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TRANSCRIPT
10/3/2012
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New AEM Polymers and Developments -Meeting Demands of Modern Engine
Technology
Klaus KammererTechnical Consultant Vamac® & Viton®
DuPont Deutschland GmbH
DuPont™ Vamac® Ultra
DKT 2012, Nuremberg
10/3/2012
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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
HeatRes.70 hrs
Oil Resistance% Swell in IRM 903 Oil
No Req 170 120 100 80 60 40 20 10
Butyl
70
100
125
200
225
250
Styrene ButadieneNatural Rubber
Neoprene
Vamac®
Viton ®
Silicone
EPDM
Fluorosilicone
Polyacrylate (ACM)
HNBR
Epichlorohydrin
Nitrile
NBR/PVC
CPE
V Solutions SpaceSealing & Hose Applications
HiTemp-ACM
150
175
165
Applications with min. temperature requirements of 165 degrees
Applications with reduced swell
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4
AEM G -Type Terpolymer
(CH2-CH2)x– (CH-CH2)y –(R)z| |
O=C C=O| |
OCH3 CO2H
Ethylene Methyl Acrylate Acidic Cure Site
Chemical Structure
(A) Monomers Choice and Ratio
(B) Molecular Weight Distribution Optimization.
New products
(C) Adjustments at Finishing step.
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High Viscosity GradesStandard GradeML (1+4) 100°C, Tg
Vamac® G16.5 MU, -30 °C
Vamac® GXF17.5 MU, -31 °C
Vamac® GLS18.5 MU, -24 °C
High Viscosity GradeML (1+4) 100°C, Tg
Vamac® Ultra IP(formerly VMX-3040)
29 MU, -31 °C
Vamac® Ultra HT(formerly VMX-3038)
30 MU, -32 °C
Vamac® VMX-311030 MU, -25 °C
Vamac® VMX-312130 MU, -26 °C
Low oil swell version of Ultra HT
Major Features
Main Application(s)
Best Compression Set, Fast Cure
Low HardnessMolded parts, Seals &
Gaskets, High pressure hoses
Best Dynamic Fatigue Resistance
High Temperature Turbo Charger Hoses
Best Compression Set, Fast Cure,
Low Oil swell
Molded parts with best fluid and lubricant
resistance
Vamac® - Standard and High Viscosity ‘Ultra’ Grades
‚VMX‘ ���� developmental or experimental grades
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High Viscosity GradesStandard GradeML (1+4) 100°C, Tg
Vamac® G16.5 MU, -30 °C
Vamac® GXF17.5 MU, -31 °C
Vamac® GLS18.5 MU, -24 °C
High Viscosity GradeML (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-311030 MU, -25 °C
Vamac® VMX-312130 MU, -26 °C
Low oil swell version of Ultra HT
Major Features
Main Application(s)
Best Compression Set, Fast Cure
Low Hardness Molded parts, Seals &
Gaskets, High pressure hoses
Best Dynamic Fatigue Resistance
High Temperature Turbo Charger Hoses
Best Compression Set, Fast Cure,
Low Oil swell
Molded parts with best fluid and lubricant
resistance
Vamac® - Grades used for Molded Applications
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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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Very sticky, non-industrial recipe.
Different levels of curative, all other ingredients identical.
���� At 20% lower curative level, Ultra IP compound is 11.1% higher in MH.
