Michiel s PEA

8/18/2019 Michiel s PEA

1/52

New Amine Technology to Improve

Liquid Epoxy infusion process and EnhanceProductivity for larger offshore Rotor blades

Polymer Science of Everyday ThingsEnergy Generation and storageACS National meeting, August 19-23 , 2012

Huntsman CorporationPerformance Products Division

Everberg, Belgium

Martin M MichielsCommercial Director Alternate Energy


2/52

Page 2 ACS National meeting, Aug 19 – 23,2012, Philadelphia Performance Products

Presentation Outline

Huntsman Introduction

Introduction to Rotor blades,

materials history Materials and Basic chemistries

used today

Why develop new amine epoxycuring agents

Next generation amine hardener

development and performanceproperties.

Summary


3/52


Introduction: Business Portfolio

Polyurethanes

Adhesives,Coatings &Elastomers

Appliances

Automotive

Composite

Wood ProductsFootwear

Furniture

Insulation

TPU

AdvancedMaterials

FormulatedSystems

Specialty

Components

Base Resins

Pigments

TitaniumDioxide

PerformanceProducts

PerformanceSpecialties

PerformanceIntermediates

MaleicAnhydride &

Licensing

Apparel &Home Textiles

SpecialtyTextiles

Differentiated Inorganic

Textile EffectsCompany2011revenue:> $ 10 b

Wide range of:

Polyetheramines

Specialty Amines

New

CycloaliphaticAmines


4/52Page 4 ACS National meeting, Aug 19 – 23,2012, Philadelphia Performance Products

Global Presence

Operating more

than 75manufacturing andR&D facilities in

30 countriesworldwide.


5/52Page 5 ACS National meeting, Aug 19 – 23,2012, Philadelphia Performance Products

Geographically Diverse2Q12 LTM Revenue Distribution

U.S. & Canada33%

Europe29%

Asia Pacific21%

Rest of World

17%

~12,000 Employees

EAME

45%

APAC

30%

U.S. &

Canada

18%

Rest of

World

7%


6/52


Specialty Amines Global Producer

JEFFLINK ®

Amines

JEFFAMINE ®

Polyetheramines

SURFONAMINE ®

Amines

Huntsman Performance Products Division (HPP) is WW one of

the largest producer of amines

Manufacturing in America, Europe, Middle East and Asia

Wide variety of amine products and technologies

Worldwide investment in dedicated facilities to guarantee globalsupply

Global leader in Polyether amineproducts

ELASTAMINE ®

Amines

JEFFCAT ®

Amines


7/52



Introduction



used today




Summary


8/52


Introduction to rotor blades

Since early recorded history (200 BC) , people have beenharnessing the energy of the wind.

Miguel de Cervantes immortalised the windmill with Don Quijote ofLa Mancha.

De La Mancha windmills

are still standing todaybut much has changedsince the 17th century

wind farms

Wind turbines arebecoming increasing

larger


9/52


0

80,000

160,000

240,000

320,000

400,000

0

20,000

40,000

60,000

80,000

100,000

2011 2012 2013 2014 2015 2016

C u m u l a

t i v e m

i l l . E u r o

m

i l l . E u r o

Forecast world Offshore 2011 Onshore 2011

Forecast onshore Cumulative marketSource: BTM Consult - A Part of Navigant - March 2012

The Global Wind Energy MarketTurnover exceeded 65 billion USD


10/52


0

50,000

100,000

150,000

200,000

250,000

0

9,000

18,000

27,000

36,000

45,000

1983 1990 1995 2000 2005 2011

C u m u

l a t i v e M W

M W

p e r y e a r

Year

Source: BTM Consult - A Part of Navi ant - March 2012

What is the market size ? MW/a GW/a


11/52


Introduction to rotor blades

The latest generation wind turbines has blades withdiameters approaching:

A) The width of the St Louis Gateway Arch ?B) Double the wing span of Airbus A 380 ?C) Three times the length of a football field ?

D) All of the above ?

ANSWER ?

“ D “Largest turbine prototype installed today have diameter of

155 meters and with a 6 -7 MW output.


12/52


Blade Materials :past History

First blades where made from wood andduring the 1960’s and 70’s metal was used .

