelloy® C GRPBlack Steel Stainless Steel

316Hastelloy® C GRP

(Mat & Roving)Density [gr/cm3] 7.8 7.9 8.9 1.5Tensile Modulus [GPa] 207 193 180 10 15Tensile Modulus [GPa] 207 193 180 10-15

Tensile Strength [MPa] 450 590 550 120-250

Heat Conductivity [W/mºC] 46 15 12 0.2

Thermal Expansion Coefficient [mm/mm ºC]x10-6

12 16 12 23

PE PP PVC PVDF GRPDensity [gr/cm3] 0.95 0.90 1.4 1.75 1.5Tensile Modulus [MPa] 80 80-130 300-350 1200 10 000-15 000Tensile Modulus [MPa] 80 80 130 300 350 1200 10,000 15,000

Tensile Strength [MPa] 30 30 60 50 120-250

Heat Distortion 40 45 75-100 90 100-200


Temperature [ºC]

All data are typical data and not to be construed as specifications

Fibre Reinforced Composites

Property Epoxy Unsaturated Polyester (UPR) and Epoxy Vinyl Ester Resin (EVER)

Phenolic

Cure mechanism Polymerization of resin plus hardener

Catalytic copolymerization

CondensationPolymerizationplus hardener copolymerization Polymerization

(produces water)Wet impregnation, typical

systemLiquid resins plus amine

or other hardenersStyrene-modified resins plus peroxide

catalystsLiquid phenolics plus acid

catalystsCure temperature (°C) 25 150 25 100 25 170Cure temperature (°C) 25-150 25-100 25-170

Typical cure time (min) 60-180 10-60 60-180Stability of resin (alone) Excellent Fair Poor

Cure shrinkage of system Low (2 3%) High (6 8%) HighCure-shrinkage of system Low (2-3%) High (6-8%) High

Adhesion to metal Excellent Fair Fair

Physical properties of cured laminate

Excellent Excellent Excellent/Bad (best heat resistance, most brittle), )

All data are typical data


All data are typical data and not to be construed as specifications

Epoxy Resin Route

Crude Oil Brine Salt

Naphta Electrolysis

Benzene Propylene CL2 NaOH

Cumene Allylchloride

OH O

OOH

HOClCa(OH)2

Cl

Acetone Phenol

EpichlorohydrinBisphenol-A

OH O

OHHO ClO

Polycarbonate Epoxy Resins


Standard Bisphenol-A epoxy resin

Bisphenol A

OCl

Epichlorohydrin

OCl

OHHOBisphenol A(A = Acetone)

Epichlorohydrin Epichlorohydrin

OOO O

DGEBA = Diglycidylether of Bisphenol A

BADGE = Bisphenol-A Diglycidylether

LER = standard liquid epoxy resin

D.E.R.™ 33X-series

Viscosity = ± 4000 mPa.s


Higher Molecular Weight Species

ClO+

OHHO

Resin n=0NaOH

OOO O

Diglycidyl ether of bisphenol A (DGEBA)NaOH

NaOHOO

OHO

OOO

n

Diglycidyl ether of bisphenol A - Oligomer n=1,2,3...


Typically between 5 and 15%Increase in viscosity

Mono-Hydrolyzed Resin (alpha-glycol)

OOO O

O OHCl

O

H2O

Diglycidyl ether of bisphenol A (DGEBA) OH

1,2-Diol / α-Glycol

Monohydrolyzed Resin (MHR)

function

Typically between 0.1 and 5%

OO

OH

OHO

Increase in viscosityIncrease in OH groups – can have impact on wetting, adhesion and reactivityD i E F ti lit


