vamac (aem) ethylene acrylate polymers new developments patricia panne vamac(r) new a… · heat...
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Vamac® (AEM) Ethylene Acrylate
Polymers – New Developments
A Response to Trends in the Automotive
Industry
Manchester Polymer Group Rubber Seminar, May 15th, 2017
Dr. Patricia Panne
Technical Service and Development Vamac®
DuPont Performance Materials, Germany
Agenda
Vamac® Background
Automotive Trends
Vamac® Product Line
VMX2122 – Latest Ultra Dipolymer
VMX5000 Series – Latest High Temperature Resistant AEM
2
Agenda
Vamac® Background
Automotive Trends
Vamac® Product Line
VMX2122 – Latest Ultra Dipolymer
VMX5000 Series – Latest High Temperature Resistant AEM
3
Heat and Oil Resistance of Elastomers
Oil Resistance ( Volume Swell )
No Req. 140 120 100 80 60 40 20 10
Heat
Resis
tan
ce
SBR
IR
IIR
EVM EPDM
VMQ
CR NBR
ECO
FVMQ
FFKM
FKM
CSM
CPE
300 275 250 225 200 175 150 125 100 70
EVM High VA
HT-ACM
ACM HNBR
A B C D E F G J K
K J
H
G
F
E
D
C
B
A
Type C
VI %
Class
Vamac® AEM VMX5000
Mid-Performance High-Performance
1 Classification inspired by ASTM D2000 standard 2 Maximum temp. at which a vulcanizate can be aged for 70 hrs and still retain at least 50% of its elongation 3 % volume swell in ASTM IRM 903 Oil, 70 hrs exposure
4
Vamac® Application Board
Breathing Tubes
Molded Air Duct Fiber Reinforced
Turbo Charger Hose
Transmission Oil
Cooler Hose (TOC)
Positive Crankcase
Ventilation (PCV)
Tubing
Oil Pan Gasket Bonded Piston Seal
(Automatic Transmission)
Transmission
Lip Seal
Torsional Vibration
Damper
NHFR W&C
Jacketing
Boots Connectors Grommets 5
Polymer Structure of Vamac®
-(-CH2CH2-)- -(-CH-CH2-)- -(-R-)-
C=O C=O
OCH3 OH
ethylene
methyl
acrylate acidic cure-site
TERPOLYMER: diamine cure DIPOLYMER: peroxide cure
-(-CH2CH2-)- -(-CH-CH2-)-
C=O
OCH3
ethylene
methyl
acrylate
• Amorphous random ethylene copolymer
• (A) Polar acrylic monomer imparts fluid resistance
• (E) Ethylene provides low temperature properties
• (M) Saturated polymer chain for thermal stability
Post cure required: 4hrs at 175C Limited or no post cure
6
Key Performance Features
Continuous service temperature of 175C
Short term excursions to as high as 200C
Low temperature flexibility (-35C / -40C)
Low compression set at 150C
Excellent compressive stress relaxation (CSR) properties in sealing
Low swell in hot motor oil, and automatic transmission fluid (ATF)
Good acid condensate & exhaust gas blow-by resistance
Vibration dampening, and flex fatigue resistance
Outstanding ozone/ weather resistance
Non-halogen, and low-smoke emissions
7
Agenda
Vamac® Background
Automotive Trends
Vamac® Product Line
VMX2122 – Latest Ultra Dipolymer
VMX5000 Series – Latest High Temperature Resistant AEM
8
Automotive Trends and Effect on Elastomers
Regulations: over the years more stringent requirements regarding CO2 emission,
NOx, and fuel economy have evolved
New and improved technologies: smaller engines, turbocharger etc.
New fluids: biofuels, lubricants etc.
Recycling: introduction of pollution control devices, e.g. PCV*, EGR**
More aggessive environment that creates a significant challenge to most materials
in air managment loop through acid condensation.