Polyester (UPR)started in the early 80’s


13/52



Introduction



used today




Summary


14/52


Current Blade Materials Technology

Polyester (UPR)Early 80’s

Liquid Epoxies

Wet Lay-upLate 80’s

Infusion MoldingStart 1995

Prepreg

Solid epoxy ResinFull prepreg 1996


15/52


WW the LER

infusion movedfrom 25% in2000 to 71 % in2010


16/52


Today LER Infusion technologyis the dominant product and process technology used

1999 2000 2001 2002 2003 2004 2005 2006 2007 2008

Tonnes

Polyester

Infusion

Total pre preg

Wet lay up


17/52


What is Unsaturated Polyester Resin(UPR)?


18/52


NH

H

R1

+

O

R R

HO NH

R1

Epoxy Primary amine

Aminoalcohol,secondary amine

When the curing agent is a primary diamine like a JEFFAMINE ® PEAs, two

reactions take place.

2. In a second step, the secondary aminecan react with another epoxy, or oxirane,

group to further build molecular weight

and to give crosslinking

Basic Epoxy-Amine Crosslinking ReactionThermoset Network

N

N

OH

OH

OH

N

N

OH

OH

N

HO

N

OH

N

N

OH

OH

N

HON

OH

OH

OH

OH

N

HO

N

OH

N

OH

HO

N

HO

N

HON

N

OH

OH

N

1. Linear MW build up: the oxirane ring of the epoxy resin opens up to

produce an aminoalcohol


19/52


Commitment to Polyether Amines made thisrapid development of using the infusion

processing possible

In 1992, Texaco Chemical/ Huntsman demonstrated inEurope the concept of using Polyether amines

combined with cyclo aliphatic amines for infusionprocess

In June1994, first commercial application of LERinfusion blade production using PEAs together withcyclo aliphatic amines had started

In 1995 fully commercial series production started.

Since 1995 Huntsman guaranteed its manufacturingcapacity to be available for the growth of that industry


20/52


Conventional Hardeners Used Today

NH2

NH2

JEFFAMINE ® polyoxypropylene amines

Low viscosity, good fibre wetting

Low temperature curing, long pot life

Lower glass transition temperature (Tg),toughness, higher elongation

Cycloaliphatic amines, such as isophorone

diamine (IPDA)

Low viscosity

Faster cure

Higher Tg, less flexible Curing at an elevated temperature is

necessary to give the best properties

Accelerators

(x

)H2NO

NH2

CH3 CH3


21/52



22/52


Fatigue testing Montana state


23/52


Fatigue testing Montana stateUniversity (1)

Copyright Montana State

Fatigue testing Montana state


24/52


Fatigue testing Montana stateUniversity (2)

Copyright Montana State


25/52



Introduction

Introduction to Rotor blades,materials history

Materials and Basic chemistriesused today




Summary

Diameter evolution continues to grow


26/52


Diameter evolution continues to grow

Why Develop New Amine Epoxy


27/52


Why Develop New Amine EpoxyCuring Agents

Increasing size evolution for rotor blades leads to industryrequests for LER infusion systems that can achieve

A longer pot life - open time – with good cure speed

Lower viscosity - fast infusion

Reliable cure with lower exotherm

Faster property development (green strength)

Reduced manufacturing cycle time – increasedproductivity

Improve mechanical properties like thoughness andbetter fatigue resistance, improved processing


28/52


Largest Prototype OffshoreTurbine

Siemens SWT 6.0- 154 MW

154 m diameter, 75 m long,246 feet.

Copyright Siemens Windpower


29/52



Introduction






Summary


30/52


Large rotor blade requirements (1)

Vacuum infusion process – mould design

Multi-point injection line

Moulds:

Current Heated with hot water, which means temperature limited to70 - 75ºC

New design is Electrically heated , computer controlled procesoption to heat to 80-85 ºC

Max. cure temperature is 80ºC because of heat sensitive sandwichstructures inside

Lower exotherm is required to avoid scorching and stress from shrinkage.Exotherm should not exceed 80ºC

During injection, temperature on the mould is kept low (40ºC or below) bycooling to avoid exothermic issues.

