熱塑性復合材料

RecentDevelopmentsinHigh-PerformanceThermoplasticCompositesAllanMurray,EcoplexusInc.KlausGleich,SouthernResearchInstituteACCE2003

OverviewIntroductionMaterialsProcessTechnologyApplicationsWhyUseCompositeMaterials?ThermoplasticCompositesBenefits Uniqueproperties Vibrationdampening Lightweight Potentialforlowcost Shelflife Recyclable Durability Fatigue Corrosion ToughnessLimitations Cost Materials Manufacturing Tooling Designknow-how Manufacturingknow-how UsetemperatureThermoplasticCompositesManyPolymerOptions

Polyethylenes Polypropylenes Nylons Polycarbonates Acrylics Polyesters

Polyimides

Polysulfones

Polyketones Polyurethanes thelistcontinuesManyPropertyOptions ultimatestrain>100% nomicrocracking nodelamination dampening nowateruptake lowdielectricproperties meltformable

weldable

elastomeric-plastic-elasticbehavior thelistcontinuesCostChallengeHigh-PerformanceThermoplasticCompositesPropertiesarefiberdominatedOrientedlongorcontinuousfiberreinforcementHighvolumefiberfraction(upto65%byvolume)Keybenefits:Reducingthermallimitations(e.g.creep)causedbytheTPmatrixsystemReducingcostsandweightandretainingtoughness,formability,weldability,shortcycletimes,recyclabilitybenefitsofthethermoplasticmatrixThermoplasticMaterialsCommercialMaterialsGMT(GlassMatReinforcedThermoplastics)PultrudedProductsLFT(LongFiberReinforcedThermoplastics)CFT(ContinuousFiberReinforcedThermopastics)WirecoatedproductsCommingledfibersPowdercoatedmaterialsFilmstickingSlurryprocessesLong-Fiber

ThermoplasticCompositesNewHot-meltProcessProducesFullyWet-outCompositeProductsWideRangeofPolymersandFibersContinuousTapeandRodProductsDiscontinuousProductswithAnyFiberLengthGlassProducts<$1.00/lbCarbonProducts<$8.00/lbPilotProductionforThermoplasticCompositesShortFiber,LongFiberandContinuousFiberComposites

Typicalshortfiberthermoplasticmaterial,granuleswithfiberlengthofapprox.2to4mm,resultingfiberlengthinapartofapprox.0.4mmLongfiberthermoplasticmaterial,pelletsof?”and1“fiberlength,resultingfiberlengthinapartofapprox.4-6mmininjectionmoldingandapprox.20mmincompressionmoldingContinuousreinforcedthermoplasticmaterial,tapeusedforwovensheets(thermoforming),filamentwindingorpultrusionTypicalPultruded

PrepregsFiber:E-glass,S-glass,Carbon,Aramid,polymerfibersMatrix:PE,PP,PA(6,6/66,12,…),PET,PBT,PC,PEI,PPS,SMA,blends,…Fibercontent:20%-60%standard,someupto84%Productforms:Tape,pellets(0.5”,1”),woventapesmorecomplextextilestructuresindevelopmentTwintex-TheComminglingConceptTwintex?PrepregConsolidatedCompositeTemperature+PressureSource:VetrotexTwintex–TheComminglingConceptEGlassadaptedsizingPlasticfilamentAdditives:-couplingagent-UVstabilizer-naturalorblackSource:VetrotexTwintex–TheManufacturingProcessGlassTPCommingling

RovingExtruderBushingSource:VetrotexTwintex-CommingledFiberProductsFiber/matrixcombinations:E-glass/PP,E-glass/PETFibercontent:60%and75%byweightProductforms:Roving,fabric,pelletsLimitations:MatrixmaterialmustbeusableforafiberspinningprocesslimitationsinMFI/viscosity,additivetypeandadditivecontentTwintexVetrotex

TwintexSource:Saint-GobainVetrotex,“TwintexPPandPETMechanicalProperties(nonstandard)”

PhysicalPropertyDataPowderImpregnatedPrepregs–

TheHexcel

TowFlex-TechnologySource:HexcelFiberCreelRacksFluidizedBedPowderCoatingChamberIROvenPullerTake-upSystemChargedResinPowderToWeavingToTapesToPelletsHexcel