Material requirements have been changing towards:
Higher heat resistance
Improved fluid resistance
Improved acid resistance
Excellent low temperature performance
Excellent sealing performance under a variety of conditions
*PCV – Positive Crankcase Ventilation
**EGR – Exhaust Gas Recirculation 9
Turbocharger System with Recycle Loops
Exhaust Fresh Air
Air filter
Inlet manifold
Turbo charger
Exhaust manifold
Intercooler
Catalyst
PCV system
EGR Low Pressure System
Copyright © 2013 DuPont. All rights reserved. ® and ™ indicate registered trademarks or trademarks of DuPont
PCV – Positive Crankcase Ventilation
Recirculates vapor from engine compartment
Contains engine oil, fuel and combustion byproducts
Under normal conditions it is routed to air intake manifold
Under some conditions it is routed to suction side of compressor
EGR – Exhaust Gas Recirculation
Minimizes NOx Formation
Can Improve Fuel Efficiency
Contains combustion byproducts – CO,
CO2, NOx, SOx, Water, etc
Acid Condensates Build up in Recirculation Loops.
Can be very aggressive to some materials in turbocharger system.
10
Agenda
Vamac® Background
Automotive Trends
Vamac® Product Line
VMX2122 – Latest Ultra Dipolymer
VMX5000 Series – Latest High Temperature Resistant AEM
11
Product Grade List
Vamac® Standard Grades
Vamac® Ultra Family (higher viscosity / better processing)
12
Grade
Vol Swell % 1 IRM903,
1wk/150°C
Mooney Viscosity 2
( MU ) Tg 3
( °C ) Cure Key Feature Vamac® GLS 30 18.5 -23 Diamine Low oil swell Vamac® G 55 16.5 -30 Diamine General purpose Vamac® GXF 60 17.5 -30 Diamine Dynamic fatigue resistance Vamac® DP 55 22 -27 Peroxide Limited / No-Post Cure
Grade
Vol Swell % 1 IRM903,
1wk/150°C
Mooney Viscosity 2
( MU ) Tg 3
( °C ) Cure Key Feature Vamac® Ultra LS 30 33 -23 Diamine High viscosity / Low oil swell Vamac® Ultra HT-OR 30 31 -24 Diamine High temp / Oil resistance Vamac® Ultra IP 55 29 -30 Diamine Improved processing Vamac® Ultra HT 60 29 -30 Diamine High temperature Vamac® Ultra XF 60 23 -30 Diamine Intermediate viscosity VMX2122 55 28 -29 Peroxide Improved dipolymer VMX4017 80 11 -41 Diamine Low temperature
1 ASTM D471 2 ASTM D1646, ML1+4 at 100C 3 ASTM D3418 (DSC)
Various Vamac® Terpolymers have been introduced recently as the Vamac® Ultra
product family, with significant improvements vs. conventional Vamac® grades
The same polymerisation technology has now been applied in the development of an
improved Vamac® E/MA DiPolymer called VMX2122
VMX2122 shows clear advantages vs Vamac® DP in different aspects
Summary VMX2122 vs Vamac® DP
13
0
2
4
6
8
10
12
14
16
18
1 2 3 4 5 6 7 8 9 1011121314151617181920212223242526272829303132333435363738394041424344454647484950
O-r
ing
s, m
an
ua
lly d
em
ou
lde
d
Clear improvement with all VMX2122 based compounds in demoulding
Very limited number of VMX2122 based O-rings needed to be removed manually,
comparable to results usually obtained with Vamac® Ultra Terpolymers.
Vamac® DP compound
VMX2122 based compounds
Injection Molding Trials – Vamac® DP vs. VMX2122
similar formulations
50 Shots
40 Cavity Mold
14
-25
-20
-15
-10
-5
0
5
10
15
20
Vamac® DP VMX 2122
Pro
per
ties
ch
ange
, %
Heat ageing in air 168hrs@160°C
Hardness Change (pts.)
