Performance of Vamac and Viton in Sealing Applications

Transcription

1 Performance of Vamac and Viton in Sealing Applications DuPont Performance Polymers Conference May 20th 2010 Albergo Cocca Hotel Sarnico (Bg) Pepa Mayor-Lopez

2 Index Index 2 Market outlook for Viton and Vamac Applications Sealing performance Heat resistance Chemical resistance Compression Set and Compressive Stress Relaxation Low Temperature Sealing 2K molding

3 Major European* Applications for Viton 3 Molded parts 17% Other seals & coatings 2% Process aids 8% O-Rings 32% Hoses 15% Expansion joints 1% Gaskets 9% Valve stem seals 4% Shaft seals 12% All applications involve combinations of high and low temperature and/or aggressive fluids -> 60%+ automotive market *based on 2004 data

4 Vamac Application Split - Global 4 Seals & Gaskets W&C Other Turbo Hose Boots Dampers Other Hose Major growth segments: Fuel Hose Crankcase Ventilation Hose Oil Cooler Hose - Turbo hoses (volume wise) - Crankcase venting and vacuum hoses (blow-by environment) - Oil cooler Hoses - Fuel hose covers - Seals & gaskets -> 90%+ automotive market

5 Why Gaskets 5 Bridge a gap between two substrates statically dynamically Provide this sealing function at high temperature long term in chemically harsh environments without leakage at low temperature at acceptable economy

6 The Vamac and Viton Space 6 Heat and Oil Resistance of Elastomers Type C Mid-Performance High-Performance K 300 Kalrez Heat Resistance 1 J H G F E D EPDM Applications with min. temperature requirements of 165 degrees EVM V Solutions Space Sealing & Hose Applications VMQ EVM 4 Vamac Viton FEPM FVMQ ACM 3 HNBR ACM C 125 CSM,CPE ECO B A VI % Class IIR SBR IR Neoprene NBR No Req A B C D E F G J K Oil Resistance 2 1. Maximum temp. at which vulcanizates can be aged for 70 hrs with changes in tensile strength no greater than ± 30%, elongation no greater than -50%, and hardness no greater than ± 15 points Applications with reduced swell 2. % volume increase in ASTM IRM 903 Oil, 70 hrs exposure 3. New ACM grades 4. High VA content grades

7 V Solutions Automotive Applications 7 Fuel Systems Filler line and filler neck hose and covers Viton, Vamac O-rings and gaskets Viton Injector O-rings Viton Fuel sender seals Viton Fuel cap seals Viton Fuel filter seals Viton Oil and Grease, Powertrain Shaft seals Viton, Vamac Transmission seals Viton, Vamac Ball bearing seals Viton, Vamac Oil drain turbo hoses Viton, Vamac EOC &TOC hoses Viton, Vamac Boots, molded goods Vamac Dampers Viton, Vamac MLS head cylinder gaskets Viton Oil pan gaskets Viton, Vamac Cam cover gaskets Viton, Vamac Oil filter seals Viton, Vamac `Others Viton, Vamac Air Mgmt, Engine, Exhaust Turbo charger and other hoses Viton, Vamac AIM gaskets Viton, Vamac Intercooler seals Viton, Vamac Quick Connectors Viton, Vamac Ventilation seals Viton, Vamac Others Viton, Vamac Non-Auto Trans Hoses - Viton, Vamac O-rings, gaskets Viton, Vamac Others - Viton, Vamac

8 V Solutions Industrial Applications 8 Oil & Gas O-rings, V-rings and gaskets Viton Packers Viton Chemical Processing, Utilities & Industries Bio fuel storage & handling - O-rings, gaskets, hoses, custom parts Viton Flue duct expansion joints Viton Hydraulic hoses -Vamac Clean Environment Vamac for photovoltaic production membrane FDA-compliant parts made from select Viton polymers Wire & Cable Halogen free, flame retardant - Vamac compounds Jacketing - Viton, Vamac