Once the peak exotherm is reached (80ºC max.), then put some heat onthe moulds


31/52


WTG rotor blade requirements (2)

Vacuum infusion process – processing criteria

Formulation viscosity

Initial mix viscosity:

200 - 350 mPa.s at 25ºC

150 - 200 mPa.s at 30ºC, 100-150 mPa.s at 40ºC

Reactivity

Injection temperature / injection times

30ºC / 1 to 1.5 hrs

40ºC / 1 to 1.5 hours

System open time: min. 1.5 hours

Exotherm of blade system should not exceed 80ºC Baking cycles:

Max. 6 hrs at 70ºC to 80ºC (mould temperature – oven temperature)


32/52


WTG rotor blade requirements (3)

Vacuum infusion process – performance criteria Glass transition temperature

Onset Tg of 70ºC to 75ºC

Which means: midpoint Tg of 75ºC to 80ºC. Inflection Tg is about 2ºC >midpoint Tg

Tensile properties of binder (not filled) system – received from formulators

70 MPa tensile strength

5-8 % elongation

3 GPa tensile modulus

Green strength

For demoulding, the curing system should have reached min. 80% of fullcured properties

Using the min. 80% (80-90%) rule on the onset Tg of 70ºC-75ºC wouldmean that a curing system would need to have an onset Tg of min. 62ºC(calculated from the averages - 85% cure of onset Tg of 72.5ºC)


33/52


Conventional Hardeners Used Today

NH2

NH2

JEFFAMINE ® polyoxypropylene amines

Low viscosity, good fibre wetting

Low temperature curing, long pot life

Lower glass transition temperature (Tg),toughness, higher elongation

Cycloaliphatic amines, such as isophorone

diamine (IPDA) Low viscosity

Faster cure

Higher Tg, less flexible Curing at an elevated temperature is

necessary to give the best properties

Accelerators

(x

)H2NO

NH2

CH3 CH3

Epoxy Infusion Formulations


34/52


p yMaterials

Hardeners

Commercial 2-component amine hardener A

Commercial 3-component amine hardener B

Longer open time 2-component developmentalhardeners C & D Based on:

Commercial JEFFAMINE ® polyetheramine (PEA)

New developmental polyetheramines Standard Cycloaliphatic amines

Developmental Cycloaliphatic amines

Accelerator

Epoxy resin

Diluted Bisphenol A/F epoxy resin

EEW = 161-181. Viscosity = 1100-1450 mPa.s

New Amine Hardeners


35/52


Slower – more Latent - Polyetheramine

Slow PEA Curing Agent B

New polyether backbone structure, with larger group

hindrance (aminoalkyl termination) and lower viscosity

Benefits:

Gives improved performance in terms of

Better control of reactivity - thus longer working times

Lower exotherm

Improved Tg performance

Larger groups -

more hindrance,

slower reaction

H2N

NH2

New Amine Hardeners


36/52


Cyclo Curing Agent C Cyclo Curing Agent D

Benefits:

Low viscosity and low colour liquids

Faster curing, at lower mold temperature

Provide enhanced Tg, modulus and hardness

Provide faster build-up of Tg and strength

Improved demoulding time

Improved mechanical properties

Rigid

SegmentH2N

NH2

Novel Cycloaliphatic Amines

New Amine Hardeners


37/52


RFD Curing Agent E

Novel aliphatic amine with both rigid (cycloaliphatic) and

flexible (polyetheramine) segments

Benefits:

Higher Tg capability - up to 20°

C higher than conventionalPEA

Excellent mechanical properties

Faster viscosity growth and strength development

H2N NH2

Rigid

Segment

Flexible Segment

Novel Rigi-Flex Amine

Epoxy Performance PropertiesT i O i


38/52


Testing Overview

Thermal properties (Tg) by Differential Scanning Calorimetry (DSC) On cured castings using different baking cycles

Tg development as function of baking time & temperature(green strength)

Isothermal viscosity - cure profiles - at 30°C, at 40°C

Gel time - exotherm temperature testing

Mechanical property testing – after different baking cycles

Tensile properties

Flexural three-point bend test Durometer hardness

Development of strength as function of baking time &temperature (green strength)

New Polyetheramine ComparisonVi i B ild 0 C F i f Ti


39/52


Viscosity Build at 40 ° °° ° C as Function of Time

PEA Curing Agent A is faster curing than conventional PEA

PEA Curing Agent B is our slowest curing PEA – LATENCY EFFECT

C ure P rof ile at 40°C w ith di luted B is A/F e po xy resin

0

0.5

1

1.5

2

0 5 0 100 150 2 00 2 50 3 00

T i m e ( m i n )

V i s c o s i t y ( P a . s )

A ccelerator (87 m Pa.s) Conventional PE A (66 m Pa.s)PE A Curing Agent A (111 m Pa.s) S low PEA Curing A gent B (115 m P a.s )

( In it ia l mix v iscosi ty is s how nin the legend in paren th eses)