Tensile Strength at Break Change (%)
Elongation at Break Change (%)
VMX2122 - HFFR Formulation
Formulation phr
Vamac® DP/VMX2122 100
Naugard® 445 1
Armeen® 18D 0.5
Stearic acid 1.5
ATH (Martinal® OL-111) 160
Vinyl silane 1
Perkadox® 14-40B-GR 4.5
Rubber chem HVA-2 1.5
General W&C Formulation:
Properties Vamac® DP VMX2122
Polymer Mooney ML (1+4) 100°C 22 24
Compound Mooney ML (1+4) 100°C 41 51
Hardness 76 79
TS [MPa] 9.8 11.5
EB [%] 261 267
15
-60
-50
-40
-30
-20
-10
0GLS Ultra LS Ultra IP VMX2122
Elo
ng
ati
on
at
bre
ak c
han
ge,
%
Potential Benefits for Hoses
Vamac® DP based compounds typically have inferior properties compared to
diamine cured Vamac® Terpolymers. VMX2122 can meet existing AEM
specifications.
Higher viscosity of VMX2122 vs Vamac® DP improves green strength of compounds
and collapse resistance of uncured hoses.
Amine Curatives are known to attack polyester‘s strength significantly. Peroxide
cured AEM would allow use of polyester reinforcement cost save over aramide
reinforcement
Fluid Ageing, 1008 h /150°C
Fuchs Titan® EG CVT28
Pentosin® FFL-4
16
VMX2122 – Potential Application
Oil Hoses
Seals
Halogen Free Flame Retardant (HFFR) Applications
Low Limited Oxygen Index (LOI) – 37%
Good low and high temperature resistance
Fluid resistance (IRM 903 168hrs@100°C <30%)
Abrasion resistance (100-120 mm3)
Wire & Cable
Oil Hoses Applications
Higher green strength than Vamac® DP
Pressureless cure possible (salt bath)
Polyester reinforcement possible
Excellent retention of properties after fluid aging
Seal and Gasket Applications
Existing AEM specifications can be met
TS >12 MPa, EB>250%
Good compression set without post cure
20-30% after 70hrs@150°C
17
Agenda
Vamac® Background
Automotive Trends
Vamac® Product Line
VMX2122 – Latest Ultra Dipolymer
VMX5000 Series – Latest High Temperature Resistant AEM
18
Vamac® pre-compounds for high heat resistance
The VMX5000 series is an industry first
Vamac® pre-compounded with polymeric filler Filler promotes oxidative stability Mechanism: diffusion limited oxidation Colorability Light-weighting 0.5 – 2um sized particles
Product Grade List
19
Grade
Vol Swell % 1 IRM903,
1wk/150°C
Mooney Viscosity 2
( MU ) Tg 3
( °C ) Cure Key Feature VMX5394 30 70 -24 Diamine Steam autoclave curable / Low Swell VMX5315 60 70 -30 Diamine Steam autoclave curable / Extrusion VMX5015 60 67 -30 Diamine Compression molding 4 VMX5020 60 53 -30 Diamine Injection molding 4
1 ASTM D471 2 ASTM D1646, ML1+4 at 100C 3 ASTM D3418 (DSC) 4 Not suitable for steam autoclave cure
VMX5000 Series
VMX5394 VMX5015
VMX5315 VMX5020
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21
Heat Ageing, Arrhenius Curve
Heat Resistance, Carbon Black filled Vamac® Ultra and HT-ACM
compounds, compared with VMX5000, Time vs. Temperature
HT-ACM values are average values
from several different evaluations.
Used standard formulations from
the HT-ACM literature.