9 Viton Fluoroelastomer

10 Viton - Key Features 10 Continuous service temperature of 205ºC Short term excursions to as high as 300ºC Low swell in hot motor oil / ATF Very low swell in motor fuels gasoline, bioalcohols, diesel, biodiesel Low temperature flexibility (-30ºC to -40ºC) Low compression set at 200ºC Excellent sealing properties Compression set, compressive stress relaxation

11 Gasket requirements-heat Resistance 11 >10000 h >3000 h ** >1000 h Hours of Service* >240 h >48 h C 232 C 260 C 287 C 315 C Test Temperatures * Approximate number of hours at which typical vulcanizate of Viton will retain 50% of its original elongation at break. Data based on a standard 66% fluorine type (A family). ** car: km at 60 km/hour. normal car lifetime

12 Sealing performance Compression Set Compression Set Resistance Compression set 22 hours at 150 C - B ISO 815-1:2008 Compression set 22 hours at 175 C - B ISO 815-1:2008 Compression set 22 hours at 200 C - B ISO 815-1:2008 CS (%) GAL-200S GF-600S GLT-600S GFLT-600S A-601C (~70 Sh A; Curing: 10'/180 C; Post-cure: 16h/230 C)

13 Sealing performance - Compressive Stress Relaxation 13 CSR is a measure of the residual counter force against compression after exposure to heat and/or fluid under constant deformation It is a more realistic representation of sealing capability and durability of elastomeric materials in use Gaining attention as a screening tool

14 Gasket requirements-long Term Durability 14 Compression set is the first indication, but a more realistic picture is given by CompressionStressRelaxation % retained sealing force ASTM-D6147 Method 150 C GLT GLT-600S hours ,000 1,500 2,000 2,500 3,000 3,500 4,000 4,500 5,000

15 Compression Stress Relaxation in MJO 291* at 200 C Stress Relaxation in Mobil Jet Oil 291 at 200 C Retained Sealing Force (%) GLT GLT-S A601C Time (hours) *Aerospace Gas Turbine HTS Oil (HTS, High Thermal Stability)

16 Gasket requirements-chemical Resistance 16 excellent hydrocarbons (solvents, fuels ) very good chlorinated solvents mineral acids aromatic solvents oxidising fluids fair to good hot aqueous fluids, e.g. acids and steam critical chemical attack strong bases strong organic acids, aldehydes ammonia and amines high volume swell low molecular weight ether, ester and ketones Viton Extreme TM Fluoroelastomers or Kalrez are preferred

17 Volume Swell in Fuel Mixtures 17 volume swell 168h, 23 C (%) fuel C M-15 0 A B GF GFLT GLT NBR HNBR FVMQ Viton Fuel M-15 composition is 85% Fuel C and 15% methanol

18 Elongation change Aged in Ref. Oil 300* at 200 C (oil changed weekly) 18 Original GLT Original A601C GLT after 1008 hours at 200 C 0% Elongation Change (%) -20% -40% -60% -80% Embrittlement of A601C after 1008 hours at 200 C -100% 168 hours 336 hours 504 hours 1008 hours A601C GLT *Aerospace Gas Turbine Reference Oil (HTS, High Thermal Stability, oil)

19 A proposed mechanism of chemical attack on standard fluoroelastomers 19 Base Attack on VF 2 / HFP FKM (VF 2 /HFP Sequences are the weak link in FKM) F H CF3 F F H CF3 F - H + C C C C C C C C (-) F H F F F F F {BASE} {MgO, Ca(OH)2} F H CF3 F Continued Crosslinking - F - - of C=C sites leads to a C C C C loss of Elongation and F F Eventual Embrittlement

20 Gasket requirements -Low Temperature Flexibility 20 Low temperature measurements ( C) GLT-S GFLT-S TR-10 ( C) Test-unit Initial tension A B GF-S Test-Gas (4 bar air) Tg (DSC, inflection) Sealing dry O-ring Sealing soaked in unleaded fuel Sealing soaked in fuel C Static sealing possible at about 15 C below polymer Tg Conditioning in fuel plasticizes the seal and lowers sealing temperature e.g. GLT-S seals to : about 45 C (dry) about 48 C (conditioned in unleaded fuel) about 54 C (conditioned in Fuel C) Test-O-Ring Leak-sensor Leak-flow