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
Vulcofac® ACT 55 3 3
MDR, 15 min @ 180°C, arc 0.5° 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
Compounds used for IM Tests
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Demoulding Steps
Auto Brush Manual
O-rings are counted
Next shot
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Vamac® G – Ultra IP, manually demolded O-rings
Vamac® G compound was injected firstIncreasing number of O-rings sticking
Mould was cleaned before molding Vamac® Ultra IP compound���� Decreasing number of O-rings sticking
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- Properties of Vamac GLS compound =100%- VMX-3110 was used with identical formulation and a t reduced curative level (1.25 phr Diak™ No.1)
Polymer 100 phrNaugard®445 2 St. Acid 1.5Vanfre® VAM 1Armeen® 18 D 0.5W759 10FEF-550 60DIAK™ No1 1.75 ACT 55 2
� Combination of high MH and shorter tc90 allows for much faster mold release
� Physical properties generally improved
Physical Properties, VMX-3110 vs. Vamac® GLS
60
70
80
90
100
110
120
130
140
MH tc90 Tensile Elongation Tear Strength
Vamac® GLS
VMX-3110
VMX-3110, - 30% curative
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Diamine Curative (DIAK TM No.1) Reduction
-Similar Compression Set resistance at abt. 30% Cura tive reduction ���� Compound cost reduction
Vamac® GLS vs. VMX-3110, Compression Set
0
10
20
30
40
50
60
Vamac® GLS, 1.75 phrDIAK 1
VMX-3110, 1.75 phrDIAK 1
VMX-3110, 1.25 phrDIAK 1
CS
et in
%
Cset, ISO 815 (6mm plied), 70h@150°C
VW PV3307, 22h@150°C
Cset Daimler (VDA67521B), 22h@150°C
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Compounding Possibilities - Reduction of Process Aid Levels
Vamac® Ultra grades are much cleaner in Injection Mo lding than standard grades, and tend to stick to the mould much less du e to their higher viscosity.���� This allows reduction of process aids which are abs olutely 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 lin es 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
Edenol® T810T stabilized 15 15 15 15 15
DiakTM No 1 1.3 1.3 1.3 1.3 1.3 1.3
Vulcofac® ACT 55 3 3 3 3 3
Alcanpoudre® DBU-70 3
- General Purpose 60 Shore A sealing compound- Effect of different plasticiser volatility and bas ic 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)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
Control Edenol T810T no VanfreVAM
no Armeen18D
no StearicAcid
AlcanpoudreDBU-70
ML (dNm)
Ts2 (min)
Tc50 (min)
-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)
- 45% reduction
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Reduction of process aids ���� reducing cure time(or avoiding flow lines)
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
May be good enough for some applications like moulded air ductsAllows reduction of post-cure time and oven capacity
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Sealing Performance - Compressive Stress RelaxationCSR in Air, 150°C, ISO 3384
0
20
40
60
80
100
0 168 336 504
Time in hours
For
ce R
eten
tion
(%)
GLS, high DIAK
VMX-3110, high DIAK
CSR in Air, 150°C, ISO 3384
0
20
40
60
80
100
0 168 336 504
Time in hours
For
ce R
eten
tion
(%) VMX-3110, no plasticizer
HT-ACM
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
Both formulations without plasticiser���� VMX-3110 significantly better than HT-ACM
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Compounds without plasticizer
- Better property retention for Vamac® Ultra IP- Little to no Hardness and Modulus Change- Compounds with tighter x-link density exhibit bette r property retention
Heat Ageing, Vamac® G vs. Ultra IP
Heat ageing 504 h @ 175 °C Vamac® G Ultra IPUltra 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
Heat ageing 168 h @ 190 °C
Hardness change (pts) 3 -1 -3
M 100% Change (%) 29 6 11
Tensile Strength Change (%) -30 -21 -34
Elongation Change (%) -40 -24 -35
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Vamac® vs. ACM – Heat Ageing at 150 °C
- Absolute value higher for Vamac® Ultra grades compa red to HT-ACM.- No long-term heat ageing advantage for HT-ACM at 1 50°C- Standard ACM (commercial compound, 55 ShA) falls b elow 100% remaining EaB after 1000 h at 150°C
Elongation after Heat Aging
0
50
100
150
200
250
300
350
400
450
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500
Heat Aging, Hours at 150 degC
Elo
ngat
ion
afte
r H.A
. (%
)
Vamac® G
Ultra IP
Ultra HT (VMX-3038)
HT-ACM
Standard ACM
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Vamac® Ultra vs. ACM – Heat Ageing at 150 °C
Significant Hardness increase of HT-ACM upon ageing .Vamac® Ultra grades with excellent retention of Hard ness.
Vamac vs. HT-ACMHardness Change after Heat Aging
-5
0
5
10
15
20
25
30
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500
Heat Aging Hours at 150 degC
Har
dnes
s C
hang
e (p
ts)
G
GXF
Ultra IP
VMX-3038
HT-ACM
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Vamac® grades for Turbo Charger Hoses
Vamac® GXF was introduced in 2003, and has sincethen 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 compoun ds.