Decrease in Epoxy Functionality

Bisphenol-A Liquid Epoxy Resins

D.E.R.™ 332 Epoxy Resin

D.E.R. 330Epoxy Resin

D.E.R. 331™ Epoxy Resin

Epoxide Equivalent Weight [gr/eq]A S TM D 1652

171 – 175 176 ‐ 185 182 – 192A.S.T.M. D‐1652

Viscosity @ 25 °C [mPa.s]A.S.T.M. D‐445

4000 – 6000 7000 ‐ 10000 11000 ‐ 14000

340 / average EEW 1 97 1 89 1 82340 / average EEW 1.97 1.89 1.82

Mix with D.E.H.™ 24 hardener [phr] 14.0 13.5 13.0

Mix‐viscosity @ 25 °C [mPa.s] 900 1250 2250

Time to gel, 500 grams [min] 43 40 25

Heat Deflection Temperature [°C] 107 104 111

with Nadic‐Methyl‐Anhydride [°C] 156

with BF3‐MEA [°C] 168


Bisphenol-A Liquid Epoxy Resins

Resin D.E.R.™ 330 Epoxy Resin D.E.R. 331™ Epoxy Resin

D.E.H.™ 24 Hardener wt% Change wt% Change

Days; 7 28 120 7 28 120Days; 7 28 120 7 28 120

Sulphuric Acid (30%) 0.56 1.24 2.85 0.69 1.80 3.10

Acetone 0.17 0.74 4.48 0.45 2.10 7.70

Sodium Hydroxide (50%) 0.00 ‐0.06 ‐0.11 0.00 0.04 0.02

Jet‐fuel 0.03 ‐0.01 0.09 0.02 ‐0,01 0.09

Distilled Water 0.40 0.79 1.68 0.41 0.88 1.70

Thermal Degradation

Hours 100 200 300 500 100 200 300 500

eight loss @ 160 °C 0 95 0 95 1 32 1 41 0 71 1 00 1 40 1 60weight loss @ 160 °C 0.95 0.95 1.32 1.41 0.71 1.00 1.40 1.60

weight loss @ 210 °C 2.11 3.77 7.39 3.40 5.40 6.80 7.80


Recent Innovation More FlexibilityRecent Innovation – More FlexibilityColor 30 APHAAmine number 472 mg KOH/gViscosity 15 mPa.s @ 25 °CDensity 0.96 g/cm3Mol. Weight 230AHEW 63 gr/eq

D.E.R.™ 330 epoxy resin 100 100

D.E.H.™ 23 amine hardener 32 25

IPDA ‐ 5

Mix‐viscosity [mPa.s @ 23°C] 320 620

Tg [°C]; DSC 90 98

D.E.H. 23

80

90

100Flexural Strength [MPa] 102 131

Flexural Modulus [GPa] 3.14 3.38

Tensile Strength [MPa] 66 9 73 8

50

60

70

80Tensile Strength [MPa] 66.9 73.8

Izod impact Strength [cm‐kg/cm] 7.08 8.17

Elongation at Break [%] 10.0 8.0

20

30

40

20 2 28 32 36 0

Glass Transition Temperature [°C]

Heat Deflection Temperature [°C]


20 24 28 32 36 40 44

Theoretical mixing Ratio : 31.1 phr D.E.R. 330 epoxy resinEmpirical mixing ratio : 32.0 phr D.E.R. 330 epoxy resin

™ Trademark of The Dow Chemical Company

Glass Transition Temperature, TgTg = The Temperature Range where a polymer changesTg = The Temperature Range where a polymer changesg p g p y g

from Glass to Rubber

* Secondary Bonds are Broken * Molecular Mobility Increases

g p g p y gfrom Glass to Rubber

* Secondary Bonds are Broken * Molecular Mobility Increasesy* Free Volume Increases* Strength Decreases* Flexibility Increases* Internal Stress is Relieved

y* Free Volume Increases* Strength Decreases* Flexibility Increases* Internal Stress is Relieved

25

30 Slow CureCure is diffusion controlled

Glassy

15

20 VitrificationFast Cure

Tg = Cure Temp.

Liquid /Rubber

5

10

When the Tg of the Growing Polymer Reaches the Cure Temperature, The Polymer VitrifiesExtend of cure is determined by the Tg, Average Functionality

Liquid /Rubber

Cure is KineticallyC t ll d


0

0 2 4 6 8 1 0 1 2 1 4Cure Time

te d o cu e s dete ed by t e g, e age u ct o a tyControlled

Recent Innovation High TemperatureRecent Innovation – High Temperature4,4'-Methylenedianiline (MDA) is a suspected carcinogen. It is included in the "substances of very high concern" list of the European Chemicals Agency (ECHA)

DiethyleneTolueneDiamine(ECHA).Pure methylenedianiline is a highly toxic, colorless solid.May be fatal if swallowed, inhaled or absorbed through skin. Causes irritation to the skin, eyes and respiratory tract. Combustible solid or liquid when heated. p y qMay cause methemoglobinemia. Affects blood, cardiovascular system, central nervous system, liver and kidneys and may cause cancer.

