DuPont Vamac & DuPont Viton Performance in Automotive Fluids. Welcome to the Global & Interactive Collaboratory

Transcription

1 DuPont Vamac & DuPont Viton Performance in Automotive Fluids Welcome to the Global & Interactive Collaboratory Laurent Lefebvre Patrick Paglia DPP - Global Automotive Air Duct Market Leader DPP - Technology Associate Plastlab Orbassano, November 23 rd, 2012

2 2 Agenda Performance of Vamac ethylene acrylic & Viton fluoroelastomers in: 1. Engine & Transmission Synthetic Oils 2. Biofuels & Flex Fuels 3. Blow-By & Exhaust Gas Acid Condensates 4. AdBlue Urea 5. Coolant

3 3 Agenda Vamac & Viton Performance in: 1. Engine & Transmission Synthetic Oils 2. Biofuels & Flex Fuels 3. Blow-By & Exhaust Gas Acid Condensates 4. AdBlue Urea 5. Coolant

4 Auto Powertrain Engine Seals & Gaskets based on Vamac & Viton Rear Engine Seal Oil Pan Gasket Oil Filter Seal Parts based on Vamac Parts based on Viton Air Intake Manifold Gasket Cylinder Head Gasket Parts based on Vamac &/or based on Viton Cam Cover Gasket Valve Stem Seal Cylinder O-rings Cranck shaft Seal Camshaft Seal Torsional Vibration Damper Water Pump Seal

5 Main Engine Static Rubber Seals & Gaskets 1. Rubber Gasket 2. Rubber Gasket NBR AEM ACM NBR HNBR FKM Cylinder Head Cover (Rocker Cover, Cam Cover) Cylinder Head Cylinder (Engine Block) Oil Filter 4. Rubber Gasket NBR HNBR AEM ACM FKM 3. Rubber Gasket NBR AEM ACM LSR Oil Pan Additional engine static seals & gaskets : Front cover gasket Oil filler cap seal Oil drain plug Grommets

6 6 Trends in Engine Seals & Gaskets More aggressive fluids in the engine and in the engine oil: - New high temperature synthetic oils (fuel economy, low viscosity) - Presence of fuel/biofuel in engine oil (GDI engines) - Higher level of Blow-by and Exhaust Gas acid condensates - Heat resistance Low temperature Oil resistance Sealing performance (Compressive Stress Relaxation) New opportunities in engine seals for High Performance Elastomers (FKM, AEM, HT-ACM): Cam Cover, Front Cover, Oil Pan,

7 7 Automotive Engine Oils Automotive lubricant composition: base oils (75% to 85 %) : mineral or semisynthetic or FULLY SYNTHETIC package of additives content increase (15% to 25%) : viscosifiers, antiwear, antioxidants, detergents, corrosion inhibitors, dispersing agents, antifoaming agents, alkalinity, anti-freeze agents, extreme pressure agents If the synthetic oil can be dealt with, the additive package can be detrimental to several elastomers

8 8 New Engine Oils Lubricants classified 0W20, 0W30 & 5W30 (fuel economy) & low SAPS* oils to meet EURO V standards (including diesel particle filter technology) New engine oil with Euro V *last generation lubricants based on Low Sulphated-Ash, Phosphorus and Sulphur technology

9 Volume swell (%) 9 Vamac - Performance in Engine Oils recommended by VW Group Volume swell after C (Standard Compounds, 10 phr plasticiser, 70 sh.a) Vamac G Vamac GLS Standard Fuel Economy Fuel Economy Low SAPS oils -5 Castrol GXL 10W40 Shell Helix Plus 5W40 Elf Excellium LDX 5W40 Castrol SLX Long life II 0W30 Castrol SLX Long life III 5W30 (low SAPS) Mobil 1 ESP Formula 5W30 (low SAPS) VW & VW VW & VW VW & VW

10 Hardness change (pts) 10 Vamac - Performance in Engine Oils recommended by VW Group Hardness change after C (Standard Compounds, 10 phr plasticiser, 70 sh.a) 9 Vamac G Vamac GLS 7 5 Low SAPS oils Shell Helix Plus 5W40 Elf Excellium LDX 5W40 Castrol SLX Long life II 0W30 Castrol SLX Long life III 5W30 (low SAPS) Mobil 1 ESP Formula 5W30 (low SAPS)

11 Elongation change (%) 11 Vamac performance in Engine Oils recommended by VW group Elongation change after C (Standard Compounds, 10 phr plasticiser, 70 sh.a) Low SAPS oils Vamac G Vamac GLS Shell Helix Plus 5W40 Elf Excellium LDX 5W40 Castrol SLX Long life II 0W30 Castrol SLX Long life III 5W30 (low SAPS) Mobil 1 ESP Formula 5W30 (low SAPS)

12 Volume swell (%) 12 Vamac - Performance in Engine Oils recommended by BMW group 15 Volume swell after C (Standard Compounds, 10 phr plasticiser, 70 sh.a) 13 Vamac G Vamac GLS 11 9 Low SAPS oils Fuchs Titan SuperSyn SL 5W30 Shell Helix Ultra AB 5W30 Fuchs Titan GT1 5W30 (low SAPS) Castrol SLX LL04 0W30 (low SAPS) Mobil 1 ESP Formula 5W30 (low SAPS) BMW Long life 01 BMW Long life 04

13 Volume swell (%) 13 Vamac - Performance in Engine Oils recommended by Daimler group 15 Volume swell after C (Standard Compounds, 10 phr plasticiser, 70 sh.a) Vamac G Vamac GLS Low SAPS oils Elf Excellium LDX 5W40 Fuchs Titan SuperSyn SL 5W30 Shell Helix Ultra AB 5W30 Fuchs Titan GT1 5W30 (low SAPS) Elf Solaris LSX 5W30 (low SAPS) Mobil 1 ESP Formula 5W30 (low SAPS) MB MB MB & MB

14 Volume swell (%) 14 Vamac - Performance in Engine Oils recommended by Fiat & Iveco Volume swell after C (Standard Compounds, 10 phr plasticiser, 70 sh.a) Vamac G Vamac GLS Urania Turbo LD 15W40 (Iveco) Selenia 20 K 10W40 (Fiat) Selenia WR 5W40 (Fiat) Urania FE 5W30 (Iveco) Turbo charged or multivalve engines Fuel economy for new multijet diesel engines

15 Volume swell (%) 15 Vamac performance in engine oils recommended by PSA group Volume swell after C (Standard Compounds, 10 phr plasticiser, 70 sh.a) Vamac G Vamac GLS Low SAPS oils Total Quartz Diesel W40 Total Quartz Future W30 Total G11077 Lube MA3 5W30 Total Quartz Ineo ECS 5W30 (low SAPS) Total G03232 Lube MA4 5W30 (low SAPS)

16 Properties 16 Vamac performance in aggressive engine oil Total Lube MA5, 0W20 Vamac DOTG free Compounds, 50 phr FEF / 10 phr plasticiser, 65 sh.a Fluid ageing results after C in Total Lube MA5, 0W Vamac G Vamac GLS Vamac Ultra IP Vamac VMX 3110 Vamac VMX 3110, 30 phr FEF / 10 phr plast. Vamac DP peroxide Diamine cured Vamac Ultra & peroxide cured Vamac DP are the best options X 10 Compounsd based on Vamac with low carbon black level has better retention of properties Volume swell (%) Hardness change (points) Elongation -51 change (%) Absolute Elongation x10 (%) Compounds based on Vamac with metal deactivators can be an alternative in case of high level of bivalent metal ions in lubricants

17 Volume Swell, % 17 Vamac performance in aggressive engine oil Mobil 1, 0W Volume Change after ageing at 150 C in Mobil 1, 0W Vamac G/ DOTG Vamac G/ ACT55 Vamac GLS/ ACT55 Vamac Ultra IP/ ACT55 MX-3110/ ACT55 Vamac DP/ Peroxide