21 Viton Fluoroelastomers Typical Applications 21 High High fluorine fluorine for for best best chemical chemical resistance resistance (e.g. (e.g. steam steam and and acid) acid) Broadest Broadest fluid fluid resistance resistance (e.g. (e.g. down down hole) hole) Low temperature flexibility TR-10 ( C) Best compression set and processing GF-S ETP-S (F) B GFLT-S GBL-S GBLT-S A AL GAL-S GLT-S Easy Easy processing processing low low fluorine fluorine (e.g.standard (e.g.standard o- o- rings) rings) High High fluorine fluorine with with low low temperature temperature functionality functionality (e.g. (e.g. fuel fuel systems) systems) Volume swell upon immersion in M15 / 7 d / room-temperature (%) Best fluid resistance red for Viton made with APA («-S» for APA technology); «G» for peroxide curing vs. bisphenol curing, «LT» for low temperature Best Best low low temperature temperature performance performance (e.g. (e.g. fuel fuel injector injector o-rings) o-rings)

22 Viton Relative Performance 22 Viton product A AL B F GAL-S GBL-S GF-S GLT-S GBLT-S GFLT-S TBR-S ETP-S Curing system bisphenol bisphenol bisphenol bisphenol peroxide peroxide peroxide peroxide peroxide peroxide bisphenol peroxide Fluorine content 66% 66% 68.5% 70% 65.5% 67.5% 70% 64.5% 66% 67% 60% 66% Heat resistance All Viton products have outstanding thermal properties Chemical resistance* * BEST Base resistance BEST BEST Low temperature properties BEST Compression set resistance BEST Relative cost of polymer low low low low low low low medium medium medium low high BEST Excellent Very good Good Fair Poor S indicates products made with Advanced Polymer Architecture * Consult the Chemical Resistance Guide at or contact your Viton specialist.

23 Selection Based on Application Needs 23 Base resistance: Best resistance to aggressive amine based anti-corrosion additives? yes Hydrocarbon resistance (automotive fuels, etc.)? no High resistance to oxygenated-fuels (MeOH, MTBE), steam, acids? yes no yes no ETP-S GFLT-S TBR-S Low temperature flexibility better than -20 C? Low temperature flexibility better than -20 C? yes no yes no GFLT-S GBLT-S F GF-S GLT-S A B AL GBL-S black for standard Viton ; red for Viton made with APA («-S» for APA technology)

24 On-line Viton Selection Guide 24

25 Viton Fluoroelastomer Offering Examples -

26 Standard O-Rings 26 Important criteria static seals compression set processing Low temperature flexibility TR-10 (deg. C) ETPS F and GFS B GFLTS GBLS and BL GBLTS A AL GLTS Volume swell after 7 days at room temperature in M15 (%) A Type A-201C, A-202C->VTR >NGDP NGDP (Next Generation DiPolymer) Broader operating window with better compression set Triangle strategy

27 Low Temperature Applications e.g. FIOR 27 Important criteria static seals sealing at temperatures at or below 40 C fuel resistance Low temperature flexibility TR-10 (deg. C) ETPS F and GFS B GFLTS GBLS and BL GBLTS A AL GLTS Volume swell after 7 days at room temperature in M15 (%) GLT-S Types GLT-200S/GLT-600S Biodiesels : Peroxide curable Viton without metal oxide Oxygenated fuels: High fluorine types

28 Low Temperature Applications 28 C Low temperature properties of LT types GLT GLT- 600S GBLT- 600S GFLT GFLT- 600S TR-10 Tg