Ancamine DL-50 (MDA-blend)Highly viscous / solid = light to dark brown @ 50,000 - 55,000 mPa.s (AHEW = 51 gr/eq)

DETDALow viscosity liquid = clear amber liquid @ 100 200 mPa s (AHEW = 46 gr/eq)


Low viscosity liquid = clear amber liquid @ 100 - 200 mPa.s (AHEW = 46 gr/eq)Need 10% less per 100 kilo epoxyMuch lower viscosity = allows blending and use at much lowers temperatures (room temperature)

D.E.H.™ 650 Curing Agent


R t I ti Hi h T tL b li di EC Di i Recent Innovation – Higher TemperatureLabeling according to EC Directives:Hazard Symbol: Xn ‐ Harmful

N ‐ Dangerous to the EnvironmentRisk Phrases: R 21/22 ‐ Harmful in contact with skin and if swallowed.

R 48/22 ‐ Harmful: danger of serious damage to health by prolonged exposure if swallowedR 36 ‐ Irritating to eyes

ASTM D‐7903 point Flex

MDA Ref. D.E.H.™ 650

R 36 Irritating to eyes.R 50/5 ‐ very toxic to aquatic organisms, may cause long‐term adverse effect in aquatic environment

D E H ™ 650 hardener @ 37 °Cp

Tg (DSC, °C) 167 178

Flexural Strength [MPa]

110 116

D.E.H. 650 hardener @ 37 C

Modulus [MPa] 2707 3137

Strain [%] 8.3 6.3

Stress @ Break [MPa]

106 116[MPa]

K1c Fracture Toughness

0.76 0.61

MDA-reference @ 57 °C


Pot-life 150 grams


Bisphenol-F Epoxy Resins

OH OH

OCl

O

O

O

O

Bisphenol F(F = Formaldehyde)

EpichlorohydrinDiglycidylether of Bisphenol-F

O

OO

OO

O

O

O

O

O

O

para - para

O

OO

O

OO

nO

O

ortho - para

ortho - ortho


D.E.R.™ 354 liquid epoxy resin


Epoxy Novolac Resins

OH OHOH

O

O O

O O

O

OCl

+n

n

Phenol Novolac Epichlorohydrin Epoxy Novolac Resin

n = 0 - 0.2 for D.E.R.™ 354 liquid bisphenol-F epoxy resinn = 0.4 for D.E.N.™ 425 LIQUID epoxy novolac resinn = 0 8 for D E N 431 epoxy novolac resinn = 0.8 for D.E.N. 431 epoxy novolac resinn = 1.6 for D.E.N. 438™ epoxy novolac resinn= 1.8 for D.E.N. 439 epoxy novolac resin

Higher epoxy functionality ===> Higher crosslink density Excellent solvent/chemical resistance.Higher Temperature ResistanceGel at lower conversion


Gel at lower conversion


MTHPA versus DETDAD E H ™ 70 [MTHPA] D E H 650 [DETDA]D.E.H. 70 [MTHPA] D.E.H. 650 [DETDA]

Resin D.E.R.™ 330 D.E.N.™ 438™ D.E.R.™ 330 D.E.N.™ 438™

EEW [gr/eq] 176 – 185 176 - 181 176 – 185 176 - 181

Mix-ratio [phr] D.E.H. 70 / MI85 / 1

D.E.H. 70 / MI85 / 1

26.0 26.3

Cure Schedule; Hours @ °C 2 hrs @ 85 °C3 hrs @ 150 °C

2 hrs @ 85 °C2 hrs @ 150°C2 hrs @ 200 °C

2 hrs @ 120 °C2 hrs @ 177 °C

2 hrs @ 120 °C2 hrs @ 177°C2 hrs @ 225 °C2 hrs @ 200 C 2 hrs @ 225 C

Glass Transition Temperature [°C] 148 149 182 220

Coefficient of Linear Expansion [ppm/°C] 70 66 74 69

%Water Absorption, 2 weeks boil [%] 1.45 1.49 2.35 2.47

Flexural Strength [MPa] 128 138 108 110

Flexural Modulus [GPa] 3.27 3.51 2.64 3.06

Strain @ Yield [%] 6.7 6.7 6.9 6.1

Cured density [gr/cm3] 1.190 1.224 1.140 1.210


Gelation versus Functionality

Active Groups per Molecule 2 Functional Epoxy Groups

OO

OHO

OOO

n

5 Functional Amine-Hydrogen Groups

Functionality ≤ 2 Linear Molecular Weight BuildFunctionality ≤ 2 Linear Molecular Weight Build

