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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
20
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