18 % Change in Elongation 18 Vamac performance in aggressive engine oil Mobil 1, 0W20 0% Change in Elongation after ageing at 150 C in Mobil 1, 0W20-20% -40% -60% -80% -100% Time (Hours) Vamac G/ DOTG Vamac G/ ACT55 Vamac GLS/ ACT55 Vamac Ultra IP/ ACT55 MX-3110/ ACT55 Vamac DP/ Peroxide Vamac compounds retained > 50% of original properties after 150 C in oil Vamac DP showed the best retention of elongation after ageing in Mobil 1, 0W20 Vamac G & GLS with ACT55 showed the highest elongation loss after oil ageing

19 Percent Retained Sealing (%) 19 Vamac performance in aggressive engine oil Mobil 1, 0W Compressive Stress Relaxation after 150 C in Mobil 1, 0W Time (Hours) Vamac G/ DOTG Vamac G/ ACT55 Vamac GLS/ ACT55 Vamac Ultra IP/ ACT55 Vamac VMX-3110/ ACT55 Vamac DP/ Peroxide Compounds based on Vamac Ultra IP & Vamac DP compound showed similar good CSR properties to Vamac G/ DOTG compound Compoud based on Vamac GLS with ACT55 showed the lowest CSR values

20 Force Retention (%) 20 Vamac sealing performance in engine oil Compressive Stress Relaxation in synthetic oil (Castrol SLX LL III, 5W30 / 150 C) new AEM ACM Vamac G (78 Sh.A) Vamac Ultra IP (79 Sh.A) Vamac Ultra IP (61 Sh.A) HT-ACM (79 Sh. A) According to ISO Method B Shawbury Wallace Test Equipment used Molded pips, 6 mm high & 13 mm diameter Higher force retention better sealing performance WEEK Time (h) After one week, Vamac Ultra IP shows more than double force retention level vs. HT ACM at same hardness level

21 21 Vamac in Fresh and Oxidized IRM IRM902 Fluid 150 C 10 5 Tensile Change (%), 1008 hours, fresh IRM Tensile Change (%), 1008 hours, oxidised IRM-902 Elongation Change (%), 1008 hours, fresh IRM Elongation Change (%), 1008 hours -20 Vamac G Vamac GLS Vamac HVG Vamac DP Vamac did not show any major negative impact caused by oxidation of IRM-902

22 Viton in Engine Oil with/without Aeration Elongation change (%) after 1008 C in Mobil 1 Trisynthetic 0% Viton AL type Viton GAL200S Viton GBL200S Viton GF200S -10% -20% -30% -40% -50% -60% -70% Non Aerated Mobil 1 Trisynthetic 5W30 Aerated Mobil 1 Trisynthetic 5W30-80%

23 23 Oil Immersion Applications - Which Viton? Degree of Base Resistance required Engine Oil Suggested Polymer x Viton B-651C un-aged B-651C, 500 hrs Shell Helix Ultra 10W40 engine oil B-651C, 500 hrs BP Cecilia 20 5W40 engine oil GF-S, 1000 hrs BP Cecilia 20 5W40 engine oil Engine is aerated which helps neutralize the amine based additive packages so standard Viton grades tend to work in the engine

24 24 Viton resistance to lubricants FKM Dipolymer: A-types % Fluorine -CF 2 -CF- -CH 2 -CF 2-66% H 2 HFP-grades CF 3 FKM Terpolymer: (G)AL-, (G)B-, (G)F-types -CF 2 -CF- -CH 2 -CF 2 - -CF 2 -CF 2-66% to 70% CF 3 Acidic H in electron withdrawing environment of vicinal F-atoms allowing X-linking with bisamines or bisphenols but is also vulnerable to attack by bases causing further X-linking, hardening, drop of properties & potential seal failure. {Base}

25 25 Sealing performance of Viton vs other elastomers

26 26 Trends in Engine Seals & Gaskets More aggressive fluids in the engine and in the engine oil: - New high temperature synthetic oils (fuel economy, low viscosity) - Presence of fuel/biofuel in engine oil (GDI engines) - Higher level of Blow-by and Exhaust Gas acid condensates - Heat resistance Low temperature Oil resistance Sealing performance (Compressive Stress Relaxation) New opportunities in engine seals for High Performance Elastomers (FKM, AEM, HT-ACM): Cam Cover, Front Cover, Oil Pan,

27 27 Mixture Engine Oil 15W40 / Diesel + Biodiesel Vamac Volume Swell Fluid ageing tests : 1, 3 & C Volume Increase Vamac G gasket Vamac GLS gasket VMX 3038 turbocharger hose 15W40 -- Test Tube W40 -- Pressure Vessel W40 -- with 7% B20 (Ford) W40 -- with 7% Diesel Engine Oil - 15W40 Valvoline "Premium Blue" Diesel Fuel - local supply in Akron, OH (USA) RME Biodiesel fuel - B20 from Haltermann s in Texas (USA) Increase in volume with switch from test tube to pressure vessel Further increase in volume with addition of diesel or biodiesel RME No difference between conventional diesel & biodiesel B20

28 28 Mixture Engine Oil 15W40 / Diesel + Biodiesel Vamac : Elongation & Elongation Change Fluid ageing tests : 1, 3 & C Absolute Values % change from original Percent Elongation Vamac G gasket Vamac GLS gasket VMX 3038 turbocharger hose Vamac G gasket Vamac GLS gasket VMX 3038 turbocharger hose W40 -- Test Tube % 0% 0% % -31% -12% % -42% -21% % -53% -33% 15W40 -- Pressure Vessel % 0% 0% % -31% -17% % -51% -41% % -63% -40% 15W40 -- with 7% B20 (Ford) % 0% 0% % -33% -25% % -53% -32% % -70% -42% 15W40 -- with 7% Diesel % 0% 0% % -36% -20% % -53% -30% % -62% -44% Change in control test going from test tube to pressure vessel appears to have bigger effect than addition of diesel or biodiesel Vamac Ultra grades (VMX3038) deliver the best mechanical properties after long term fluid ageing

29 29 Vamac sealing performance in Oil / Fuel Blends New test specifications include elastomer testing in Oil / Fuel blends, very often in a 90% / 10% blending ratio. Fuels comprise biofuels like Ethanol. Vamac G Vamac GLS HT-ACM AEM shows advantages over ACM in Compressive Stress Relaxation Tests in Oil / Fuel blends.

30 Permeation Test Setup Vent Method used to measure permeation of oil and gas mixtures through elastomer compounds Purge Gas Test Fluid in Cup Permeant Collection Cup 40 C temperature Compound Sheet Collect and Analyze via GC

31 31 Permeation: Comparison AEM, ACM, HNBR Permeation Values for different elastomers in blend of 98% Motorcraft oil 0W30 with 2% CE10 Measured at 40 C Units are in g / mm thickness / m 2 / day AEM ACM HNBR Ethanol Octane Toluene Total CE10 : 45% toluene 45% isooctane 10% ethanol w/o ethanol

32 32 Transmission System New transmission systems with more gears (e.q. VW 7-speed transmission) in order to improve driving comfort and fuel efficiency Increasing market -> more parts Transmission Seals (eg bonded piston seals) at abt Shore A Resistance of rubbers to new ATFs (like Dexron VI, Pentosin FFL serie)

33 33 Dual Clutch Transmission Prediction in EU

34 34 Example: VW DCT - DSG (Direct Shift Gearbox) The 6-speed wet DSG is DQ250 (2003, BorgWarner) which is for torque lower than 350 Nm. The 7-speed dry DSG is DQ200 (2008, LUK) which is for torque lower than 250 Nm. DQ200 is compact & light and is designed for smaller and economical engines. Roughly use 6% less fuel than MT and 20% than AT. (Volkswagen Automatic Transmission Dalian Plant) DQ250 DQ200