VMX5000 series vs. conventionally filled AEM compounds
When time is held constant – Significant increase in temperature rating with
"Improved Offering”
• 6 weeks – from 167°C to 182°C rating (15ºC)
• 3 weeks – from 175°C up to 190°C rating (15ºC)
• 1 week – from 185°C up to 205°C rating (20ºC)
When temperature is held constant – significant increase in time until failure
• 160°C – from 1800 hours up to 3600 hours (2 x)
• 175°C – from 504 hours up to 1680 hours (3.3 x)
• 185°C – from 168 hours up to 750 hours (4.5 x)
Heat Ageing
22
Molded ISO compression set buttons: - Age for specified time in air
- Cut sample in half
- Visual check for oxidation
- Used silica – not black
Diffusion limited oxidation – AEM/Silica vs 5000 series
Ultra HT: oxidation has progressed fully through the sample
VMX5000: Oxidized layer remains about the same thickness for 3 weeks
Press Cure 1 day @ 190°C 1 week @ 190°C
press cure 1 day @190°C 3 weeks @ 190°C
Ultra HT,
filled with
Silica
VMX5015
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Hardness
• VMX5000 pre-compounds lead to Hardness of approxmately 75 Shore A after
vulcanisation (no CB)
• Lower Hardness compounds are obtained by adding Vamac® polymer, e.g. Vamac®
Ultra IP, Ultra HT, GXF
Compounding VMX5000 Series
50
55
60
65
70
75
80
40 50 60 70 80 90 100
Hardness, Sh.A, 3s
VMX5000 content (% of total polymer content)
Formulation
Vamac® VMX 5015 (%) 73 Vamac® Ultra IP (%) 27 4-ADA 0.93 Stearic Acid Reagent (95%) 0.33 Vanfre® VAM 0.67 DiakTM no 1 0.67 Alcanpoudre® DBU-70 1.33
Hardness Shore A, 3s 62 Tensile Strength [MPa] 19.4 Elongation at break [%] 280 Modulus at 100 % [MPa] 3.7 Tear strength type C - [kN/m] 16.9
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Formulation
• Lower Diak™ 1 levels than typical (≤ 1phr)
• Recommended Antioxidant: 4-aminodiphenylamine (ADPA)
• NOT recommended: use of diarylamine type AO (e.g., Naugard® 445 or IPPD)
Compounding VMX5000 Series
75A Hose 60A Gasket
VMX5000 181.8 118
AEM 36
DiakTM 1 0.5 - 0.6 0.6 - 1.0
Vulcofac® ACT-55 1 1 - 2
Alcanpoudre® DBU-70
1 - 2
Armeen® 18D 0.5 0 - 0.5
Stearic acid 0 - 0.5 0 - 0.5
ADPA 0.5 - 1.5 0.5 - 1.5
Plasticizer* 2 – 5 0 - 5
Vanfre® Vam 1 1
Carbon Black 2 2
• Polymer: 100phr AEM, Ultra HT,
Ultra IP and GXF suitable dilutents,
fasted cure with Ultra IP
• Curative: ≤0.55phr for best fatigue
resistance; 0.8phr for best
compression set; ≥0.8 phr improved
VW c.s. however heat resistance
affected
• Accelerator: DBU-70 faster cure,
helps processing release
* Alcanplast® PO 80, Tegmer® 812
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Compression Set Resistance: 60 Shore A Gasket
Compression Set as a function of - Time & Temperature
- Surface area / volume ratio
- Filler
VMX5020
black
VMX5020
red
Standard
Ultra LS
VMX5020 100 100
Vamac® Ultra IP 50 50
Vamac® Ultra LS 100
4-ADA antioxidant 1.4 1.4
DPA Antioxidant 2
Stearic Acid 0.5 0.5 1
Phosphoric Acid Ester (Process
Aid) 1 1 1
Monoalkylamine 0.5
FEF N-550 10
MT N 990 15 50
Amino Silane 70% 0.25
Silica VN2 10
Red inorganic pigment 1.5
Plasticizer T810TM 5 5 5
HMDC Curative 1.25 1.25 1.4
DBU (70%) 2 2 2
0
10
20
30
40
50
60
CS ISO815B, 168 h@ 170°C
CS ISO815B, 1008 h@ 170°C
CS O-ring, 168 h @180°C
VMX5000, black
VMX5000 red
Standard Ultra LS
Advantage in heat ageing performance has significant effect on long term compression set
on ISO buttons
Standard fillers lead to significant increase in C.Set between 1 and 6 weeks at 170°C
O-ring has higher surface area / volume ratio compared to ISO button
Growth of the oxidized layer plays more of a role in C.Set for O-rings
Exceptional C.Set for colored compounds possible with novel VMX5000 filler system
26
Heat and Oil Ageing: 60 Shore A Gasket
Heat Ageing 3 weeks at 185°C