Cycloaliphatic Amine Curative ComparisonVi it B ild t 40°°°°C F ti f Ti


40/52


Viscosity Build at 40 ° °° ° C as Function of Time

The initial mix viscosity is shown in the legend in parentheses

Initial viscosity and viscosity build, with a diluted Bis A/F epoxyresin, EEW 161-181, 1200 mPa.s

C u r e P r o f i le a t 4 0 °C , w it h D i lu t e d B i s A / F E p o x y R e s in

0

1

2

3

4

0 2 0 4 0 60 8 0 1 00 1 2 0 1 4 0

T im e (m in )

V i s c o s

i t y ( P a . s

)

A c c e le ra to r (8 7 m P a .s ) C yc lo C u r in g A g e n t C (1 5 5 m P a .s )

IP D A a m in e (1 8 3 m P a .s ) C yc lo C u r in g A g e n t D (1 9 8 m P a .s )

R F D C u r in g A g e n t E ( 1 4 7 m P a . s )

Gel Time Tests – 200 gram Mass atRoom Temperature


41/52


Room TemperatureGel Time Tests (200 g)

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

9,000

10,000

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0

Time (hours)

B r o o k

f i e

l d V i s c o s

i t y

i n

m P a . s

Conventional I (2 comp.) Conventional II (3 comp.)

Form. III with New PEA A / IPDA Form. IV with Conv. PEA / Cyclo C

Form. V with New PEA A / Cyclo C Form VI with RFD Curing Agent E

Form. VII with Slow PEA B / IPDA

All formulations use a 1:1 amine-hydrogen to epoxide stoichiometry.

Latency behaviour

New Polyetheramine ComparisonThermal Properties by DSC


42/52


Formulations and thermal (Tg) properties with a diluted Bis A/Fepoxy resin, EEW 161-181, 1200 mPa.s

1 2 3

Part A: pbw Diluted Bis A/F epoxy resin 100 100 100

Part B: phr

Conventional PPG diamine 35.5

PEA Curing Agent A 31

Slow PEA Curing Agent B 33

Tg, °C, @ 6 hrs at 70°C 63.5 76 70

Tg, °C, @ 6 hrs at 80°C 65 78.5 76.5

Thermal Properties by DSC

New PEA Curing Agent A provides about 12°C higher Tg

compared to the conventional PPG based diamine

DSC heating rate of 20°C/min. Inflection method used for Tg

Temperature Rise During Gel TimeTesting 200 g Mass at RT


43/52


Testing – 200 g Mass at RT

Tem perature Rise D uring G el Time Testing (200 g)

10

30

50

70

90

110

130

150

170

190

0.0 1.0 2 .0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time (hours)

T e m p e r a

t u r e ( º C ) n e a r c e n

t e r

Conventional I (2 comp.) Conventional II (3 comp.)

Form. III w ith New PEA A / IPDA Form. IV w ith Conv. PEA / Cyclo C

Form. V w ith New PEA A / Cyclo C Form VI w ith RFD Curing Agent E

Form. V II with Slow PEA B / IPDA

All formulations use a 1:1 am ine-hydrogen to epoxide stoichiom etry.

Low exotherm

Formulation Overview –Properties with Conventional Baking Cycles


44/52


Formulation Convent. I Convent. II III IV V VI VII VIII

Part A: pbw2 comp. 3 comp.

New PEA A /

IPDA

Conv. PEA /

Cyclo C

New PEA A /

Cyclo CRFD-E

Slow PEA B /

IPDA

Slow PEA B /

Cyclo C

Diluted Bis A/F

eepoxy resin 100 100 100 100 100 100 100 100

Part B: (wt.%) Optimum phr 34 33 29.5 31 29 39 35 32

Initial mix

vviscosity, mPa.s

At 30°C 172 260 194 248 210 358 195 175 At 40°C 111 109 103 137 127 147 106 110

1st heat

iinflection Tg, °C

@ 6 hrs at 70°C 77 (**) 79 (**) 82.5 (*) 78 (*) 84 (*) 84.5 (*) 80 83

@ 6 hrs at 80°C 81 (*) 82 89 84.5 90 90.5 84 86.5

Properties with Conventional Baking Cycles

(*) About 2 to 4°C difference between 1st and 2nd heat.(**) About 5°C to 8°C difference between 1st and 2nd heat.