TowFlexTypicalfibers:Carbon,E-glass,S-glassTypicalresins:PP,PA6,PPS,PEI,PEEKTypicalproductforms:FlexibleTowpregWovenfabricBraidedSleevingUnidirectionalTapeTowFlexGlassCarbonHexcel

TowflexPhysicalPropertyDataSource:HexcelComposites(March2003)

www.HProcessTechnologyCurrentCompositeMaterialsandProcessesCompositePerformanceversusFiberLengthShortFiberContinuousFillersLongFiberSource:OCFTheLongFiberAdvantage

Stressistransferredtothefibers-thestructuralmembersofthecompositeLongfiberscreatea“skeletalstructure”withinthemoldedarticlethatresistdistortionandprovideunmatchedstrength,toughness,andoverallperformanceSource:TiconaContinuousFiberAdvantageIncontinuousorientedfiberstheloadisultimately‘fully’transferredtothefiberAsaresulttensilecreepislimitedinfiberdirectionManufacturingProcessesforHigh-PerformanceTP-CompositesLowvolumemanufacturingprocessesDiscontinuousprocessesThermoformingThermoplasticS-RIM,RTMandVARTMThermoplasticfilamentwindingVacuumbagmoldingNetshapepreforming(modifiedP4)ManufacturingProcessesforHigh-PerformanceTP-CompositesHighvolumemanufacturingprocessesDiscontinuousprocessesInjectionmoldingwithLFT-pelletsandconcentrates(highperformanceresin/fibercombinations)Inlinecompounding(highperformanceresin/fibercombinations)Backmolding/localreinforcementCompressionmoldingLFT-pelletsandconcentrates(highperformanceresin/fibercombinations)Inlinecompounding(highperformanceresin/fibercombinations)Backmolding/localreinforcementStampformingPreheatedpreformsMatchedmetaltoolsPotentialtomanufactureverythinsections(0.5to1mm)DrapablematerialrequiredContinuousprocessesPultrusionLFT-extrusionMaterialsUsedForLiquidMoldingProcessesMaterialsusedforliquidmoldingprocessesCyclicsReactivenylonFulcrumRequirementforthesematerialsViscositylessthan3000mPa.s(cP)(betterlessthan1000mPa.s(cP))CyclicsCyclicformofPBT,PET,PCandothersOnlyPBTcommercialavailableBasedonaringshapedcyclicalformOneortwopartsystemsSolidatroomtemperature–lowviscosityresinatelevatedtemperature(approx.150cP)PolymerizeintothePolymerusingacatalystIsothermalprocessTypicalprocesstemperature:180–200oCReactiveNylonFormoreinformationseepresentationon“ReactiveThermoplasticVARTM/RTM/S-RIM”FulcrumISOPLASTmatrix(Dowproprietaryengineeringthermoplasticpolyurethane)Thermoplasticviscosityissuesaddressedbyabilitytoreversepolymerizationinthemeltstage,reducingviscositytoensuregoodimpregnationRepolymerizesuponcooling,retainingtraditionalthermoplasticcompositeadvantagesHighimpactresistanceRecyclabilityHighelongationtofailure(~2.5%,versus~1-1.5%forthermosets)Zero-emissionsprocessingFulcrumisthecombinationofISOPLASTandpultrusion,withspecifichardwaredesignProvides10-foldlinespeedimprovementovertypicalthermosetpultrusionlinesAllowsthermoforming,welding,andovermoldingoffinishedpiecesThermoformedFulcrumComponentsFiguresfrom“FulcrumThermoplasticTechnology;MakingHigh-PerformanceCompositeviaThermoplasticPultrusion”DowPlastics,January2000DowFulcrum45v.%and55v.%datafromM76.6wt.%and66wt.%datafrom“FULCRUM:ThermoplasticCompositeTechnology,MakingHigh-performanceCompositeviaThermoplasticPultrusion”DowPlastics,January2000PhysicalPropertyDataReactiveThermoplasticVARTM/RTM/S-RIMSimilarthethermosetprocessReactionofatleasttwocomponentscreatesathermoplasticresinthatcanbemelted,pre-shaped,welded,…LowviscosityisrequiredPossiblematerials:Nylon,TPU,C-PBT(Cyclics)ProblemsConnectedWithThermoplasticRTMReactioncanbestoppedormadeincompletebyMoistureChemicalsinfibersizingMostofthethermoplasticcompatiblesizingsarenotdevelopedforsuchtypeofprocessesAvailabilityofcompatiblesizingsinformoffabricisverylimitedOxygenOnlylimitedsupportofmaterialmanufacturersMaterialcosts(incaseofc-PBT)ThermoformingHeatinOvenThermoformingOperationFinishedProduct

