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

20

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

23

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

24

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

25

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

28

29

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.