29 Shaft Seals / Valve Stem Seals 29 Important criteria dynamic seals aggressive oils metal adhesion Low temperature flexibility TR-10 (deg. C) ETPS F and GFS B GFLTS GBLS and BL GBLTS A AL GLTS Volume swell after 7 days at room temperature in M15 (%) B Types B-651C->B-435C, B-135C APA GBL-S or GF-S

30 30 Chemical Resistance - e.g. PHEG, CPUI, oil & gas Important criteria broad chemical resistance processing Low temperature flexibility TR-10 (deg. C) ETPS F and GFS B GFLTS GBLS and BL GBLTS A GAL-S AL GLTS Volume swell after 7 days at room temperature in M15 (%) GF-S or ETP-S families Viton GF-200S / GF-600S Viton Extreme ETP-600S

31 Superior Chemical Resistance of ETP-600S 31 Gear 150 C Wheel Bearing 150 C 40 C 40 C MEK@ 23 C 40 C

32 Vamac Ethylene Acrylic Elastomer

33 Vamac - Key Features 33 TEMPERATURE RESISTANCE: High temperature durability Good low temperature flexibility FLUID RESISTANCE: Good Oil and Blow-by Gas Resistance Excellent Water Resistance up to C Outstanding Ozone/ Weather Resistance New synthetic Engine Oils causing lower volume swell Low gas & oil permeability MECHANICAL PROPERTIES: Good mechanical properties. Good abrasion resistance SEALING PERFORMANCE: Excellent compression set resistance Very good compressive stress force retention ADHESION PROPERTIES: Excellent adhesion to metals: allow use of water-based bonding agents to reduce output of VOCs (Volatile Organic Components). Good adhesion to polyamide VIBRATION DAMPING PERFORMANCES: High /Consistent vibration Damping Capability

34 Fluid Resistance: General Guidelines 34 Vamac has good resistance to - Lubricating oils and greases ( mineral or synthetic based ) - Transmission / power steering fluids - Diesel fuel - Kerosene - Water up to 110 C (in continuous) - Dry and wet sour gases - Diluted acids and bases - Blow-By & EGR Fluids to avoid AROMATIC HYDROCARBONS: gasoline, benzene, toluene POLAR ORGANIC FLUIDS: esters, ketones, amines HIGH and LOW ph-value WATER BASED SOLUTIONS: risks of hydrolysis

35 Seals and Gaskets Offering for Engine and Transmission Seals 35 Rocker Cover Gasket Transmission seals Vamac Ultra IP & VMX 3110 especially for low hardness applications 2K moulding Vamac /Zytel Viton if continuous heat exposure > 180 C

36 Mechanical Properties: Compression Set Shore A, C, ASTM D 395 (Method B, 13 mm plied) CS (%) HNBR Silicone ECO at 125 C ECO ACM Vamac

37 Sealing Performance of Vamac vs HT-ACM in Hot 150 C 37 Force Retention (%) Compressive Stress Relaxation in 150 C Vamac G (78 Sh. A) Vamac Ultra IP (79 Sh. A) Vamac Ultra IP (61 Sh. A) HT-ACM (79 Sh. A) Acc. To ISO 3384 Method B Shawbury Wallace Test Equipment Cylindrical Specimen, 6 mm high & 13 mm diameter Higher force retention stands for better sealing performance Time (h) Force Retention Ranking: Vamac Ultra IP > Vamac G >> HT ACM

38 VMX-3110 Compressive Stress Relaxation in Air (60 Sh.A) 38 F o r c e R e te n tio n (% ) CSR in Air, 150 C, ISO 3384 GLS, high DIAK VMX-3110, high DIAK Time in hours Vamac GLS and VMX-3110 with identical formulations (1.75 phr DIAK No1 & 20 phr of plasticiser) VMX-3110 provides significant improvement CSR in Air, 150 C, ISO 3384 Both formulations without plasticiser VMX-3110 significantly better than HT-ACM F o rc e R e te n tio n (% ) VMX-3110, no plasticizer HT-ACM Time in hours

39 Sealing performance of Vamac vs HT-ACM in New Synthetic Engine Oil 39 Compressive Stress Relaxation in oil (Castrol SLX LL III, 5W30 / 150 C) Force Retention (%) new AEM ACM 30 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 stands for 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.

