DuPont Vamac Ultra. New AEM Polymers and Developments - Meeting Demands of Modern Engine Technology

1 DuPont™ Vamac® Ultra New AEM Polymers and Developments Meeting Demands of Modern Engine Technology Klaus Kammerer Technical Consultant Vamac® & Vi...
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DuPont™ Vamac® Ultra

New AEM Polymers and Developments Meeting Demands of Modern Engine Technology Klaus Kammerer Technical Consultant Vamac® & Viton® DuPont Deutschland GmbH 10/3/2012

DKT 2012, Nuremberg

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Agenda

• Overview on Vamac® ethylene acrylic elastomer (AEM) Terpolymers • Injection Molding grades • Grades for Turbo Charger Hoses • Heat & Fluid Ageing • Compounding Variations • Comparison to other Polymers, Compressive Stress Relaxation • Test results after Immersion in new Automotive fluids

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Vamac® on the Elastomer’s Map Classification by ASTM D-2000 V Solutions Space Heat Res.

Sealing & Hose Applications

250

Viton®

70 hrs 225

Silicone

Applications with min. temperature requirements of 165 degrees

200

Fluorosilicone HiTemp-ACM

Vamac®

175

Polyacrylate (ACM)

165 150

EPDM HNBR CPE

125

Applications with reduced swell

Neoprene 100

70

Butyl

Epichlorohydrin Nitrile NBR/PVC

Styrene Butadiene Natural Rubber No Req

170

120

100

80

60

40

20

10

Oil Resistance % Swell in IRM 903 Oil 10/3/2012

4

4

Chemical Structure

New products AEM G -Type Terpolymer

(CH2-CH2)x–

(CH-CH2)y | O=C | OCH3

(A) Monomers Choice and Ratio –(R)z | C=O | CO2H

(B) Molecular Weight Distribution Optimization.

(C) Adjustments at Finishing step. Ethylene

Methyl Acrylate Acidic Cure Site

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Vamac® - Standard and High Viscosity ‘Ultra’ Grades High Viscosity Grades Standard Grade ML (1+4) 100°C, Tg

High Viscosity Grade ML (1+4) 100°C, Tg

Vamac® G 16.5 MU, -30 °C

Vamac® GXF 17.5 MU, -31 °C

Vamac® GLS 18.5 MU, -24 °C

Vamac® Ultra IP (formerly VMX-3040) 29 MU, -31 °C

Vamac® Ultra HT (formerly VMX-3038) 30 MU, -32 °C

Vamac® VMX-3110 30 MU, -25 °C

Vamac® VMX-3121 30 MU, -26 °C Low oil swell version of Ultra HT Major Features

Best Compression Set, Fast Cure

Best Dynamic Fatigue Resistance

Best Compression Set, Fast Cure, Low Oil swell

Main Application(s)

Low Hardness Molded parts, Seals & Gaskets, High pressure hoses

High Temperature Turbo Charger Hoses

Molded parts with best fluid and lubricant resistance

‚VMX‘  developmental or experimental grades 10/3/2012

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Vamac® - Grades used for Molded Applications High Viscosity Grades Standard Grade ML (1+4) 100°C, Tg

Vamac® G 16.5 MU, -30 °C

Vamac® GXF 17.5 MU, -31 °C

Vamac® GLS 18.5 MU, -24 °C

High Viscosity Grade ML (1+4) 100°C, Tg

Vamac® Ultra IP (VMX-3040) 29 MU, -31 °C

Vamac® Ultra HT (VMX-3038) 30 MU, -32 °C

Vamac® VMX-3110 30 MU, -25 °C

Vamac® VMX-3121 30 MU, -26 °C Low oil swell version of Ultra HT Major Features

Best Compression Set, Fast Cure

Best Dynamic Fatigue Resistance

Best Compression Set, Fast Cure, Low Oil swell

Main Application(s)

Low Hardness Molded parts, Seals & Gaskets, High pressure hoses

High Temperature Turbo Charger Hoses

Molded parts with best fluid and lubricant resistance

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Vamac® G vs. Ultra IP, Injection Molding Test

Mold Design: O-Ring 214, 40 Cavities Dimensions:

24.99 x 3.53 mm

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Compounds used for IM Tests Vamac® G

100

Vamac® Ultra IP

100

Naugard® 445

2

2

Vanfre® VAM

1

1

Armeen® 18D

0.5

0.5

Stearic acid

1.5

1.5

Spheron® SO A N-550

30

30

DiakTM No 1

1.5

1.2

3

3

Vulcofac® ACT 55

MDR, 15 min @ 180°C, arc 0.5°

Very sticky, non-industrial recipe.