35 Volume Swell in % 35 Vamac - Performance in Transmission Fluids Volume Swell after C (Standard Vamac compounds, 10 phr plasticiser) Vamac G Vamac GLS P ento sin C H F 11S T o tal F luide A T X D exro n II P etro C anada GM D exro n III R D L 2746 Esso A T F LT C astro l SA F XO 75W90 Esso Gear o il B V 75W80 P etro - C anada D exro n VI R D L 3434 C astro l T ransmax Z 75W90 T o tal T ranself Synthese F E75W90 M o bilube P T X 75W90 Traditional fluids New fluids

36 36 Vamac - Performance in New DCT Fluids Castrol BOT 351 C3 > Castrol BOT 428B > Pentosin FFL-2

37 Vamac performance vs other elastomers in ATF Compounds # HNBR #1 HNBR #2 Vamac Ultra IP Vamac VMX3110 ACN % : 34% 43% - - Curing agent Peroxide Peroxide Diamine Diamine 75 phr FEF N550 Yes Yes Yes Yes 5 phr plasticiser Yes Yes Yes Yes Tg by DSC ( C) Comp. Set ISO 815 after 150 C (%) Fluid ageing Petro Canada Dexron VI RDL3434, C Hardness (sh.a) Delta Hd, in Shore-A TS (MPa ) Delta TS in % EaB (%) Delta EaB (%) Volume Swell (% ) HNBR has higher property loss than Vamac after ageing in ATF Dexron VI Swell comparable between Vamac VMX3110 (or GLS) & HNBR with 34% ACN

38 Force Retention (%) 38 Vamac sealing performance in Transmission Fluid OIL AGING (Dexron VI / 150 C) Vamac G (78 Shore A) Ultra IP (79 Shore A) Ultra IP (61 Shore A) HT-ACM (79 Shore A) Acc. To ISO 3384 Shawbury Wallace Test Equipment Cylindrical Specimen, 6 mm high, 13 mm diameter Time (h) Ranking: Vamac Ultra IP > Vamac G >> HT ACM

39 39 Oil Immersion Applications - Which Viton? Degree of Base Resistance required Engine Gear box & Transmission Axle & Wheel bearing Suggested Polymer x Viton B-651C un-aged B-651C, 500 hrs Shell Helix Ultra 10W40 engine oil B-651C, 500 hrs BP Cecilia 20 5W40 engine oil GF-S, 1000 hrs BP Cecilia 20 5W40 engine oil B-651C, 500 hrs Dexron III ATF GF-S, 1000 hrs Dexron III ATF B-651C, 1000 hrs Mobile Axle lube GF-S, 1000 hrs Mobile Axle lube GFLT-S, ETP600S Dexron III ATF ETP600-S, 1000 hrs Mobile Axle lube

40 Percent retained Elong. (%) Percent retained Elong. (%) 40 Viton in Automatic Transmission Fluids 120 Ageing in ATF Petro Canada Dexron III at 150 C 100 GLT-S GF-S GBL-S 20 A-401C Hours Ageing in ATF Petro Canada Dexron VI at 150 C GLT-S GF-S GBL-S B-651C A-401C Hours

41 % Change 41 Viton in Non Aerated & Aerated Automatic Transmission Fluid Elongation change after Aging in Dexron 150 C ( With and Without Aeration) 30% 20% 10% 0% -10% -20% GFLT600S GF600S -30% -40% -50% A361 B651C -60% -70% A361C B651C GF600S GFLT600S Time (Hours) A361C (Aerated) B651C (Aerated) GF600S (Aerated) GFLT600S (Aerated)

42 42 Viton resistance to lubricants (continued) HFP-grades FKM Dipolymer: A-types) -CF 2 -CF- -CH 2 -CF 2-66% CF 3 FKM Terpolymer: (G)AL-, (G)B-, (G)F-types % Fluorine -CF 2 -CF- -CH 2 -CF 2 - -CF 2 -CF 2-66 to 70% CF 3 H 2 acidic H in electron withdrawing environment of vicinal F-atoms allowing X-linking with bisamines or bisphenols PMVE-grades *H/H: degree of acidity FKM GLT-S /GFLT-S -CF 2 -CF - -CH 2 -CF 2 - -CF 2 -CF to 67 % O CF 3 Reduction of acidity (PO-cure mandatory)

43 43 Agenda Vamac & Viton performance to : 1. Engine & Transmission Synthetic Oils 2. Biofuels & Flex Fuels 3. Blow-By & Exhaust Gas Acid Condensates 4. AdBlue Urea 5. Coolant

44 44 Automotive Fuel System Fuel Injector Charcoal Canister Ventilation Line Fuel Regulator Fuel Injection Rail Fuel Filter Roll Over Valve Ventilation Line Fuel Tank Filler Neck Purge Valve Return Line Feed Line Ventilation Line In Tank Pump

45 45 Viton Fuel Applications Fuel Filter Seal Fuel Injector O-ring Fuel Rail Seal Fuel Tank Valve Seal Fuel Sender Seal Fuel Cap Seal Quick Connect O-ring Filler Neck Hose Fuel Vapour Line Fuel Return Line

46 Air Intake Manifold Gasket 3 different type of AIM Gaskets: Gasket between AIM and Exhaust Gas Recirculation (temperature < 250C) Gasket between AIM and Electronic Throttle Valve Control (temperature : 60C) Gasket between AIM and Flange (temperature : 120C)

47 Gram of CO 2 / MJ 47 New Environmental Legislations Reduced CO 2 emissions drives the adoption of bio-fuels Side benefit in reduced engine wear (inherent lubricity of FAME s) Different types of oxygen-containing fuels & biodiesel Ethanol / Methanol / Butanol Oxygenates : MTBE or ETBE Biodiesel (B5 to B20) % - 70% 20 0 Source: Bilan énergétiques et gaz à effet de serre des filières de production des biocarburants Price Waterhouse Coopers / Institut Français du Pétrole

48 48 Material Performance to Fuel/Biofuel Fuel Permeation: Material Choices for Reducing Permeation Losses fuel system elastomer films to M15 23 C Silicone (VMQ) NBR / HNBR Fluorosilicone (FVMQ) Permeation rate g-mm/m 2 /d (Log chart) Nylon Viton A 35 Viton B 12 Viton GF 3 THV Tefzel ETFE Teflon PTFE higher fluorine = lower permeation Teflon FEP

49 49 Fuel and Permeation Resistance of Fluoroelastomers to Methanol & Ethanol Blends Environmental factors driving current fuel system designs Need to lower hydrocarbon emissions which includes the use of oxygenates like ethanol and methanol Need to reduce dependence on fossil fuels and increase use of alternative renewable fuel sources like ethanol and methanol Ethanol is used in the US, Brazil Methanol is used in China Drive towards global automotive platforms Development of global specifications for fuel systems Elastomers in fuel systems must perform in global flex fuels including ethanol and methanol fuel blends.