ThermoformingWeightperformance:Goodweight/performanceratioforfabricreinforcedsheetsduetocontinuousfibersReducedweight/performanceratioforextrudedsheetsdependingontheresultingfiberlengthDesignflexibility:Limited,especiallyforcomplexgeometriesSimulationtoolsavailableProcessability:StabilizationagainstoxidationnecessaryFiberdisalignmentswithcontinuousfiberspossibledependingongeometry,material,toolingandprocessconditionsRecyclability:Highrateofproductionscrap(fixation)NodirectrecyclabilityUseinotherprocesseslikeplasticationofregranulationTPS-RIM,RTM,VARTMWeight/performance:ExcellentDesignflexibility:Limitedtopreformingcapability,flowlengthandflowbehavioroftheresinProcessability:ReactioncanbesensitivetomoistureandfibersizingRecyclability:ProductionscrapduetopreformingstepdependingonpreformingmethodNodirectrecyclability;canbeusedinotherprocessesTPFilamentWindingWeight/performance:ExcellentDesignflexibility:LimitedtosymmetricpartsthatcanbewoundonamandrelProcessability:HigheroxidativestabilizationrequiredRecyclability:LowrateofproductionscrapNodirectrecyclabilityScrapcanbeusedinotherprocessesVaccumBag/HandLay-UpWeight/performanceExcellentduetocontinuousfiberreinforcementDesignflexibilityLimitedtodrapabilityandtotheposibilityofmanuallylayupProcessabilityHighervoidcontentduetolowpressureconsolidationUsingautoclavetoreducevoidcontentOftenfiberdisalignmentsRecyclabilityHighrateofproductionscrappossibledependingonthesizeofthematerialsheetsandthepartgeometryNodirectrecyclabilityScrapcanbereusedinotherprocessesLFT-InjectionMoldingWeight/PerformanceLowerendofthermoplasticcompositesduetoreducedfiberlengthinthefinalpartImprovementspossiblebyusinglocalreinforcements(usingpultrudedsections,sheetsortapesofcontinuouscompositeslocalizedstrengtheningandstiffening,reductionofwarpage)DesignFlexibilityHighFlowchannelsandpositionsofgateshavetobecarefullydesignedProcessabilityHighlystableRecyclabilityLowproductionscraprateCanbereusedinthesameprocessCompressionMoldingWeight/PerformanceMediumRetainingfiberlengthgivesexcellentpropertiesforarandomorientedmaterial,butislowerthanusingafabricLocalreinforcementorfabricreinforcedGMTimproveit(usingpultrudedsections,sheetsortapesofcontinuouscompositeslocalizedstrengtheningandstiffening,reductionofwarpage)DesignflexibilityHighSpecialsimulationtoolsavailableProcessabilityVerystableprocessRecyclabilitySomeproductionscrapduetotrimoperationsScrapcanbeaddedandreusedinthesameprocess(GMTonlysheetscanbereusedinthesameprocess,butnotrecommended)CurvSelf-reinforcedpolypropyleneConsistsof“hotcompacted”polypropylenefiberortapeSurfaceoftapeorfibermeltsduringcompactiontoformthe“matrix”thatbindsthedirectionalelementstogetherOrientedmorphologyprovidesoversix-foldincreaseintensilestrengthandnearly5-foldincreaseintensilemodulusoverisotropicpolypropylene,with~2%weightpenaltyNearlydoublestensilestrengthof40%randommatshortglasspolypropylene,withcomparablemodulusand22%weightsavingsEliminationofglassreinforcementhasseveraladvantages:IncreasedrecyclabilityReducedweightLowertemperaturesandpressuresforthermoformingReducedirritationintheworkplaceHighstraintofailure,withgoodimpactstrengthDatafrom“ANewSelf-ReinforcedPolypropyleneComposite”Jones,RenitaS.andDerekE.RileyCurvfromBPdocument“ANewSelf-ReinforcedPolypropyleneComposite”Jones,RenitaS.andDerekE.Riley,2002