A A B B A A B B

A BNo Cross linking

Functionality > 2 Cross Linking


Functionality > 2 Cross LinkingCross linking leads to gelation

Gelation

∞Covalently Bonded Polymer Network

Molecular Weight Infinitely High∞Molecular Weight Infinitely High

Gel = “One” macromolecule

S l L l l i h f i

Polymer Properties develop at Gel-Point

Sol = Low molecular weight fraction

y p p

Solvent Soluble Solvent In-soluble

Sol Gel

M No Physical StrengthFluid Behavior50% of Shrinkage

Physical StrengthElastic Behavior50% of Shrinkage

Gel PointMonomers


Gel-point can be Predicted

/ Carothers: % Cure @ Gel Ξ 2 / favg

Flory: % Cure @ Gel Ξ 1[1 + (f-2)]1/2

Gelation is Controlled by Functionality

[1 + (f-2)]

react 3 moles of D E R ™330 epoxy resin = 6 reactive groupsreact 3 moles of D.E.R. 330 epoxy resin = 6 reactive groupswith 2 moles of amino-ethyl piperazine = 6 reactive groupsaverage functionality = 12 groups / 5 mole = 2.4Gel Point ~ 2/2.4 ~ 83% cure at Gelreact 7 moles of D E R ™330 epoxy resin = 14 reactive groupsreact 7 moles of D.E.R.™330 epoxy resin = 14 reactive groupswith 2 moles of tetra-ethylene-pentamine = 14 reactive groupsaverage functionality = 28 groups / 9 mole = 3.11Gel Point ~ 2/3.11 ~ 64% cure at Gelreact 14 moles of D.E.N.™425 epoxy resin = 35 reactive groupswith 5 moles of tetra-ethylene-pentamine = 35 reactive groupsaverage functionality = 70 groups / 19 mole = 3.68Gel Point ~ 2/3.68 ~ 54% cure at Gel


Gel Point 2/3.68 54% cure at Gel

Higher Functionality is Early Mould Release™ Trademark of The Dow Chemical Company

Crosslink Density:

High Crosslink DensityHigh Crosslink DensityHigh Crosslink DensityHigh Crosslink DensityHigh Chemical & Heat ResistanceStrong, RigidHeat Cure Needed

D.E.N.™438™

D.E.R.™324

Low Crosslink DensityLow Crosslink DensityModerate Chemical & Heat Resistance Flexible ToughFlexible, ToughCure at Lower Temperatures

Fl l St th 21 000 iHigh X-Link DensityD.E.R.™ 331 / Imicure(1) EMI 24Cure @ 150 °C

Flexural Strength 21,000 psiFlexural Modulus 540,000 psiElongation @ Break 2 %Glass Transition 160 °C3 h t b il 1 % t i

Low X-Link DensityD.E.R.™ 331 / Jeffamine(2) D-400C @ 30 °C

3 hr acetone boil 1 %wt gain

Flexural Strength 11,200 psiFlexural Modulus 406,000 psi


Cure @ 30 °C Elongation @ Break 60 %Glass Transition 30 °C3 hr acetone boil 29 %wt gain


Tg versus Cured Property

Tg < Service Temperature Tg > Service Temperature

Epoxy Cycloaliphatic Amine Epo Pol amide Epoxy-Cycloaliphatic Amine Cured @ 100°CTg = 110°CService Temperature 80°C

Epoxy-Polyamide Cured @ 25°CTg = 30°CService Temperature 40°C

Glassy, RigidLow Impact ResistanceHigh Internal StressHigher Barrier Properties

Rubbery, ToughHigh Impact ResistanceLow Internal StressLower Barrier Properties

Functionality TgGel PointCrosslinking

Gel PointDry TimePot Life

Chemical ResistanceStrength

RheologyChemical ResistanceShrinkage

% CureGlass/RubberInternal Stress


ShrinkageReactivity

D.E.N.™ 440 High FunctionalityEpoxy Novolac Resin

Part A D.E.N.™ 438™ epoxy novolac

D.E.N. 440 epoxy novolac

Epoxy Resin 80.2 80.2

Part B

D.E.N.™ 425 (f=2.5)

Part B

D.E.N. 431 19.8 19.8

DICY 5.6 5.6

UREA 2 8 2 8D.E.N. 431 (f=2.8)

D.E.N. 438™ (f=3.6)

UREA 2.8 2.8

Uncured rheology properties

D.E.N. 439 (f=3.8)

D.E.N. 440 (f=4.5 !!!)