50 50 Bioethanol Feed Stocks Switch grass Sugar cane Corn

51 Perm rate (g-mm/m²/day) 51 Bioethanol Resistance of Viton Permeation Rate Permeation of Fuel C / Ethanol Blends 1008 hours at 40 C Fuel C CE-10 CE-25 CE-50 CE-85 E GLT-S A-601C GBLT-S GFLT-S B-601C F-605C GF-S low fluorine (wt %) high Peak permeation at ~25% Ethanol in Fuel C

52 Volume Change, % Bioethanol Resistance of Viton Volume Swell Volume Change in Bioethanol & fuel blends 1008 hours at 40 C (weekly fuel change) 25 Fuel C 20 CE-10 CE-25 CE CE-85 E GLT- 600S A-601C GBLT- 600S B-601C GFLT- 600S VTR F-605C GF- 600S low fluorine (wt %) high 52

53 Volume Change, % Bioethanol Resistance of Viton Volume Swell Temperature Dependence Effect of Temperature Volume Change, CE C C C C 0 GLT- 600S A-601C GBLT- 600S B-601C GFLT- 600S VTR F-605C GF- 600S low fluorine (wt %) high 53

54 54 Biobutanol Feed Stocks Sugar beets Wheat Corn or Maize Sugar cane Switchgrass

55 Volume Change, % 55 Biobutanol Resistance of Viton Volume Swell Volume Change 10 1-Butanol at 40 C (weekly fuel change) hours 336 hours 504 hours 672 hours 1008 hours GLT- 600S A-601C GBLT- 600S B-601C GFLT- 600S VTR F-605C GF- 600S low fluorine (wt %) high

56 Volume Change, % Biobutanol Resistance of Viton Volume Swell Volume Change Fuel C / 1-Butanol (80/20) at 40 C (weekly fuel change) 168 hours 336 hours 504 hours 672 hours 1008 hours GLT- 600S A-601C GBLT- 600S B-601C GFLT- 600S VTR F-605C GF- 600S low fluorine (wt %) high 56

57 Volume Change, % 57 Performance of Viton with Different Bioalcohols Volume Change in Bio-alcohols & fuel blends hours at 40 C Butanol Ethanol Fuel C Fuel C/Butanol (80/20) Fuel C/Ethanol (75/25) 0 GLT- 600S A-601C GBLT- 600S B-601C GFLT- 600S VTR F-605C GF- 600S low fluorine (wt %) high

58 58 Biodiesel Feed Stocks Jatropha Palm & Coconut Canola Sunflower Rapeseed Soybean Kelp Algae

59 What is Biodiesel? Don t be confused by the name Unlike Bioethanol and Biobutanol which are chemically identical to their petroleum derived counterparts, Biodiesel and Petrodiesel are chemically different and have significantly differing effects on elastomers Biodiesel is an ester based fluid Petroleum Diesel is a hydrocarbon fluid 59

60 Specifications Similar but different specifications in U.S. and European Union Europe DIN EN US ASTM D6751 ASTM spec is broader (probably to allow for wider range of starting oils) Both have Water < 500ppm Acid number < 0.5 mg KOH/g Na + K < 5ppm 60

61 Volume Change, % 61 Fresh vs. Old RME Volume Change "Fresh" B100 RME at 125 C "Fresh" RME 336 Hrs "Fresh" RME 1008 Hrs "Old" RME 336 Hrs "Old" RME 1008 Hrs GBL-S Ca(OH)2 A401C

62 62 Viton performance in pure & fresh Biodiesel Pure & Fresh Biodiesel is not aggressive to FKM compounds High Swell of standard FKM is caused by a seconder order effect: - Contamination (water, residual catalyst, ) - Degradation products (acids, aldehydes, )

63 Volume Change, % 63 Effect of Water Aged in wet B100 RME at 125 C Volume change (%) 120 fuel change at test interval hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours 20 0 "NMO" GBL-S "NMO" GF-S GBL-S Ca(OH)2 Wet = addition of 0.5% distilled water to RME "NMO"= No Metal Oxide formulation A401C F605C

64 Volume Change, % 64 Effect of Water on Compounds Based on Viton 80 Volume Change "wet" B20 RME at 125 C ( fuel change at test interval) hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours 0 GBL-S (NMO) GF-S (NMO) GBL-S Ca(OH)2 (wet = addition of 0.5% water to RME) A401C F605C 64 64

65 Volume Change, % 65 Effect of Water on Compounds Based on Viton Volume Change "wet" B5 RME at 125 C ( fuel change at test interval) 336 hours 672 hours 1008 hours 2016 hours 3024 hours GBL-S (NMO) GF-S (NMO) GBL-S Ca(OH)2 (wet = addition of 0.5% water to RME) A401C F605C 65

66 Volume Change, % 66 Effect of Metal Oxide Level Volume Change "wet" B100 RME at 125 C ( fuel change at test interval) 336 hours 672 hours 1008 hours 1512 hours 2016 hours 3024 hours GBL-S NMO GBL-S (Ca(OH) 2-1.5) GBL-S (Ca(OH) 2-3.0) (wet = addition of 0.5% water to RME) 66

67 Volume Change, % 67 Best-in-Class for Aggressive BDF Volume Change "wet" RME hours at 125 C ("best-in-class") GBL-S (NMO) GF-S (NMO) B5 RME B20 RME B100 RME (wet = addition of 0.5% water to RME) 67

68 68 Degradation pattern in wet RME Carboxylic acid is formed by the hydrolysis of FAME. Carboxylic acid moves into FKM compound and reacts with metal oxide/hydroxide forming metal carboxylates. Metal carboxylate causes dehydrofluorination and double bond formation in the polymer chain. 1. R M E + H 2 O R C O O H + C H 3 O H [ H + o r O H - C a t a l y z e d ] 2. 2 R C O O H + M O [ M 2 ] [ R C O O - ] 2 F K M M F R C O O H + d e h y d r o f l u o r i n a t e d F K M 3. 2 R C O O H + M ( O H ) 2 [ M + 2 ] [ R C O O - ] 2 + H 2 O F K M M F R C O O H + d e h y d r o f l u o r i n a t e d F K M

69 69 Oxidative degradation of FAME s Biodiesel Oxidation Increases with the level of unsaturation (Iodine N o ) Initial oxidative attack at allylic hydrogens in a chain reaction Formation of hydroperoxides which decompose to aldehydes, alcohols and shorter chain carboxylic acids J. A. Waynick et. al. Characterization of Biodiesel Oxidation and Oxidation Products, Southwest Research Institute Project , August 2005 FAME shelf life reported as ~6 months if stored properly Oxidation begins immediately without A/O protection

70 70 Proposed mechanism Peroxides from oxidation of FAME react with double bonds in the polymer chain causing chain scission via haloform cleavage. 2+ M( - OOC-R) 2 (R-COO - ) 2 M 2+ dehydrofluorination CF 3 (R-COO - ) 2 M 2+ MF RCOOH (R-COO - ) 2 M 2+ (R-COO- ) 2 M 2+ ROOH R O O (R-COO - ) 2 M 2+ CF 3 MF RCOOH (R-COO - ) 2 M 2+ - ROH O (R-COO - ) 2 M 2+ CF 3 MF RCOOH (R-COO - ) 2 M 2+ HO - O O - H (R-COO - ) 2 M 2+ CF 3 MF RCOOH (R-COO - ) 2 M 2+

71 71 Uncured GBL NMO Cured GBL NMO Different height peak was observed at -53.5ppm -59ppm Uncured GBL Ca(OH)2 Cured GBL Ca(OH)2 After immersion in RME, Ca(OH)2 GBL-S showes higher volume swell than NMO GBL-S. Significantly more double bonds were formed in Ca(OH)2 GBL-S after immersion in RME compared to NMO GBL-S.