PhysicalPropertyDataPultrusionWeight/performanceGoodtoexcellentduetocontinuousreinforcementDesignflexibilityLowdesignflexibilityLimitedtoconstantcrosssections,butcanbeshaped(pull/press)ProcessabilityOnlylimitedexperienceavailableDependsonstabilizationofthematerialaswellasusedmaterialformRecyclabilityLowrateofproductionscrapexpectedNodirectrecyclabilityCanbeusedinotherprocessesLFT-ExtrusionWeight/performanceMediumweightperformanceDependsonretainingfiberlengthDesignflexibilityLowdesignflexibilityLimitedtoconstantcrosssectionsCanbepostshapedorpullformedProcessabilityNotalotofexperienceAstableprocessisexpectedusingtherightdiedesignRecyclabilityLowrateofproductionscrapCanbereusedinthesameprocessEconomicsProcessCycleTimeToolingCostsScrapRateOverallEconomicsThermoformingMediumLowHighGoodforlowvolumeproductionwithnoorlimitedthicknessvariationTPS-RIM,RTM,VARTMMediumtolong,uptoseveralminutesVARTM:low,singlesitedtoolRTM:lowtomediumS-RIM:MediumDependsonpreformingtechnique;oftenhighforcomplexshapedpartsGoodforlowvolumeproductionTPFilamentWindingMediumtolong,dependingonnumberoftapesandheatingsystemLowtomediumLowGoodforsymmetricalpartsinlowtomediumvolumeproductionVacuumBag/HandLay-upLong;manualpreparationcanbehoursforapartLow,singlesidedtoolMediumtohighGoodforprototyping.Notrecommendedforproductionscale.InjectionMoldingLFTILCShortcycletimes;typically50–80sec.High;steeltoolswithejectorpinsandslidesVerylowExcellentforhighvolumeproductionCompressionMoldingGMTLFTILCShortcycletimes;typically35–60sec.High;steeltoolswithejectorpinsandslidesLow–mediumdependsoncutouts.ScrapcanbereusedExcellentforhighvolumeproductionoflargecomponentsPultrusionContinuousprocess;notenoughexperienceonthroughputMediumLowLimitedexperienceavailableExtrusionContinuousprocess;throughputmainlylimitedbycoolingcapacityofcalibrationdieMediumtohighLowExpectedtobecosteffectiveforprofilesApplicationsApplicationsForHigh-PerformanceThermoplasticCompositesAerospaceanddefense:Radomes,wingandfuselagesextions,anti-ballisticsInfrastructureandConstructionWindowprofiles,rebar,beams,structures,compositeboltsConsumer/recreationalOrthotics,safetyshoes,sportinggoods,helmets,personalinjuryprotextion,speakercones,enclosures,bedsuspensionslatsAutoandtruckBumperbeams,skidplates,loadfloor,seatstructuresTransportationRailcarstructure,bodystructureandclosuresEnergyproductionandstorageOilandgasstructuratube,windturbinesBMWM3BumperBeamSource:JacobKunststofftechnikGmbH&Co.KGwww.jacob-kunststofftechnik.de-Beamandcrushcolumnsmanufacturedusing

Hexcel

TowFlexPA6Partsweldedbyhighfrequencyvibrational

welding2versions:

StandardM3basedonglassfiberreinforcement(approx.40cars/day)M3CSL(limitedto1600total)usingCarbonfiberreinforcement

HelmetsMilitaryhelmetforNorwegianArmyMadebyCatoComposites50,000/yearTEPEXantiballistic302Aramid/PA6continuousreinforcementSource:Bond-LaminatesGmbHSource:Bond-LaminatesGmbHWhitewaterhelmetMadebyPrijonTEPEXdynalite701Glas,Carbon,Aramid/PA6.6ContinuousreinforcementAircraftApplicationsFixedwingleadingedgeforAirbusFokkerSpecialProducts/AirbusTEPEXsemipreg107Nonfullyconsolidated,flexiblelayersofcontinuousfiberreinforcedthermoplasticsGlass/PPSWingaccesspanelforAirbusFokkerSpecialProducts/AirbusTEPEXsemipreg207Nonfullyconsolidated,flexiblelayersofcontinuousfiberreinforcedthermoplasticsCarbon/PPSMineSweeperArmouringMadefromTEPEXantiballistic302Aramid/PA6ContinuousreinforcedMadebyKvaernerSource:Bond-LaminatesGmbHSafetyShoesCompositeToecapHistory:CompositeToecapswereman