η* @ 80oC (Pa*s) 1.5 6.4G* @ 1rad/s (MPa@25°C)) 0.005 0.21

Cured polymer tiproperties

Tonset (oC) 117 117

Tg (oC)160oC cured 193 215

Flexure Modulus (GPa) *2 93 *3 53


Flexure Modulus (GPa) 2.93 3.53

KIC (MPa*m0.5) *0.58 *0.52


SummaryThe Dow Chemical Company Epoxy business is Committed and Reliable partners for our Clients

• High Quality standard Raw Materials• D E R™ 33x epoxy resins• D.E.R 33x epoxy resins• D.E.N.™ 43x epoxy novolac resins• D.E.H.™ curing agents (incl. D.E.H. 70 anhydride hardener)

• Higher Temperature Performanceg p• D.E.H. 650 curing agent• D.E.N. 440 epoxy novolac resin• FORTEGRA™ epoxy toughening technology

• Viscosity• Diluents (mono-, di- or multi-functional); D.E.R.™ 7xx series• Bisphenol-F epoxy resin(s); D.E.R. 354, 351, 352

• Cure rate• Room temperature / Latent master-batch accelerated resins; D.E.R. 34xx• Long(er) pot-life amine hardeners (D.E.H™ 23 or D.E.H. 2132 curing agent)

Fl ibilit


• Flexibility• Amines (e.g. D.E.H. 23), diluents (e.g. D.E.R. 732P) or

D.E.R. 3913 Flexible epoxy resins™ Trademark of The Dow Chemical Company

Контакты

Meet us for face-to-face discussion at the EXPO; Booth G05

Дау Юроп, Московское ПредставительствоДмитрий Белобородов[email protected]

Dow Europe GmbHToine Dinnissen

[email protected]

ЗАО "НЕО Кемикал"Юлия ТашкиноваЮлия Ташкинова

[email protected](8313) 32-06-74, 33-68-68, 32-59-63


DOW Epoxy ProductsN P d t TName Product Type

D.E.R.™ 31x / 31xx Liquid epoxy resin with non‐reactive diluents / additives

D.E.R. 32x / 32xx Liquid epoxy resin with reactive diluent(s)

D.E.R. 33x / 33xx Unmodified bisphenol‐A Epoxy Resin

D.E.R. 34x / 34xx Accelerated liquid epoxy resin

D.E.R. 35x / 35xx Bisphenol‐F epoxy resin containing liquid epoxy resin, might contain reactiveD.E.R. 35x / 35xx Bisphenol F epoxy resin containing liquid epoxy resin, might contain reactive diluent (3rd digit can indicate the main reactive diluent type)

D.E.R. 36x / 37x Few “exotic” grades

D.E.R. 38x Only D.E.R. 383 = US version of D.E.R. 330y

D.E.R. 39xx Specialty epoxy resin

D.E.R. 5xx Brominated epoxy resin

D E R 6 S lid iD.E.R. 6xxx Solid epoxy resins

D.E.R. 9xx Emulsions, Dispersions or water‐emulsifiable epoxy resins


DOW Curing Agents

Name Product Type

D.E.H.™ 1xx / 1xxx Polyamide and Amidoamine curing agents

D.E.H. 2x Polyamine building blocksy g

D.E.H. 2xx / 2xxx Modified polyamine(s) / blends

D.E.H. 3x AEP and Accelerators

D E H 4 / 4 F l d E A i ddD.E.H. 4xx / 4xxx Formulated Epoxy – Amine adducts

D.E.H. 5x Simple adduct / blend (her. Dow)

D.E.H. 5xx Formulated Epoxy – Amine adducts; US only (her. GNS)

D.E.H. 6xx Fast & Low temperature curing agents

D.E.H. 7x Anhydride

D.E.H. 8x Phenolic hardeners (powder coatings)D.E.H. 8x Phenolic hardeners (powder coatings)

D.E.H. 8xx Curing agents for aqueous systems.


Recent Innovation - Low Viscosity

Designation Type

D E R ™ 72 f i l i dil


D.E.R.™ 72x mono‐functional reactive diluents

D.E.R. 73x di‐functional reactive diluents

D.E.R. 74x Multi‐functional reactive diluents


140225 composites expo 2014

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