72 72 What About Lower Temperature Biodiesel Resistance? Long term 40 C study 40 C is warm but not unreasonably high for storage and transport 6000 hours B100 and B20 RME Fuels with added water and acid Acid and water close to as-made spec limits (ASTM D6571(B100) and D7467 (B5 B20 blends) B100 acidified to TAN 1.5 (vs. 0.5 spec) B20 acidified to TAN of 0.3 and 0.6 (vs. 0.3 spec) Water at 800 ppm (for B TAN) or 1000 ppm (vs. 500 ppm separate phase water spec) NB: acid and water levels don t consider starting levels in RME Fuel changed every 504 hours (3 weeks) Compounds of A-401C, GBL-S (NMO, Ca(OH) 2 and ZnO)

73 Volume Swell [%] 73 B20 (TAN 0.3) at 40 C Results Swell of Various Viton Compounds in Wet, Acidified B20 at 40 C (initial TAN of 0.3 with 800 ppm water) A401C GBL-S NMO GBL-S CaOH GBL-S ZnO Time at 40 C [hrs] B20 near specification limits for acid and water is aggressive toward metal oxide containing compounds even at 40 C

74 74 Tentative Conclusions Biodiesel blends such as B20 appear to be more aggressive at low temperatures toward metal oxide containing fluoroelastomers than B100 when water and acid are present. Biodiesel blends such as B20 are aggressive toward metal oxide containing fluoroelastomers when at or near the acid and water limits in ASTM D7467 even at relatively modest temperatures. Metal oxide free formulations continue to show robust behavior toward biodiesel and biodiesel blends independent of acid and water content The recommendation to use specially formulated peroxide cured compounds (NMO compounds) for critical applications and for applications where the cost and consequence of failure are high should not be limited to high temperature applications.

75 75 Historic Data on FKM in Flex Fuels Historic data exists on: FKM in various fuel-oxygenate blends at R.T. FKM in various fuel-ethanol blends at elevated temperatures This data indicates that fuel-methanol blends are more aggressive to FKM than the current fuel-ethanol blends which are available in the US.

76 76 Test Conditions Fuels Fuel C CM15A (15% Aggressive Methanol/ 85% Fuel C) CM30A (30% Aggressive Methanol/ 70% Fuel C) CM50A (50% Aggressive Methanol/ 50% Fuel C) CM85A (85% Aggressive Methanol/ 15% Fuel C) Aggressive Methanol Formula for Ford Aggressive Methanol ml anhydrous methanol 5.0 ml Aggressive water ml formic acid Aggressive water: 1.0 liter of distilled water g NaCl (600 ppm Cl g Na2SO4 (600 ppm SO4) g NaHCO3 (600 ppm HCO3)

77 77 Test Conditions Test time and temperature Immersion C Permeation C Long-term immersion (APA polymers only) C in CM15A Fuel changed weekly Samples tested at 168, 672, 2000, 3000, 4000 and 5000 Hours Sample after 5000 Hours dried out for C

78 78 Original Physical Properties of FKM Compounds Physical Properties FKM FKM FKM FKM FKM FKM A401C B601C FKM F605C GF600S GLT600S * GBLT600S GFLT600S Physical R.T 50% Modulus [MPa] % Modulus [MPa] Break [MPa] Break [%] Hardness, Shore A [Pts] Compression Set, O-Ring C, % Low Temperature Tg by MDSC, C TR-10, C Static O-Ring Test, C Test Specimens Cured: C Bisphenol-cured Grades Postcured: C Peroxide-cured Grades Postcured: C * : withdrawn grade shown for academic purpose 78

79 Percent Loss in Tensile 79 Fuel Immersion Tensile Loss C 0% -10% FKM A401C FKM B601C FKM F605C FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S -20% -30% -40% -50% -60% -70% -80% Fuel C CM15A CM30A CM50A CM85A Methanol 79

80 Percent Change in Elongation 80 30% Fuel Immersion Elongation Loss C 20% 10% 0% -10% Viton A401C Viton B601C Viton F605C Viton GF600S Viton GLT600S Viton GBLT600S Viton GFLT600S -20% -30% Fuel C CM15A -40% CM30A CM15A -50% CM85A Methanol -60%

81 Percent Volume Change 81 Fuel Immersion Volume Change C Fuel C CM15A CM30A CM50A CM85A Methanol FKM A401C FKM B601C FKM F605C FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S 81

82 Permeation, g-mm/m2/day 82 Permeation 40 C (units, g-mm/m2/day; tested for 672 hours) Fuel C CM15A CM30A CM50A CM85A Methanol FKM A401C FKM B601C FKM F605C FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S 82

83 83 Swell & Permeation Normalized Values EtOH containing fuels % Fuel C CE 10 CE 25 CE 50 CE 85 2 Ethanol 0 Swell Permeation A-401C Swell Permeation GLT-600S Strong dependance of permeation on monomers types HFP vs. PMVE Roughly 100 % higher permeation for PMVE (low temperature) grades About 10 % more swell with GLT-600S 83

84 84 Swell & Permeation Normalized Values MeOH containing fuels % 1 1 Swell Permeation Swell Permeation A-401C GLT-600S Fuel C CM 15A CM 30A CM 50A CM 85A Methanol Strong dependance of permeation on monomers types HFP vs. PMVE Roughly 50 % more swell with PMVE (low temperature) grades About 10 % more swell with GLT-600S 84

85 Low temperature measurements ( C) 85 Low Temperature Properties GFLT-S GLT-S A B GF-S Tg (DSC, inflection) Sealing dry O-ring Sealing soaked in unleaded fuel Sealing soaked in fuel C -40 Static sealing possible at about 15 C below polymer Tg -50 Conditioning in fuel plasticizes the seal and lowers sealing temperature TR-10 ( C) e.g. GLT-S seals to : about 45 C (dry) about 48 C (conditioned in unleaded fuel) about 54 C (conditioned in Fuel C) 85

86 86 Low Temperature Properties 0.0 Initial, Unaged in fluid Aged 22 hrs in E100 at 23 C Aged 22 hrs in E22 at 23 C Aged 72 hrs in E22 at 60 C Tg post cured compounds C B600 - MT AL600 - MT AL600 - green Renault, Fuel Injector O-ring, 19 % compression level 86

87 Percent Change 87 Fuel Immersion Tensile Loss C in CM15A 0% -10% -20% Dry Out Data -30% -40% -50% -60% -70% Hours FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S 87

88 Percent Change 88 Fuel Immersion Elongation Loss C in CM15A 10% 0% Dry Out Data -10% -20% -30% -40% -50% Hours FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S

89 Volume Change, % 89 Fuel Immersion Volume Swell C in CM15A FKM GF600S FKM GLT600S FKM GBLT600S FKM GFLT600S 168 hr 672 hr 2000 hr 3000 hr 4000 hr 5000 hr 5000 hr - Dryout 89

90 % Volume Swell. 90 Results of Vamac in FAM-B & in Biodiesel Vamac volume swell after 1 23 C in Fuel/RME Biodiesel G standard G/GLS (50/50) standard GLS standard % RME in the blend Fuel #2 + RME *Significant swell and property loss in gasoline *After redrying, properties go back to original excellent value *Swell can be reduced only to a limited extent with Vamac GLS & VMX 3110 *2% and 5% blends of biodiesel fuels are compatible with Vamac G *For the 20% blend use of Vamac GLS is appropriate

91 91 Agenda Vamac & Viton performance to : 1. Engine & Transmission Synthetic Oils 2. Biofuels & Flex Fuels 3. Blow-By & Exhaust Gas Acid Condensates 4. AdBlue Urea 5. Coolant

92 92 Blow By Gas Origin Blow By Gas is a leakage flow between the piston and the cyclinder wall originated through the pressure difference between combustion chamber and the crankcase. Blow By Gas accumulates with oil & fuel particles. In the past, Blow By Gas was released into the environment. Nowadays only closed crankcase ventilation systems are allowed. Blow By Gas composition varies and depends on : *engine types, fuel or diesel engine (fuel more critical) *engine performance and management *driving style (speed, r.p.m, number of cold starts) *design of ventilation (dead areas, air volume flow) 92

