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DKT 2012TPE ForumTPE versus Gummi:Freundlicher oder feindlicher Wettbewerb?TPE versus Rubber:Friendly or unfriendly competition?H.-J. Graf (SP), WOCO GmbH, Bade Soden Salmünster, (D)H. Magg, Lanxess Deutschland GmbH, Leverkusen (D)E. Osen, Freudenberg Sealing Technologies GmbH, Weinheim, (D)C. Thomas, Meteor Gummwerke GmbH, Bockenem (D)

Introduction History of TPE Uniqueness of TPE TPE Family Tree Basic Properties of TPE Morphology – Property dependency Positioning of TPE Property Map Stress Relaxation TPE Versus Rubber Compounds / Compounding Forming Property Description SummaryDr. Hans-Joachim Graf

History of TPVPatent History US 4,594,390 A is the Patent Base of Monsanto / AES onTPV Title: Process for the preparation of thermoplasticelastomers Published 02.05.84 US 4,803,244 Union Carbide on Silane crosslinked TPV Published Nov. 16, 1987 Since then, the price has moved sligthly downward,because of Korean Competitors, but not much. But a lot of compounders are established today Example: Allod – based on SEBS.Dr. Hans-Joachim Graf

Uniqueness of TPEStructure of TPECrosslinks of polymer materials determines their modulusThermoplastic elastomers have crosslinked domains onlyDr. Hans-Joachim GrafSource: E. Osen, KHK 04

Uniqueness of moplasticPolymersBetween Rubber and Thermoplastic:TPE is a “Dual Phase” material, which contains athermoplastic continuous phase surrounding rubber dropletsDr. Hans-Joachim Graf

Uniqueness of TPETPE Family TreeSource:R. Eller, TX, Feb. 2000Dr. Hans-Joachim Graf

Uniqueness of TPETPE Family TreeSource:R. Eller, TX, Feb. 2000Dr. Hans-Joachim Graf

Uniqueness of TPEBasic Properties of TPESource:Franck/Biederbick,Kunststoff-Kompendium 88 Hard-elastic, brittle Hard elastic, tough Tough, still to hard for application as Elastomer Soft-elastic, area of application Very soft, not applicable for service Viscous melt, forming area Chemical aging and decompositionDr. Hans-Joachim Graf

Uniqueness of TPEBasic Properties of TPEDr. Hans-Joachim ederbick,Kunststoff-Kompendium 88

Uniqueness of TPEBasic Properties of TPESource:Franck/Biederbick,Kunststoff-Kompendium 88EPDM/PPSBSSISSEBSETRPURDr. Hans-Joachim Graf

Uniqueness of TPEMorphology - Property DependencySource: K. Walton, RCT 77Dr. Hans-Joachim GrafSource:A.Y.Coran, R.P.PatelThermoplastic Elastomers 96

Uniqueness of TPEMorphology - Property DependencySource: W. Michaeli et.al.KHK Sept. 2011Dr. Hans-Joachim Graf

Positioning of TPEProperty MapSwelling in Oil / ASTM III, 72h, 100 C (%)Source:Wittig, GAK 1997EPDMEPDM Compounds:- Hardness from 20 ShAup to 95 ShAis possible, opposite tooriginal slideHardness ( ShA / ShD)Dr. Hans-Joachim Graf

Positioning of TPEProperty MapSource:R. Eller, W. KlingensmithIISRP Annual Meeting 2001Comparison of aTPE/TPV based onEPDM/PP with aNR-compound.Why not peroxideand/orresin cured rubber?Dr. Hans-Joachim Graf

Positioning of TPEStress relaxation behaviourSource:H. DomininghausPlastverarbeiter 89MetalThermoplastic MaterialsTPEGraph suggestslittle performanceof vulcanized rubberElastomerElongationApplicability of Stress/Strain on different Materials until elasticity limit,but with complete recovery after removing of the loadDr. Hans-Joachim Graf

Positioning of TPEStress relaxation behaviourSource:H. DomininghausPlastverarbeiter 89MetalThermoplastic MaterialsTPEElastomerElongationApplicability of Stress/Strain on different Materials until elasticity limit,but with complete recovery after removing of the loadDr. Hans-Joachim Graf

Positioning of TPEStress relaxation behaviourSource: C. ThomasDIK TPE SeminarEPDMKraft - Weg DiagrammTPE T472Kraft - Weg Diagramm30,030,010%20%25,025,030%40%20,020,0Kraft [N]50%Kraft 00,05,010,015,0-5,0Weg [mm]Dr. Hans-Joachim Graf20,025,00,00,0-5,05,010,015,0Weg [mm]20,025,0

Positioning of TPEStress relaxation behaviourSource: E. Jourdain,Autom.Elast.Conf. 04, ehavior)behavior)Dr. Hans-Joachim Graf

Positioning of TPEStress relaxation behaviourCompression Stress Relaxation of different rubbers compared withStandard and high performance TPE.Relative load under compression [%]Conditions: 25% deformation/100 C hot air/continuous measurementTime [h]Dr. Hans-Joachim GrafSource: E. OsenKHK 2006

TPE versus RubberCompounds / Compounding TPE Rubber (TSR) Continuous MatrixPP PO TP Polar Polymers Developments mostly onHeat / Media resistant TPE Suppliers Since 2000 numeroussuppliers established similarto the TP-IndustryDr. Hans-Joachim Graf Material developments areseldom Developments forimprovementMachines Compounding to meetspecifications Material replacement duringlife cycle is difficult:Expensive testing Customer declines Economical restrictions(Ownership of mixingequipment)