Vamac® Ultra HT (recently fully commercialised, formerly VMX-3038) was developed for turbo charger hose application with h igher 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 fo r 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 100 phrNaugard® 445 2 Ofalub® SEO 1 Stearic Acid 1 Spheron® SO A N-550 45Alcanplast® PO80 2 Diak™ No. 1 1.1Vulcofac® ACT 55 2
It is recommended to further reduce HMDC curative l evel for Ultra HT and VMX-3121 by 20%
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Original Properties
Press-Cure 10 minutes at 180 °CPost-cure 4 hours at 175 °C
Vamac® GXFUltra HT
(VMX-3038) VMX-3121
Hardness Shore A (1 sec) 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
Tg by DSC (°C) - 31 - 31 - 25
• The two high viscosity grades provide higher Tensil e 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
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Heat Ageing
94 hours at 200 °C Vamac® GXFUltra HT
(VMX-3038) VMX-3121
Delta Hardness (pts.) 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
336 hours @ 180 °C Vamac® GXFUltra HT
(VMX-3038) VMX-3121
Delta Hardness (pts.) 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
- Best retention of properties and absolute values f or VMX-3121- Significant improvement of DeMattia results after heat ageing at 200 °C
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Immersion in Fluids – Weight Change
-20
0
20
40
60
80
100
120
140
LubrizolOS206304
Castrol LL35W30
FAM-B FAM-B, afterredrying
Vamac® GXF
Ultra HT
VMX-3121
Swell in engine oil reduced by abt. 50%.Swell in reference fuel FAM-B still high, but signi ficant lower compared to Vamac® GXF.
Formulations as shown before
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Resistance of AEM to new Automotive Fluids
Environmental regulations and the requirements to i mprove 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 resista nce to different fluids.
The following slides shall give a few examples.
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Volume Change in OEM Blow-By CondensatesCondensate 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
0
20
40
60
80
100
120
140
160
180
Vamac® VMX-3110 Standard ACM HT-ACM
Cond. 1 (Fuel/oil)
Cond. 2 (Acid) All compounds without plasticiser and similar filler content.
- Tests carried out in lab autoclavs, 72 h at 120°C.- Results for volume change in % before drying.
� Higher swell for ACM in fuel/oil blend� Higher swell of ACM in acid/water/EtOH blend, standard ACM with Carboxyl/Chlorine cure sites
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Resistance to Acetic Acid (1m), 504 h @ 100 °C
HT-ACMVamac® Ultra
HTVMX-3121
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 90
Tegmer® 812 2 2
Rhenosin® W 759 5
DiakTM No 1 0.6 1 1
Vulcofac® ACT 55 2 2 2
0
5
10
15
20
25
30
HT-ACM Ultra HT VMX-3121
Volume Change (%)
Resistance to Acetic Acid required by major European OEM.
Pure ester based polymers like ACM tend to higher swell compared to AEM.
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Resistance to AdBlue® Urea Solution
Test conditions:
- Lab autclavs- 168 hours at 120 °C
-100
-80
-60
-40
-20
0
20
40
60
80
100
HardnessChange(pts.)
TensileChange (%)
ElongationChange (%)
VolumeChange (%)
Vamac® Ultra IP
Vamac® G
Vamac® GLS
Selective Catalytic Reduction systems use water bas ed urea solutions for reduction of NOx.OEMs request very often additional resistance to Di esel fuel.
AEM meets existing specifications of OEMs. Vamac® Ul tra IP outperforms standard Vamac®grades.
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� High viscosity AEM Ultra polymers offer significant ly better properties over standard Vamac® grades and may extend the range of applicatio ns for AEM
� Blending of Ultra Grades with standard grades may b e possible at various ratios for optimum price/performance ratio
� Faster Cure and cleaner molding processes
� Cleanliness and lower tendency to stick to molds al low 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 applica tions with contact to mixtures of aggressive fluids
Summary
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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 DuPon t believes to be reliable and falls within the normal range of prope rties. It is intended for use by persons having tec hnical skill, at their own discretion and risk. This data should not be us ed to establish specification limits nor used alone as the basis of design. Handling precaution information is given wi th the understanding that those using it will satis fy themselves that their particular conditions of use present no healt h 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 u nder end-use conditions prior to specification is e ssential. 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 involvi ng permanent implantation in the human body. For ot her medical applications, discuss with your DuPont customer ser vice representative and read Medical Caution Statem ent H-50103-3.
Copyright © 2011 DuPont. The DuPont Oval Logo, DuPo nt™, and The miracles of science™ are trademarks or r egistered trademarks of E.I. du Pont de Nemours and Company o r 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 BASFTegmer® is a registered trademark of HallStar