93 V o lu m e S w e ll, Retention of Elongation, % 93 Why Vamac for Blow-By Applications? ECO is the polymer that was often used in PCV tubes. Problems of ECO: - Lead was used as stabilizer - Poor heat resistance or scorch issue with ECO lead free - Acid resistance limited ECO & Vamac after 1 90 C Elongation Retention in Ford s Acid Condensate 140 ECO & Vamac after 1 90 C Swell in Blow-By condensate from Ford 120.0% 100.0% Vamac G Vamac GLS ECO ( Lead-Free ) 120 V a m a c G 80.0% V a m a c G L S 100 E C O ( L e a d -F r e e ) 60.0% 80 E C O 40.0% % 20 Vamac G Vamac G LS 0.0% Ford acid condensate chemical composition: 14.0 ml Methanoic ( Formic ) Acid 11.0 ml Nitric Acid 15.0 ml Ethanoic ( acetic ) Acid 1.0 ml Hydrochloric Acid 1.0 ml Sulphuric Acid ml Distilled Water

94 94 Source: ElringKlinger, GAK Paper, 2006 Blow-By Resistance, BMW Condensates 1 & 2 BMW Condensate I Component Weight-% Naphthalene 1 FAM-A (DIN ) 44,5 Cecilia 20 44,5 Formaldehyde-10 *) 10 *) stabilized with 10 % methanol BMW Condensate II Component Weight-% Formaldehyde-10 *) 10 Deionized water 89,7 HNO3 (65%) 0,18 Formic Acid (98-100%) 0,06 Acetic Acid (96%) 0,06 Condensates were specified in 2001, new condensates currently in specification phase. New condensates may have lower fuel content (C1) and might be lower in Formaldehyde. Acid condensates in general expected to be lower in ph, and therfore much more damaging. In Diesel engines, Blow-By acids are reinforced by additional Exhaust Gas condensate acids.

95 95 Source: ElringKlinger, GAK Paper, 2006 Blow-By Resistance, BMW Condensate 1 (fuel/oil) Autoclave, C HNBR 1 HNBR 2 HNBR 3 HNBR 4 HNBR 5 AEM 60 ShA ACM 60 ShA ACN content GLS? dhd (pts) TS original 23,3 22, ,7 16,6 11,1 9,3 TS after immersion 13,1 13,3 9,5 6,6 4,9 5,3 3,8 d TS ,2-54,7-68,4-70,2-51,7-32,8 EaB original EaB after immersion d EaB -26,4-27,3-40,4-59,4-58, Volume Swell (%) Volume swell increases as ACN content decreases, ACM and AEM clearly better in terms of volume swell - TS and EaB change high for HNBR at low ACN content, however absolute TS and EaB after immersion are still higher compared to ACM or AEM. - HNBR at ACN content >40% show good retention of properties 95

96 96 Source: ElringKlinger, GAK Paper, 2006 BMW Condensate 2 (aqueous acid) Autoclave, C HNBR 1 HNBR 2 HNBR 3 HNBR 4 HNBR 5 AEM 60 ShA ACM 60 ShA ACN content GLS? dhd (pts) TS original 23,3 22, ,7 16,6 11,1 9,3 TS after immersion 9,5 10,1 10,7 9,6 9 10,8 7,6 d TS -59,4-55,3-49,1-53,7-45,5-2,8-18,6 EaB original EaB after immersion d EaB -70, ,5-62,6-58,3-5,1-32,8 Volume Swell (%) Volume swell increases as ACN content increases, ACM better than all HNBR, Vamac outstanding - TS and EaB change high for all HNBR grades - Vamac clearly a class better than all other polymers, even though very likely Vamac GLS (high ester content) is used for this reference compound. 96

97 Source: greencarcongress.com/emissions 97 New Technologies to limit Emissions FOR PARTICLE REDUCTION Injection Combustion High pressure diesel fuel injection Optimization of the combustion chamber Diesel particle filter (EGR) Additional Systems in Engines, Opening Applications for High Performance Elastomers

98 98 Sensor Hoses for Diesel Particle Filter Sensor hose between pressure sensor and DPF Temperature and Exhaust Gas exposure Materials used : FKM, FKM/VMQ, AEM Hose made of Vamac

99 Source: greencarcongress.com/emissions 99 New technologies to limit emissions There are emission control technologies currently available to enable compliance of diesel motor vehicles to the next level of requirements FOR NOx REDUCTION : High pressure direct gasoline injection Increased recirculated gas in EGR (Exhaust gas recirculation)

100 100 Exhaust Gas Recycling Loops (Diesel engine) High Pressure Loop (HPL) Low Pressure Loop (LPL) HPL Turbo Turbo LPL Engine Engine 20% max. of EGR trapped 50% max. of EGR trapped 70% max. of Exhaust Gas Recirculating High Pressure High Temperature (> 200 C) Mainly metal pipes Low Pressure Low Temperature (< 150 C) Mainly flexible rubber / plastic tubes + rubber seals EGR loops complement a Turbo-Charger for NOx reduction It creates a significant challenge to most materials in the Air Management loop

101 101 Air Management Line - Flow and Cooling Intake Manifold TCH / CAC Duct (Cold Side) EGR Actuator/ Valve EGR Cooler Turbocharger Intercooler or Charged Air Cooler (CAC) TCH / CAC Duct (Hot Side)

102 102 Air management Trends : more acids EGR contact with Euro 4 Cold hose between IC and AIM EGR contact with Euro 6 Crankcase ventilation hose for closed PCV system Blow-by gas contact with Euro 4 Intercooler AIM seals Inlet manifold Exhaust manifold Exhaust Turbo charger Fresh air Air filter Hot hose between turbo and intercooler EGR contact with Euro 6 Vacuum tube (molded) or short connector between air filter and turbo charger EGR & Blow-by contact with Euro 6 DuPont has developed an extensive data collection of our materials performance in blow-by and EGR gases and condensates

103 103 Exhaust Gas Condensates, Test Parameters Which parameters might influence the test? ph 1 up to 5 with average 3 Size and shape with or without Aeration Sample Equipment Autoclave or reflux system Yes Finished Parts Lab Specimens Autoclave No Reflux - 1 E + 50 C 100 C 150 C Mineral Temperature Organic Mineral /Organic Liquid 168 h 504 h 1008 h 2000 h Acid Type Gas Time 60 C up to 150 C with average C HCl, HNO3, H2SO4 => mineral HCOOH, CH3COOH => organic Salts of acids Other acids Phase Vapour (= gas phase) or Condensate (= liquid phase) 168 h (short term) up to 2008 h (long term)

104 104 Autoclave Equipment used in DuPont Lab Diameter: 97 mm Length: 204 mm Volume: around 2 litres Thickness: 5 mm Material: stainless steel 316L Valves: Swagelok serie R3A, (ref. SS-4R3A adjusted bars) Two sets of lab specimens tested in the autoclaves (liquid phase & gas phase)

105 105 EGR acid solutions selected First EGR solution (ph =3.3) defined by PSA Concentration First EGR solution (ph =3.0) defined by VW Concentration mmol/l KF 0.86 NaCl 4.23 HNO H2SO NaOH 2.81 Lab tests made with fluids close to OEM reference mmol/l CH3CO2NH NH4NO (NH4)2SO HCOOH CH3CH2COOH PSA EGR chemical composition: only mineral based, ph 3.3 VW EGR chemical composition: organic based, ph 3.0 N.B.: PSA & VW EGR acid solutions above have been modified recently

106 106 Results of Vamac & Viton : Influence of acid type PSA EGR liquid contact, C Vamac G Viton A401C Viton GF-200S with MO Hardness change (points) VW EGR exposure Vamac GLS Viton GF-200S Tensile change (%) Elongation change (%) Volume Swell (%) 12 VW EGR exposure Viton A401C VW EGR liquid contact, C -2 Hardness change (points) Vamac performs well in mineral & organic acids Compounds of Viton without metal oxide have very good resistance to all acid types Compounds of Viton with metal oxide is not recommended for use with organic acids Tensile change (%) Elongation change(%) Volume Swell (%) 19 Vamac G Vamac GLS Viton A401C ("destroyed") Viton GF-200S Viton GF-200S with MO ("destroyed") 8 7 3

