Vamac (AEM) Ethylene Acrylate Polymers New Developments

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 Resistance Heat and Oil Resistance of Elastomers Type C Mid-Performance K 300 High-Performance FFKM J 275 H 250 G 225 FKM F E 200 175 VMQ VMX5000 Vamac AEM FVMQ HT-ACM D C B 150 125 100 EPDM IIR EVM CR CSM CPE EVM High VA HNBR ACM ECO NBR A 70 SBR IR VI % Class No Req. 140 120 100 80 60 40 20 10 A B C D E F G J K Oil Resistance ( Volume Swell ) 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 Boots Connectors Grommets NHFR W&C 5 Jacketing

Polymer Structure of Vamac Amorphous random ethylene copolymer (A) Polar acrylic monomer imparts fluid resistance (E) Ethylene provides low temperature properties (M) Saturated polymer chain for thermal stability TERPOLYMER: diamine cure DIPOLYMER: peroxide cure ethylene methyl acrylate acidic cure-site ethylene methyl acrylate -(-CH 2 CH 2 -)- -(-CH-CH 2 -)- -(-R-)- C=O C=O OCH 3 OH -(-CH 2 CH 2 -)- -(-CH-CH 2 -)- C=O OCH 3 Post cure required: 4hrs at 175 C Limited or no post cure 6

Key Performance Features Continuous service temperature of 175 C Short term excursions to as high as 200 C Low temperature flexibility (-35 C / -40 C) Low compression set at 150 C 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 CO 2 emission, NO x, 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 Intercooler Inlet manifold Exhaust Fresh Air Catalyst EGR Low Pressure System PCV system Air filter Exhaust manifold Turbo charger Acid Condensates Build up in Recirculation Loops. Can be very aggressive to some materials in turbocharger system. 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, CO 2, NO x, SO x, Water, etc 10 Copyright 2013 DuPont. All rights reserved. and indicate registered trademarks or trademarks of DuPont

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 Vol Swell % 1 IRM903, 1wk/150 C Mooney Viscosity 2 ( MU ) Tg 3 ( C ) Cure Key Feature Grade 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 Vamac Ultra Family (higher viscosity / better processing) Vol Swell % 1 IRM903, 1wk/150 C Mooney Viscosity 2 ( MU ) Tg 3 ( C ) Cure Key Feature Grade 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 100 C 3 ASTM D3418 (DSC) 12

Summary VMX2122 vs Vamac DP 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 13

Injection Molding Trials Vamac DP vs. VMX2122 O-rings, manually demoulded 18 16 14 12 Vamac DP compound similar formulations 50 Shots 40 Cavity Mold 10 8 6 4 VMX2122 based compounds 2 0 1 2 3 4 5 6 7 8 9 1011121314151617181920212223242526272829303132333435363738394041424344454647484950 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. 14

VMX2122 - HFFR Formulation Properties change, % General W&C 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 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 20 Heat ageing in air 168hrs@160 C 15 10 5 0-5 -10-15 -20-25 Vamac DP VMX 2122 Hardness Change (pts.) Tensile Strength at Break Change (%) Elongation at Break Change (%) 15

Potential Benefits for Hoses Elongation at break change, % 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 0 GLS Ultra LS Ultra IP VMX2122-10 -20-30 -40-50 Fuchs Titan EG CVT28 Pentosin FFL-4-60 16

VMX2122 Potential Application 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 mm 3 ) 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 Oil Hoses 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 Seals 17

Agenda Vamac Background Automotive Trends Vamac Product Line VMX2122 Latest Ultra Dipolymer VMX5000 Series Latest High Temperature Resistant AEM 18

Product Grade List Vamac pre-compounds for high heat resistance Vol Swell % 1 IRM903, 1wk/150 C Mooney Viscosity 2 ( MU ) Tg 3 ( C ) Cure Key Feature Grade 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 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 1 ASTM D471 2 ASTM D1646, ML1+4 at 100 C 3 ASTM D3418 (DSC) 4 Not suitable for steam autoclave cure 19

VMX5000 Series VMX5015 VMX5394 VMX5315 VMX5020 20

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. 21

Heat Ageing 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) 22

Diffusion limited oxidation AEM/Silica vs 5000 series Molded ISO compression set buttons: - Age for specified time in air - Cut sample in half - Visual check for oxidation - Used silica not black Press Cure 1 day @ 190 C 1 week @ 190 C Ultra HT, filled with Silica press cure 1 day @190 C 3 weeks @ 190 C VMX5015 Ultra HT: oxidation has progressed fully through the sample VMX5000: Oxidized layer remains about the same thickness for 3 weeks 23

Compounding VMX5000 Series 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 80 75 70 65 Hardness, Sh.A, 3s Formulation Vamac VMX 5015 (%) 73 Vamac Ultra IP (%) 27 4-ADA 0.93 Stearic Acid Reagent (95%) 0.33 Vanfre VAM 0.67 Diak TM no 1 0.67 Alcanpoudre DBU-70 1.33 60 55 50 40 50 60 70 80 90 100 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 VMX5000 content (% of total polymer content) 24

Compounding VMX5000 Series 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) 75A Hose 60A Gasket VMX5000 181.8 118 AEM 36 Diak TM 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 * Alcanplast PO 80, Tegmer 812 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 25

Compression Set Resistance: 60 Shore A Gasket VMX5020 VMX5020 Standard black red 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 Compression Set as a function of - Time & Temperature - Surface area / volume ratio - Filler 60 50 40 30 20 10 VMX5000, black VMX5000 red Standard Ultra LS 0 CS ISO815B, 168 h @ 170 C CS ISO815B, 1008 h @ 170 C CS O-ring, 168 h @ 180 C 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 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 Original Physical Properties 40 20 0-20 -40 Heat Ageing 3 weeks at 185 C VMX5000, black VMX5000 red Standard Ultra LS Ageing in Pentosin FFL-5 LV, 1008h at 150 C 40 20 0-20 -40-60 -80-100 Hardness Change (ShA) Tensile Change (%) Elongation Change (%) -60-80 -100 VMX5000, black VMX5000 red Standard Ultra LS Hardness Change (ShA) Tensile Change (%) Elongation Change (%) Volume Change (%) Standard Filled compound too brittle to test VMX5000 series still very elastic Best retention of Elongation (most critical value for AEM) after fluid ageing for VMX5000 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

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. 29