Different levels of curative, all other ingredients identical.

ISO 6502

ML (dNm)

0.3

0.6

MH (dNm)

10.8

12.0

Ts2 (min)

1.0

0.9

Tc50 (min)

2.1

2.1

Tc90 (min)

6.5

6.5

 At 20% lower curative level, Ultra IP compound is 11.1% higher in MH.

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Demoulding Steps

Auto

Brush

Manual

Next shot

O-rings are counted 10/3/2012

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Vamac® G – Ultra IP, manually demolded O-rings

Vamac® G compound was injected first Increasing number of O-rings sticking

Mould was cleaned before molding Vamac® Ultra IP compound  Decreasing number of O-rings sticking

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Physical Properties, VMX-3110 vs. Vamac® GLS - Properties of Vamac GLS compound =100% - VMX-3110 was used with identical formulation and at reduced curative level (1.25 phr Diak™ No.1)

140

Polymer 100 phr Naugard®445 2 St. Acid 1.5 Vanfre® VAM 1 Armeen® 18 D 0.5 W759 10 FEF-550 60 DIAK™ No1 1.75 ACT 55 2

Vamac® GLS

130

VMX-3110 VMX-3110, - 30% curative

120 110 100

 Combination of high MH and shorter tc90 allows for much faster mold release

90 80

 Physical properties generally improved

70 60 MH

tc90

Tensile

Elongation

Tear Strength 10/3/2012

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Vamac® GLS vs. VMX-3110, Compression Set Diamine Curative (DIAKTM No.1) Reduction 60 Cset, ISO 815 (6m m plied), 70h@150°C

50

VW PV3307, 22h@150°C

CSet in %

Cset Daim ler (VDA67521B), 22h@150°C

40 30 20 10 0

Vamac® GLS, 1.75 phr DIAK 1

VMX-3110, 1.75 phr DIAK 1

VMX-3110, 1.25 phr DIAK 1

-Similar Compression Set resistance at abt. 30% Curative reduction  Compound cost reduction

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Compounding Possibilities - Reduction of Process Aid Levels Vamac® Ultra grades are much cleaner in Injection Molding than standard grades, and tend to stick to the mould much less due to their higher viscosity.  This allows reduction of process aids which are absolutely needed for standard grades to get best mould release. A study was carried out to look into different ways to optimize cure speed and compression set. Reduction of process aids also reduces the flow lines in multi-cavity moulds with long compound flow ways, such as multi-cavity O-ring moulds.

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Reduction of process aids  reducing cure time (or avoiding flow lines)

Vamac® Ultra IP

100

100

100

100

100

100

Naugard® 445

2

2

2

2

2

2

Vanfre® VAM

1

1

Armeen® 18D

0.5

0.5

0.5

Stearic acid

2

2

2

2

MT Thermax® Floform N 990

20

20

20

20

20

20

Regal® SRF N 772

45

45

45

45

45

45

Rhenosin® W 759

15 15

15

15

15

15

1.3

1.3

1.3

1.3

1.3

1.3

3

3

3

3

3

Edenol® T810T stabilized DiakTM No 1 Vulcofac® ACT 55 Alcanpoudre® DBU-70

3

- General Purpose 60 Shore A sealing compound - Effect of different plasticiser volatility and basic coagent was included in the study - Stepwise reduction of process aids

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Reduction of process aids  reducing cure time (or avoiding flow lines)

ML (dNm) Ts2 (min) Tc50 (min)