40 CSR in Engine Oil / Fuel Blends New test specifications include elastomer testing in Oil / Fuel blends, very often in a 90% / 10% blending ratio. 40 CSR (SF105 W/ 10% CE85) Vamac G Vamac GLS AR-12 HT-ACM Retained Sealing Force 120% 100% 80% 60% 40% 20% 0% Hours at RT CE85 stands for Fuel C/Ethanol in a 15/85 blend AEM shows advantages over ACM in Compressive Stress Relaxation Tests in Oil / Fuel blends

41 Sealing performance of Vamac vs HNBR in Engine Oil 41 Compressive Stress Relaxation in oil (Castrol SLX 0W30 Super Longlife II, 150 C) Force retention (%) Vamac HVG Vamac G HNBR (34% ACN) Time (hours) Higher force retention for Vamac

42 CSR in Transmission Fluid Dexron VI 42 Force Retention (%) 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

43 Vamac - Low Temperature Performance Tg Vamac low temperature properties Brittleness point TR10 Gehman T10 Gehman T100 Static O-ring sealing test Temperature (degree C) G/15 phr plast. GLS/15 phr plast. IP/ 15 phr plast LT/15 phr plast. G/ 25 phr plast -62 Vamac Ultra LT for improved low temperature properties

44 Vamac - CS at Low Temperature 44

45 PSA and VW specifications engine static seals 45 Compression moulding 10 minutes at 180 C Post-cure 2 hours at 175 C Ultra IP Ultra IP/GLS Engine Static Seals - Specifications PSA S VW TL Hardness Shore A (1 second) /-5 55+/-5 Tensile properties (type 2) at 23 C Tensile Strength [MPa] > 7 > 9 Elongation at break [%] > 200 > 200 Modulus at 100 % [MPa] > 2 Tear strength - Small (Delft), (N/mm) > 10 Tear strength type A - Trouser (N/mm) > 5 Tg by DSC < -30 (Gehman T10) < -35 (bending test) Compression set 22 hours at 150 C - VW PV3307 Compression set after 5 sec recovery [%] < 50 Compression set after 30 min recovery [%] ISO 815-1:2008 Compression set 72 hours at 165 C - pips, 13x29mm Compression set after 30 min recovery [%] < 25 Compression set 1008 hours at 135 C - pips 13x29mm Compression set after 30 min recovery [%] < 40 Compression set 1008 hours at 150 C - pips 13x29mm ISO 815-1:2008 Compression set after 30 min recovery [%] < 40

46 PSA and VW specifications engine static seals 46 Ultra IP Ultra IP/GLS Engine Static Seals - Specifications PSA S VW TL Heat ageing 1008 hours at 150 C ISO 188:2007 Hardness Shore A (1 second) ISO : Hardness change (points) to +15 max Tensile properties (type 2) at 23 C ISO 37:2005 Cor Tensile Strength [MPa] Tensile Change [%] max Elongation at break [%] > 100 Elongation Change [%] max Heat ageing 168 hours at 165 C Hardness Shore A (1 second) Hardness change (points) to +10 max Tensile properties (type 2) at 23 C Tensile Strength [MPa] Tensile Change [%] max Elongation at break [%] > 150 Elongation change [%] max Fluid ageing 1008 hours at 150 C in Total Quartz INEO ECS 5W30 PSA S Hardness Shore A (1 second) ISO : Hardness change (points) to +5 Tensile properties (type 2) at 23 C ISO 37:2005 Cor Tensile Strength [MPa] Tensile Change [%] max Elongation at break [%] > 150 Elongation Change [%] max Volume Change (%) ISO 1817: to +10 Weight change (%) ISO 1817: Ultra IP/GLS blend more suitable for fluid ageing requirement