Performance with Non ConventionalBaking Conditions


45/52


Development of glass transition temperature (Tg)

Development of mechanical strength

At lower baking temperatures

In the 50°C-60°C range

After shorter baking times 1.5 to 3 hours

Baking Conditions

TG Developmentat Different Baking Conditions


46/52


1st

heat inflection point Tg data

Formulation Convent. I Convent. II III IV V VI

2 comp. 3 comp.New PEA A /

IPDA

Conv. PEA /

Cyclo C

New PEA A /

Cyclo CRFD-E

Optimum phr of Part B 34 33 29.5 31 29 39

1st heat inflect. Tg, °C

@ 1.5 hrs at 70°C 54 (77) 66.5 (79) 69 (82.5) 72 (78) 76 (84) 70.5 (84.5) @ 6 hrs at 50°C 57.5 60 56 63 65.5 63.5

@ 3 hrs at 55°C No meas.TG 48.5 47 55 63 60

@ 1.5 hrs at 80°C 75 (81) 82 (82) 76 (89) 79.5 (84.5) 84 (90) 86.5 (90.5)

83%

The values in parenthesis are the Tg value after 6 hrs

cure at the particular temperature.

90%92%84%70% 84%

at Different Baking Conditions

Reaching faster higher Tg


Tensile Properties Development @Baking for 3 hrs at 70°°°°C


47/52


Baking for 3 hrs at 70 C

The values in ( ) are the tensile properties for

baking cycle of 6 hrs at 80°C.

Formulation Convent. I Convent. II III IV V VI VII VIII

Part A: pbw

2-comp. 3-compNew PEA A /

IPDA

Conv. PEA /

Cyclo C

New PEA A /

Cyclo CRFD-E

Slow PEA B

/ IPDA

Slow PEA B

/ Cyclo C

Diluted Bis A/Fepoxy resin

(EEW 172) 100 100 100 100 100 100 100 100

Part B: (wt.%)

Optimum phr of Part B (DSC) 34 33 29.5 31 29 39 35 32

Shore D, 0 - 10 sec 78.5 - 76.5 81.5 - 80.5 78.5 - 76.5 n.a. n.a. 79 - 77 80.5 - 79.5 81.5 - 80

Tensile modulus, GPa 2.5 (3.1) 3.1 (3.0) 2.8 (3.2) 3.1 (3.0) 3.2 (3.0) 2.8 (2.8) 3.1 (3.0) 3.1 (2.9)

Max. tensile strength, M Pa 37 (76.5) 48 (78) 40.3 (83.5) 75.5 (78.7) 75 (81.7) 62 (70.5) 64 (71.2) 66.3 (69.9)

% Elongation at max strength 2.6 (4.4) 1.7 (4.5) 2.3 (4.2) 4.1 (4.3) 3.5 (4.8) 3.1 (4.1) 3.3 (4.1) 3.5 (4.3)

% Elongation at break 11 (6.3) 1.7 (6.0) 3.4 (5.5) 5.9 (5.8) 4.2 (6.7) 3.7 (5.1) 5.9 (6.2) 4.9 (6.6)

Faster development of tensile

strength and modulus



48/52



Introduction






Summary

New Amine Curing Agents for NextGeneration Rotor Blades – Summary 1


49/52


Generation Rotor Blades Summary 1

The new epoxy amine curatives offer

Property performance improvements Semi latent effect without catalytic cure

No catalytic cure → controlled cure & uniform properties

Controlled exotherm Higher Tg capability

Homogeneous, and faster Tg and strength development

H2NNH2

Rigid

Segment

Flexible polyethersegmentH2N

NH2

New flexiblepolyether segment

New Amine Curing Agents for NextGeneration Rotor Blades – Summary 2


50/52


The new epoxy amine curatives offer:

Blade process improvements

Longer infusion time

Faster property (green strength) development

Allows curing at lower baking temperatures and/orshorter baking times

Indicates faster demoulding

Which means potential reduction in manufacturingprocess time - increased productivity

Potential energy cost savings

Generation Rotor Blades Summary 2

New

Summary


51/52


JEFFLINK®

Chain extenders

NewPEAswith

higher Tgcapability

Lowviscosity – fast

infusion

Cycloamine

replacingIPDA/

Accel.

Longerpot life –reactivitycontrol

Faster Tgand

strengthbuild-up

Potentialcycletime

reduction

Potentialenergy

costsavings

Fastercure -

without

catalyst

New Amine EpoxyCuratives for the

Formulator

y

Open thedoors for

newapplications


52/52

Michiel s PEA

Documents

Transcript of Michiel s PEA