1.8 1.6 1.4 1.2

- 45% reduction

1 0.8 0.6 0.4 0.2 0 Control

Edenol T810T

no Vanfre VAM

no Armeen 18D

no Stearic Acid

Alcanpoudre DBU-70

-Significant reduction of cure times possible - Viscosity increasing, Scorch times reduced  Compromise for short cycles and processing needs to be found (for 60 ShA compounds with 15 phr plasticiser, compound flow is usually good)

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Reduction of process aids  reducing cure time (or avoiding flow lines) May be good enough for some applications like moulded air ducts Allows reduction of post-cure time and oven capacity Compression moulding 5 min at 190°C, no post-cure Comp. set, 24 h /150°C, plied (%)

50

46

40

36

40

36

PV3307, 94 h /150°C (%)

84

77

74

72

72

70

Post-cure 30 min at 175°C Comp. set, 24 h /150°C, plied (%)

22

20

19

18

19

19

PV3307, 94 h /150°C (%)

69

59

59

57

55

54

Hardness, Shore A

59

57

59

59

59

58

Tensile Strength [MPa]

13.8

13.8

14.6

15.2

15.3

14.7

Elongation at break [%]

373

372

381

362

342

350

Modulus at 100 % [MPa]

2.7

2.2

2.6

3.1

2.9

3.3

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Sealing Performance - Compressive Stress Relaxation Vamac® GLS and VMX-3110 with identical formulations (60 Sh.A, 1.75 phr DIAK™ No1 and 20 phr of plasticiser)  VMX-3110 provides significant improvement

F o rc e R eten tio n (% )

CSR in Air, 150°C, ISO 3384 100 GLS, high DIAK

80

VMX-3110, high DIAK

60 40 20 0 0

168

336

504

Time in hours

CSR in Air, 150°C, ISO 3384 Force R etention (% )

100

Both formulations without plasticiser  VMX-3110 significantly better than HTACM

VMX-3110, no plasticizer

80

HT-ACM

60 40 20 0 0

168

336

504

Time in hours

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Heat Ageing, Vamac® G vs. Ultra IP Compounds without plasticizer Vamac® G

Ultra IP

Ultra IP / low DIAKTM No.1

Hardness change (pts)

5

1

0

M 100% Change (%)

32

13

5

Tensile Strength Change (%)

-51

-21

-40

Elongation Change (%)

-54

-20

-35

Hardness change (pts)

3

-1

-3

M 100% Change (%)

29

6

11

Tensile Strength Change (%)

-30

-21

-34

Elongation Change (%)

-40

-24

-35

Heat ageing 504 h @ 175 °C

Heat ageing 168 h @ 190 °C

- Better property retention for Vamac® Ultra IP - Little to no Hardness and Modulus Change - Compounds with tighter x-link density exhibit better property retention 10/3/2012

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Vamac® vs. ACM – Heat Ageing at 150°C Elongation after Heat Aging 450

Vamac® G

400

Elongation after H.A. (%)

Ultra IP 350

Ultra HT (VMX-3038)

300

HT-ACM Standard ACM

250 200 150 100 50 0 0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

Heat Aging, Hours at 150 degC

- Absolute value higher for Vamac® Ultra grades compared to HT-ACM. - No long-term heat ageing advantage for HT-ACM at 150°C - Standard ACM (commercial compound, 55 ShA) falls below 100% remaining EaB after 1000 h at 150°C 10/3/2012

5500

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Vamac® Ultra vs. ACM – Heat Ageing at 150°C Vamac vs. HT-ACM Hardness Change after Heat Aging 30

25 G

Hardness Change (pts)

GXF 20

Ultra IP VMX-3038

15

HT-ACM

10

5

0 0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

-5

Heat Aging Hours at 150 degC

Significant Hardness increase of HT-ACM upon ageing. Vamac® Ultra grades with excellent retention of Hardness.

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Vamac® grades for Turbo Charger Hoses

Vamac® GXF was introduced in 2003, and has since then become the AEM polymer of choice for Turbo Charger hoses in Europe. The new high viscosity Vamac® Ultra family provides additional advantages in processing and physical properties of cured compounds. Vamac® Ultra HT (recently fully commercialised, formerly VMX-3038) was developed for turbo charger hose application with higher heat resistance than Vamac® GXF. The new, better oil resistant version VMX-3121 offers the possibility to reduce swell in oils & lubricants and allows for a broader application range in all kinds of hoses and tubes. Meets oil swell requirements for ACM, and offers better resistance to acids and fuels compared to ACM.