107 107 Other elastomers: Influence of acid type PSA EGR liquid contact, C Vamac GLS Standard ACM CPE Hardness change (points) Viton GF-200S 'HT-ACM' ECO Tensile change (%) Elongation (%) Volume Swell (%) Standard ACM, ECO & CPE: poor resistance to EGR in this lab evaluation HT-ACM has poor retention of mechanical properties vs Vamac VW EGR liquid contact, C PSA EGR exposure Vamac GLS Standard ACM CPE ("destroyed") -7-8 Hardness change (points) Viton GF-200S 14 1 Viton GF-200S 'HT-ACM' ECO ("destroyed") ECO Tensile change (%) Elongation change (%) Volume Swell (%) -32 VW EGR exposure CPE

108 108 Results of Vamac & Viton : Gas vs liquid phase VW EGR liquid contact, C -3-2 Hardness change (points) Tensile change(%) Elongation change (%) Volume Swell (%) 19 Vamac G Vamac GLS Viton A401C ("destroyed") Viton GF-200S Viton GF-200S with MO ("destroyed") Gas Phase is nearly as aggressive as liquid phase, even at 90 C only Gas phase is less agressive than liquid phase for Viton A401 C VW EGR gas contact, C Vamac G Vamac GLS Viton A401C Viton GF-200S Viton GF-200S with MO ("destroyed") Hardness change (points) Tensile change (%) Elongation change (%) Volume Swell (%)

109 Tensile change (%) Elongation change (%) Volume swell (%) 109 Results of Vamac & Viton : Influence of test temperature 50 VW EGR liquid contact, volume swell C C C -50 Vamac G Vamac GLS Viton GF-200S HT-ACM VW EGR liquid contact, tensile change C C C Vamac G Vamac GLS Viton GF-200S HT-ACM 276 VW EGR liquid contact, elongation change C C C Vamac G Vamac GLS Viton GF-200S HT-ACM Vamac clearly performs better than HT-ACM

110 110 VW EGR acid solution - liquid contact, C, ph = Results of Vamac & Viton : Influence of ph Vamac G Viton GF-200S 'HT-ACM' Hardness change (points) -1 Vamac GLS Standard ACM Tensile change (%) Elongation change (%) Volume Swell (%) Volume swell increases with low ph value Mechanical properties worsen with lower ph but the drop remains moderate for Viton GF-S without metal oxide and both compounds of Vamac Is ACM or HT-ACM suitable for sealing applications in contact with acid? VW EGR liquid contact, C, ph = Vamac G Viton GF-200S 'HT-ACM' Hardness change (points) Vamac GLS Standard ACM Tensile change (%) Elongation change (%) Volume Swell (%)

111 111 Vamac, Results at ph 1 Mixture of HAc / HNO 3, adjusted to ph 1, 504 hours at 100 C Lab Autoclav, liquid phase HNBR compound (44% ACN) was tested simultaneuosly Vamac G Vamac GLS Ultra IP VMX-3038 Hardness Shore A (1 sec) Delta Hardness Tensile Strength [MPa] 9,5 9,1 9,5 8,9 Delta TS [%] Elongation at break [%] Delta Elong. [%] Volume Change (%) Weight Change (%) More impact at such low ph values compared to ph3 results. Still maintains most of its elastomeric properties. Significant better results in the Gas phase.

112 112 HNBR at ph 1 HNBR slabs, after 504h at 100 C in HNO3 / HAc mixture (ph 1) Compound completely destroyed.

113 113 Acid Proof Viton Bisphenol Cured Develop a Viton technology cured with bisphenol cross-linker that displays excellent resistance to concentrated acid (BbG, EGR & aggressive biodiesel) and that is cost competitive to peroxide curable FKM

114 Low temperature flexibility TR-10 ( C) 114 Acid Proof Viton Bisphenol Cured ETP-S GF-S F GFLT-S B GBL-S A AL GAL-S GLT-S Volume swell upon immersion in M15 / 7 d / room-temperature (%) Features: Acid resistance at lower cost than Peroxide Product performance targeted Mechanical Properties : similar to original gum / PC Limit hardness increase to maximum +/- 5 Limit modulus change to maximum +/-10 % Low TºC: AL to B performance Acid Resistance Process (extrusion, molding): good processability possibility to extrude veneers

115 Volume change [%] 115 Acid Proof Viton Bisphenol Cured Product Description: VTX-9303 VTX-9303 is a bisphenol curable fluoropolymer precompound designed for extruded hose applications with 69 % Fluorine. VTX-9303 provides excellent resistance to organic acid typically contained in EGR condensates and degraded FAME (fatty acid methyl ester) based biofuels Aging in acetic acid, 1M, 168 hours, 100 C FKM VTX-9303, NMO FKM VTR-9209 with MO FKM VTX MgO 1 Post cured 230 C Acid immersion 168hrs Post cured 175 C Acid immersion 168hrs Post cured 230 C Acid immersion 504hrs Post cured 175 C Acid immersion 504hrs 115

116 Elongation at break, % Tensile strength MPa 116 Acid Proof Viton Bisphenol Cured Fluid ageing, Acetic acid 2.5pH, 168hrs@100C Tensile at 23C Tensile after fluid ageing VTX-9303, NMO VTR-9209 with MO VTX-9303, MgO 1 Fluid ageing, Acetic acid ph 2.5, 168hrs@100C Elongation at 23C Elongation after ageing High level of property retention in acid solutions VTX-9303, NMO VTR-9209 with MO VTX-9303, MgO

117 117 Acid Proof Viton : VTX 9304 for seals Product Description: VTX-9304 VTX-9304 is a bisphenol curable fluoropolymer precompound with 66 % Fluorine designed for injection moulding applications. VTX-9304 provides excellent resistance to organic acid typically contained in EGR condensates and degraded FAME (fatty acid methyl ester) based biofuels. Volume change in EGR solution nitric acid / acetic acid, ph = 1, 100ºC : 2.5%

118 118 Acid Proof Viton : VTX 9304 for seals

119 119 Acid Proof Viton : VTX 9304 for seals

120 120 Acid Proof Viton : VTX 9304 for seals

121 121 Acid Resistance - Conclusion of DuPont lab study ECO, CPE (CM): Can be significantly affected in acid condensates (EGR, Blow-by) Increased risk of failure for the parts exposed to EGR ACM, HT-ACM: Shows severe effects in the various tests Careful study for each application Vamac AEM : Viton FKM: Standard compounds demonstrate excellent resistance to exhaust acids and gases Vamac can be recommended for cost-effective EGR hose and sealing solutions Standard compounds do perform well in these acidic environments, even when highly concentrated and/or at high temperature caution with organic acids Viton recommended broadly for use in contact with EGR. Viton peroxide cured compounds without metal oxide, are the ultimate choice, but bisphenol technology to be become available

122 122 Agenda Vamac & Viton performance to : 1. Engine & Transmission Synthetic Oils 2. Biofuels & Flex Fuels 3. Blow-By & Exhaust Gas Acid Condensates 4. AdBlue Urea 5. Coolant

123 Source: greencarcongress.com/emissions 123 New Technologies to limit Emissions FOR NOx DESTRUCTION : NOx catalyst Exhaust gas treatment (with urea addition) Exhaust Washing Systems generate new Applications for Elastomers & Thermoplastics

124 124 SCR System Aggressive media detrimental to several elastomers DuPont developed an extensive set of data analysis of materials performance in this environment

125 125 AdBlue System For elastomeric materials which are used in contact to AdBlue, additional resistance to Diesel or Engine oils is very often required. This eliminates non-polar materials like EPDM.