VMX5020
black
VMX5020
red
Standard
Ultra LS
Hardness (Sh.A, 1s) 62 62 62
Tensile Strength (MPa) 18.0 17.0 16.8
Elongation at Break (%) 300 240 320
Tear Strength (N/mm) 13.7 14.8 15.7
Tg by DSC (°C) -30 -31 -25
• Standard Filled compound too brittle to test
• VMX5000 series still very elastic
-100
-80
-60
-40
-20
0
20
40
Hardness Change(ShA)
Tensile Change(%)
Elongation Change(%)
VMX5000, black
VMX5000 red
Standard Ultra LS
-100
-80
-60
-40
-20
0
20
40
HardnessChange (ShA)
TensileChange (%)
ElongationChange (%)
VolumeChange (%)
VMX5000, black
VMX5000 red
Standard Ultra LS
Ageing in Pentosin® FFL-5 LV, 1008h at 150°C
• Best retention of Elongation (most critical
value for AEM) after fluid ageing for
VMX5000
Original Physical Properties
27
Summary VMX5000 Series
• 15-20°C improvement in hot air aging resistance for Acrylic Elastomers
• Fills the gap in heat stability between VMQ/FKM and HT-ACM/AEM
• Hardness range: 55-80 Shore A
• Outstanding CSR and Compression Set Resistance (especially for thin
diameter seals)
• Colored compounds with excellent properties
• Best retention of properties after Oil ageing
• Can be blended with any AEM to achieve lower hardness, lower swell
• Retains the excellent processing of AEM
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The information provided in this data sheet corresponds to DuPont knowledge on the subject at the date of its publication. This information may be
subject to revision as new knowledge and experience becomes available. The data provided fall within the normal range of product properties and
relate only to the specific material designated; these data may not be valid for such material used in combination with any other materials, additives or
pigments or in any process, unless expressly indicated otherwise.
The data provided should not be used to establish specification limits or used alone as the basis of design; they are not intended to substitute for any
testing you may need to conduct to determine for yourself the suitability of a specific material for your particular purposes. Since DuPont cannot
anticipate all variations in actual end-use and disposal conditions, DuPont does not guarantee results, makes no warranties and assumes no liability in
connection with any use of this information. All such information is given and accepted at the buyer’s risk. It is intended for use by persons having
technical skill, at their own discretion and risk. Nothing in this publication is to be considered as a license to operate under or a recommendation to
infringe any patent.
CAUTION: Do not use DuPont materials in medical applications involving implantation in the human body or contact with internal body fluids or tissues
unless the material has been provided from DuPont under a written contract that is consistent with DuPont policy regarding medical applications and
expressly acknowledges the contemplated use. For further information, please contact your DuPont representative. You may also request a copy of
DuPont POLICY Regarding Medical Applications H-50103-5 and DuPont CAUTION Regarding Medical Applications H-50102-5.
Copyright © DuPont. The DuPont Oval Logo, DuPont™ and Vamac® are trademarks or registered trademarks of E.I. du Pont de Nemours and
Company or its affiliates. All rights reserved.
Naugard® is a registered trademark of Addivant.
Armeen® and Perkadox® is a registered trademark of Akzo Nobel.
Martinal ® is a registered trademark of Martinswerk GmbH.
Pentosin® is a trademark of Deutsche Pentosin-Werke GmbH
Fuchs Titan® is a trademark of Fuchs Petrolub AG
Vanfre® is a registered trademark of R.T. Vanderbilt.
Vulcofac® , Alcanplast® and Alcanpoudre® are registered trademarks of Safic-Alcan.