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Comparison Vamac® GXF – Ultra HT – VMX-3121

Formulations used identical for all three polymers: Polymer Naugard® 445 Ofalub® SEO Stearic Acid Spheron® SO A N-550 Alcanplast® PO80 Diak™ No. 1 Vulcofac® ACT 55

100 phr 2 1 1 45 2 1.1 2

It is recommended to further reduce HMDC curative level for Ultra HT and VMX3121 by 20%

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Original Properties Press-Cure 10 minutes at 180°C Post-cure 4 hours at 175°C Vamac® GXF

Ultra HT (VMX-3038)

VMX-3121

66

67

68

Tensile Strength [MPa]

18.3

19.8

20.3

Elongation at break [%]

362

382

362

Modulus at 100 % [MPa]

3.8

4.2

4.4

Tear Strength Die C, ISO 34-1 @ 23°C [kN/m]

23.4

25.1

23.9

C Set, ISO815, B, 168 h @ 175°C (%)

38

31

30

VW C Set, PV3307, 22 h @ 175°C (%)

61

45

51

Tension Set, ISO2285, 168 h @ 175°C (%)

76

63

60

- 31

- 31

- 25

Hardness Shore A (1 sec)

Tg by DSC (°C)

• The two high viscosity grades provide higher Tensile and Modulus, while still maintaining identical Elongation levels. • Compression and Tension Set significant better for Ultra grades. Lower HMDC level would provide same CSet as for Vamac® GXF and increase Elongation, Tear and reduce Moduli. • VMX-3121 based compound is 6°C higher in Glass Transition point 10/3/2012

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Heat Ageing Vamac® GXF

Ultra HT (VMX-3038)

VMX-3121

5

3

5

Tensile Strength [MPa]

11.7

13.8

14.2

Delta TS [%]

-36

-30

-30

Elongation at break [%]

270

298

317

Delta Elong. [%]

-25

-22

-12

DeMattia Flex Cracking @150°C, avg of 5 specimen (cycles)

147

335

1499

Vamac® GXF

Ultra HT (VMX-3038)

VMX-3121

3

2

3

Tensile Strength [MPa]

10.7

13.2

13.5

Delta TS [%]

-42

-33

-33

Elongation at break [%]

242

298

312

Delta Elong. [%]

-33

-22

-14

94 hours at 200°C Delta Hardness (pts.)

336 hours @ 180°C Delta Hardness (pts.)

- Best retention of properties and absolute values for VMX-3121 - Significant improvement of DeMattia results after heat ageing at 200°C

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Immersion in Fluids – Weight Change Formulations as shown before 140 Vamac® GXF 120 100

Ultra HT VMX-3121

80 60 40 20 0 -20 Lubrizol OS206304

Castrol LL3 5W30

FAM-B

FAM-B, after redrying

Swell in engine oil reduced by abt. 50%. Swell in reference fuel FAM-B still high, but significant lower compared to Vamac® GXF.

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Resistance of AEM to new Automotive Fluids Environmental regulations and the requirements to improve fuel efficiency have led to the introduction of new technologies such as Exhaust Gas Recirculation (EGR), Selective Catalytic Reduction (SCR) or high pressure direct fuel injection. Biofuels are used at higher levels. This leads to the presence of a new combination of more aggressive fluids in different areas of the engine. Vamac® with its high Ethylene content and the highly polar Methyl Acrylate groups provides interesting combinations of resistance to different fluids. The following slides shall give a few examples.

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Volume Change in OEM Blow-By Condensates Condensate 1 (fuel/oil)

Condensate 2 (water/acid) Weight-%

Weight-%

Naphthalene

1

Formaldehyde-10%

1

FAM-A (DIN51604-1)

88

Deionized water

89,7

Oil Lubrizol® OS206304

10

HNO3 (65%)

0,18

Formaldehyde-10%

1

Formic Acid (98-100%)

0,06

Acetic Acid (96%)

0,06

Ethanol

9

180

Cond. 1 (Fuel/oil)

160

Cond. 2 (Acid)

All compounds without plasticiser and similar filler content.