126 126 Properties, Original Standard formulations at moderate plasticizer levels Vamac G Vamac GLS Vamac Ultra IP Vamac DP Hardness Shore A (1 second) ISO : Tensile properties (type 2) at 23 C ISO 37:2005 Cor Tensile Strength [MPa] 17,1 16,9 17,7 9,5 17,7 Elongation at break [%] Modulus at 100 % [MPa] 6,9 6,8 5,7 2,1 5,5 Tear strength C - Crescent [kn/m] ISO 34-1: ,9 23,5 27,7 34,3 30,4 C Set ISO 815, C, plied disks [%] C Set VW 22 hours at 150 C VW PV 3307 [%] VMX TG by DSC [ C] ISO 22768: Diamine cured grades were formulated at ShA. With the same combination of filler and plasticizer, Vamac DP comes out at 60 ShA. Overall properties are better for the high viscosity Vamac Ultra grades IP and VMX Peroxide cured Vamac shows poorer Compression Set results.

127 127 Properties after Heat Ageing, 168 h at 175 C Vamac G Vamac GLS Vamac Ultra IP Vamac DP VMX Heat ageing 168 hours at 175 C ISO 188:2007 Hardness Shore A (1 second) ISO : Delta Hardness Tensile Strength [MPa] 15,4 14,5 14,9 8,8 14,4 Delta TS [%] Elongation at break [%] Delta Elong. [%] Modulus at 100 % [MPa] 6,7 6,8 5,5 3,2 4,8 Delta 100% [%] Excellent retention of properties for all diamine cured Terpolymers. Vamac DP shows highest level in property change.

128 128 Oil Ageing in Lubrizol OS for 504 h at 160 C Vamac G Vamac GLS Vamac Ultra IP Vamac DP VMX Hardness Shore A (1 second) Delta Hardness Tensile properties (type 2) at 23 C Tensile Strength [MPa] 12,4 13,6 14,9 9,4 15,5 Delta TS [%] Elongation at break [%] Delta Elong. [%] Modulus at 100 % [MPa] 7,9 8,4 6,5 2,0 6,0 Delta 100% [%] Volume Change ISO 1817: Weight Change Lubrizol OS is a reference fluid used to simulate resistance to engine oil Excellent retention of properties Fluid swell can be further optimized influenced by compounding

129 129 Ageing in AdBlue for 168 h at 120 C Liquid Phase Vamac G Vamac GLS Vamac Ultra IP Vamac DP VMX Hardness Shore A (1 second) Delta Hardness ISO 188: Tensile Strength [MPa] 9,8 3,5 21,2 11,0 19,6 Delta TS [%] Elongation at break [%] Delta Elong. [%] Modulus at 100 % [MPa] 10,2 2,8 9,5 Delta 100% [%] Volume Change Weight Change Tests were carried out in a lab autoclave using a Kalrez FFKM seal to avoid any leakage. Vamac GLS with its high MA content lost all its elastic properties after 1 week at 120 C. Vamac G is also loosing most of its elastic properties. The high viscosity grades Vamac Ultra IP and VMX-3038 maintain most of their properties, only the Modulus shows a significant increase. The peroxide cured Vamac DP performs best in terms of Modulus retention.

130 130 Ageing in AdBlue for 168 h at 120 C - Graphical Vamac Ultra IP Vamac VMX-3038 Vamac G Vamac GLS Hardness Change (pts.) Tensile Change (%) Elongation Change (%) Volume Change (%)

131 131 Vamac Ultra IP Short term Ageing in AdBlue 168 h at 80 C,100 C & 120 C

132 132 Vamac Ultra IP Long term Ageing in AdBlue 1008 h at 80 C No major difference between liquid & gas phase

133 133 Viton performance in AdBlue Viton is not suitable in AdBlue for temp. > 100ºC Kalrez will be the material of choice for temp. > 120 C Viton GFLT-S

134 134 AdBlue Summary Vamac has long-time proven functionality in automotive hoses and seals and meets automotive low- and high-temperature requirements (-40 C to 170 C with peaks up to 200 C), as well as good fluid resistance (e.g. engine oil and Diesel fuel) Vamac Ultra grades at medium methyl acrylate levels keep their elastomeric properties after immersion in AdBlue for 1 week at 120 C Peroxide cured Vamac DP also can be seen as a material with possible use for AdBlue, with higher CSet results may however be seen not as good for sealing applications Vamac offers an excellent price/performance ratio compared to HNBR or FKM grades that can be considered suitable for contact to AdBlue Kalrez is the best solution recommended for temp. range ºC

135 135 Agenda Performance of Vamac & Viton in : 1. Engine & Transmission Synthetic Oils 2. Biofuels & Flex Fuels 3. Blow-By & Exhaust Gas Acid Condensates 4. AdBlue Urea 5. Coolant

136 136 Coolant Fluid System Components Heater Core Pumps (Mechanical + Electrical) Thermostat / Valves Cooling Hose Fan Heater hoses Radiator Standard for EPDM hoses & EPDM / HNBR seals Transmission Cooler

137 137 Automotive Factory Fill Coolants Three main categories depending on the type of anti-corrosion package used : The old green coolant uses a mixture of inorganic additives and is referred to as IAT (inorganic additive technology). The IAT package if fast acting but is consumed thus OEMs recommended flushing and replacing after 2 years. Green coolant is no longer used as factory fill by any major automotive manufacturer. However, since it is not recommended to mix additive technologies, green coolant is still in use for service applications. OAT (Organic Acid Technology) coolants : GM changed to OAT in the mid 1990s and extended the service interval to 5 years/150m miles. They developed a specification for the OAT coolants (GM6277M) and coolants meeting this spec are allowed to use the DEX-COOL trademark. Several manufactures market their brand of Dex-cool based on their proprietary blend of additives. Dex-cool is dyed orange. Chrysler and Ford have recently adopted coolants with a mix of organic and inorganic additives denoted as HOAT (Hybrid Organic Acid Technology). The HOAT coolants generally have G-05 on the bottle. Ford HOAT coolant is dyed yellow. Chrysler, just to assure maximum confusion, dye their coolant orange. OAT technology is used by GM, Opel, Ford Europe, VW and most Asian manufacturers. HOAT is used by Chrysler, Ford, BMW, Mercedes and Volvo).

138 138 Regulations are Driving Need for Low Permeation AIM Gaskets More Stringent Environmental Regulations Necessitate Reduction in HC Loss Through Gaskets, etc. CARB LEV II, EPA Tier II, PZEV Silicone is highly permeable to hydrocarbons Regulations Also Demand Longer Vehicle Life CARB 15 Years / 150,000 Miles (EPA 12y / 120 k) While Still Meeitng Above SHED Requirements

139 139 Poor Resistance to OAT Coolants Embrittlement Failure of 66 % F FKM in Coolant Elongation (solid) & Modulus (dashed) after 135 C Coolant Aging

140 140 Advantages & Drawbacks to Traditional Bisphenol Cured FKM for AIM Sealing Exceptional Permeation Resistance Excellent Heat Resistance Excellent Compression Set Resistance and CSR Performance Requires a Post Cure at 200 C (or Hotter) to Achieve low Compression Set Poperties Detrimental to Nylon Carrier : warpage &/or dimensional change Poor Resistance to Coolant 140

141 141 No-Postcure Polymers Postcure not Required to Achieve Good Physical Properties

142 142 Stress Relaxation at 150 C FKM 66 % F vs. FKM GBL-S

143 143 Improved Coolant Resistance Elongation Resistance Improved Coolant Resistance of Viton GBL-S vs, 66 % F FKM Elongation after 135 C Aging in Dex-Cool OAT Coolant

144 144 Improved Coolant Resistance Modulus Retention Improved Coolant Resistance of Viton GBL-S vs, 66 % F FKM Modulus after 135 C Aging in Dex-Cool OAT Coolant

145 145 Improved Coolant Resistance Compression Set Improved Coolant Resistance of Viton GBL-S vs, 66 % F FKM Compression Set in Air at 150 C Aging in Dex-Cool OAT Coolant

146 146 Resistance of Viton - Zytel Adhesion to G48 146