47 PSA and VW specifications engine static seals Ultra IP Ultra IP/GLS Engine Static Seals - Specifications PSA S VW TL Heat ageing 504 hours at 150 C ISO 188:2007 Hardness Shore A (1 second) ISO : Hardness change (points) to Tensile properties (type 2) at 23 C ISO 37:2005 Cor Tensile Strength [MPa] > 8 Tensile Change [%] Elongation at break [%] > 150 Elongation Change [%] 1 3 Fluid ageing 504 hours at 150 C in Lubrizol OS ISO 1817:2005 VW TL Hardness Shore A (1 second) ISO : Hardness change (points) to +10 Tensile properties (type 2) at 23 C ISO 37:2005 Cor Tensile Strength [MPa] > 6 Tensile Change [%] Elongation at break [%] > 150 Elongation Change [%] Volume Change (%) ISO 1817: Weight change (%) ISO 1817: to +10% Fluid ageing 504 hours at 150 C in Castrol SLX Long Life III, 5W30 Hardness Shore A (1 second) Hardness change (points) to +10 Tensile properties (type 2) at 23 C Tensile Strength [MPa] > 6 Tensile Change [%] -5-3 Elongation at break [%] > 150 Elongation Change [%] Volume Change (%) 5 5 Weight change (%) to +10% Ultra IP/GLS blend more suitable for fluid ageing requirement

48 2K Technology 48 Technology: Direct overmoulding of thermoset gaskets onto thermoplastic parts Technology objectives: Primerless adhesion Easy moulding & process Ensure part final function Elastomer Target Performances: Cohesion failure on peeling or bending test Sealing performance Hot air & fluid resistance Low permeation in fluids Fast curing Easy mould cleaning

49 2K Applications Typical Applications Targeted 49 AIR MANAGEMENT AIM gasket Quick connectors OIL & GREASE Rocker Cover gasket Oil pan gasket Oil filter seal Shaft seal (*) FUEL SYTEM Fuel filter seal Fuel sender seal (*) * : pictures courtesy of Billion 2C machine manufacturer and MASSACRIER tool maker

50 2K-Zytel / Vamac : ADHESION (measured on peel laboratory samples moulded with 2K) > 3 N/mm Material Offer 50 Adhesion (N/mm) < 1 N/mm Standard PA66 Modified Zytel FE Vamac Ultra IP combined with Zytel FE (= PA 6,6 modified) allows 2K moulding. Standard PA6,6 has no sufficient adhesion to keep the seal + cover together during the moulding ejection & handling process.

51 Material Offer 51 2K-Zytel / Vamac : COMPRESSION SET (measured on peel laboratory samples moulded with 2k) 90 Compression set (%) Optimum seal properties No Post-cure 30 / 175 C 2h / 175 C 40 / 190 C

52 FAKUMA 2009: Air management flap 52 Billion, 150T Vamac Ultra IP: AEM Zytel FE270056: PA66GF35 modified Direct adhesion Short cycle times Reduced Injection pressure Process parameters: Zytel cavity: 80ºC Vamac cavity: 190 C Total cycle time: 41 sec Cure time: 30 sec

53 53 Thank you for your attention The information set forth herein is furnished free of charge and is based on technical data that DuPont believes to be reliable and falls within the normal range of properties. It is intended for use by persons having technical skill, at their own discretion and risk. This data should not be used to establish specification limits nor used alone as the basis of design. Handling precaution information is given with the understanding that those using it will satisfy themselves that their particular conditions of use present no health or safety hazards. Since conditions of product use and disposal are outside our control, we make no warranties, express or implied, and assume no liability in connection with any use of this information. As with any product, evaluation under end-use conditions prior to specification is essential. Nothing herein is to be taken as a license to operate or a recommendation to infringe on patents. Caution: Do not use in medical applications involving permanent implantation in the human body. For other medical applications, discuss with your DuPont customer service representative and read Medical Caution Statement H Copyright 2010 DuPont. The DuPont Oval logo, DuPont, The miracles of science, Viton, Vamac, are registered trademarks of E.I. du Pont de Nemours or its affiliates. All rights reserved.

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