140

- Tests carried out in lab autoclavs, 72 h at 120°C. - Results for volume change in % before drying.

120 100 80

 Higher swell for ACM in fuel/oil blend  Higher swell of ACM in acid/water/EtOH blend, standard ACM with Carboxyl/Chlorine cure sites

60 40 20 0 Vamac® VMX-3110

Standard ACM

HT-ACM 10/3/2012

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Resistance to Acetic Acid (1m), 504 h @ 100°C HT-ACM

Vamac® Ultra HT

VMX3121

Naugard® 445

2

2

2

Stearic acid

1

1

1

Vanfre® VAM

0.5

1

1

Spheron® SOA (N 550)

65

45

MT Thermax® N 990

DiakTM No 1 Vulcofac® ACT 55

Pure ester based polymers like ACM tend to higher swell compared to AEM.

90

Tegmer® 812 Rhenosin® W 759

Resistance to Acetic Acid required by major European OEM.

2

2

0.6

1

1

2

2

2

5

30 25

Volume Change (%)

20 15 10 5 0 HT-ACM

Ultra HT

VMX-3121 10/3/2012

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Resistance to AdBlue® Urea Solution Selective Catalytic Reduction systems use water based urea solutions for reduction of NOx. OEMs request very often additional resistance to Diesel fuel. AEM meets existing specifications of OEMs. Vamac® Ultra IP outperforms standard Vamac® grades.

100 80 60 40

Vam ac® Ultra IP Vam ac® G

Test conditions:

Vam ac® GLS

- Lab autclavs - 168 hours at 120 °C

20 0 -20 -40 -60 -80 -100 Hardness Tensile Elongation Volum e Change Change (%) Change (%) Change (%) (pts.)

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Summary 

High viscosity AEM Ultra polymers offer significantly better properties over standard Vamac® grades and may extend the range of applications for AEM



Blending of Ultra Grades with standard grades may be possible at various ratios for optimum price/performance ratio



Faster Cure and cleaner molding processes



Cleanliness and lower tendency to stick to molds allow for more compounding possibilities



Good combination of resistance to hydrocarbon-based fluids and water-based fluids



Good Blow-By and Exhaust Gas Condensate Resistance make standard Vamac® and Vamac® Ultra grades a good candidate for new applications with contact to mixtures of aggressive fluids

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Thank YOU !

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The information set forth herein is furnished free of charge and is based on technical data that DuPont believes to be reliable and falls within the normal range of properties. It is intended for use by persons having technical skill, at their own discretion and risk. This data should not be used to establish specification limits nor used alone as the basis of design. Handling precaution information is given with the understanding that those using it will satisfy themselves that their particular conditions of use present no health or safety hazards. Since conditions of product use and disposal are outside our control, we make no warranties, express or implied, and assume no liability in connection with any use of this information. As with any product, evaluation under end-use conditions prior to specification is essential. Nothing herein is to be taken as a license to operate or a recommendation to infringe on patents. Caution: Do not use in medical applications involving permanent implantation in the human body. For other medical applications, discuss with your DuPont customer service representative and read Medical Caution Statement H-50103-3. Copyright © 2011 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved

Vamac® and DIAK™ are registered trademarks of DuPont. Spheron® and Regal® are registered tradmarks of Cabot Corporation. Thermax® is a registered trademark of Cancarb. Naugard® is a registered trademark of Uniroyal. Armeen® is a registered trademark of Akzo Nobel. Vanfre® is a registered trademark of R.T. Vanderbilt. Edenol® is a registered trademark of Cognis Oleochemicals. Lubrizol® is a registered trademark of Lubrizol Corporation. Vulcofac®, ALcanplast®, ALcanpoudre® and Ofalub® are registered trademarks of Safic-Alcan. Rhenogran® and Rhenosin® is a registered trademark of Rhein-Chemie. AdBlue® is a registered trademark of BASF Tegmer® is a registered trademark of HallStar

10/3/2012