TPE versus RubberCompounds / CompoundingSource: HF MixingFormer Farrel Two stage compounding FCM (Farrel Continuous Mixer) Internel mixer Discharged to single-screw extruder and then pelletizedFCM orInternal MixerSingle screw extruderDr. Hans-Joachim GrafPelletizerFCM Rotors

TPE versus RubberCompounds / CompoundingTwin Screw ExtruderProduction UnitFeeding portsDr. Hans-Joachim GrafPellets/water separatorPellet drierClassifierUnderwater pelletizer

TPE versus RubberFormingSource:K NaskarDiss. U.of Twente 2004No mixingrequired?Dr. Hans-Joachim Graf

TPE versus RubberFormingSource:J. StemperPlastverarbeiter 84Processing of TPEPhysical CrosslinkingFormingMaterialTPE-GranulesPart(Inj. Molding, Extrusion, compression)Reuse of ScrapProcessing of RubberChemical CrosslinkingRaw Materials: Rubber Filler IngredientsCompoundingForming(Inj. Molding, Extrusion, compression)ScrapDr. Hans-Joachim GrafVulcanizationScrapPart

TPE versus RubberFormingSource:Wittig, GAK 1997RubberPolymerFillerAdditiveRaw MaterialSupplierVulcanizing ingCompletionPart ageEnd r. Hans-Joachim GrafAdditiveScrap !?

TPE versus RubberFormingSource:Wittig, GAK 1997RubberPolymerFillerAdditiveRaw MaterialSupplierVulcanizing ingCompletionPart ageEnd r. Hans-Joachim GrafAdditiveScrap !?

TPE versus rdness, which improves flow.Dr. Hans-Joachim Graf

TPE versus RubberForming Calculation of TPE glass run channelSource:S.Z. Yu, H.-J. GrafStandard Products priv. Comm.solution versus EPDM Cost l0.110 /ft0.020 /ftN/A1.350 /unit1.480 /unitTPE0.130 /ftN/A0.020 /ft0.270 /unit0.420 /unitSource:InternetDr. Hans-Joachim Graf

TPE versus RubberProperty DescriptionSource:G. WilliamsAutom. Elastomer Conf. 03In an experiment with a production scale twin screw extruderto study the manufacturing process of TPE the following fomulation was used(Note the large amount of oil in this formulation):Dr. Hans-Joachim Graf

TPE versus RubberProperty DescriptionSource:G. WilliamsAutom. Elastomer Conf. 03Dr. Hans-Joachim Graf

TPE versus RubberProperty DescriptionSource:G. WilliamsAutom. Elastomer Conf. 03Dr. Hans-Joachim Graf

TPE versus RubberProperty DescriptionSource:G. WilliamsAutom. Elastomer Conf. 03Reason,Reason,whywhymostmostOEMsuppliersOEM VtodaytodayDr. Hans-Joachim Graf

TPE versus RubberProperty DescriptionMaterialHardness ShATensile – MpaSupplier data inalperpendicularTPE 1553.87.53.38.6TPE 2605.45.55.47.4TPE 3604.55.55.46.4TPE 4603.85.45.8Reason, why most customers not pleased with suppliers todayDr. Hans-Joachim Graf

TPE versus RubberProperty DescriptionLoad (N)Source: S.Z. YuCooperstandard Automotive54.543.532.521.510.50Comparison of Continuous Stress Relaxation forEPDM and TPV Lips at Varying Temperatures95Flocked EPDM7555TPV with Flock Tape3515TPV with Slip Coat-5Chambre Temperature-25(C)-450 60 120 180 240 300 360Time (min)Dr. Hans-Joachim Graf

TPE versus RubberProperty DescriptionSource:J.E.PfeifferRDoACS Oct. 2002 No.8Dr. Hans-Joachim Graf

Summary Disadvantages of TPE compared to Rubber Resistance against Temperature falls short. Even a shortperiod at a temperature beyond softening changes theshape irreversibly. Limited usage, because of high creep under load, ifexposed to higher temperatures. Limited resistivity against media compared to specialrubbers Process adjustments not possible High material costs Little to none protection of know how for developmentengineersDr. Hans-Joachim Graf

Summary Processing of thermoplastic elastomers Opposite to Rubber processing, which is a cold/hot process, TPE aremanufactured in a hot/cold process. Most TPE materials need a smaller flight depth than rubber compoundsin case of injection molding, which requires machine investment. For TPE Screws with longer L/D of 15 and a flat flight screw are preferredlike similar used for PVC processing TPE parts can be manufactured in all processes typical for TP, likeextrusion, blow molding, injection molding and thermo forming.Dr. Hans-Joachim Graf

Conclusion Competition is not always friendlyTPE should be offered with more reliable data to support themanufacturer, who is responsible for the part.To achieve this, we should have more Round robin testsnot only for more reliable data, but also to benefit from the standards inrubber manufacturers laboratory practice. Possibly define better test standards Manufacturers Material departments have to increase their attentionat TPE.It is insufficient to leave it in the hands of the development engineers. More intense cooperation between material specialist atmanufacturer and supplier will be beneficial for furtherdevelopments and market penetration of TPE.Dr. Hans-Joachim Graf

Continuous Matrix . FCM (Farrel Continuous Mixer) Internel mixer Discharged to single-screw extruder and then pelletized FCM or Internal Mixer Single screw extruder Pelletizer FCM Rotors Source: HF Mixing Former Farrel . Dr. Hans-Joachim Graf TPE versus Rubber Compounds / Compounding Feeding ports Underwater pelletizer Pellets/water separator Pellet drier Classifier Twin Screw Extruder .