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1、Carbon Fiber ProcessingProductionmethods,propertiesandcompositeapplicationsProductionmethods,propertiesandcompositeapplicationsCoreyBehrensCoreyBehrensFebruary19,2007February19,20071Properties of Carbon Fibersn nHighstrengthHighstrengthn nHighstiffnessHighstiffnessn nWithstandtemperaturesto2500Withs
2、tandtemperaturesto2500o oC Cn nHighstrength/weightratioHighstrength/weightration nTensilemodulirangefrom4x10Tensilemodulirangefrom4x106 6psito100x10psito100x106 6psipsi2Methods of producing Carbon Fibern nAllcommercialC.F.sfrom3processes:n nPolyacrylonitrile(PAN)Polyacrylonitrile(PAN)n nRayon(cellul
3、ose)Rayon(cellulose)n nMesophasePetroleumPitchMesophasePetroleumPitchn nNewmethodfordiscontinuousC.F.n nVaporGrowth(highperformanceapplication)VaporGrowth(highperformanceapplication)3PAN processn nAccountsfor90%ofcommercialC.F.sn n93-95%acrylonitrileunitsn nPANdecomposesbelowitsmelttemperaturen nTru
4、eMeltprocessnotpossibleTrueMeltprocessnotpossiblen nThereforeextrudedintofilamentformThereforeextrudedintofilamentform4Process Methodn nCopolymerisfirstdissolvedinsuitablesolventCopolymerisfirstdissolvedinsuitablesolventn ne.g.Dimethylacetamidee.g.Dimethylacetamiden n15-30%polymerbyweight15-30%polym
5、erbyweightn nextrudedthroughaspinneretextrudedthroughaspinneretn nlarge#ofapprox.100large#ofapprox.100 mcapillaryholesmcapillaryholesn nenterscoagulatingbath(Wetspinning)enterscoagulatingbath(Wetspinning)n nAlsohotgasenvironmentsAlsohotgasenvironmentsn n1-2stagesoffurtherstretching1-2stagesoffurther
6、stretchingn nAlignspolymermoleculesparalleltofiberaxisAlignspolymermoleculesparalleltofiberaxisn nMolecularorientationmustbelockedintoplaceMolecularorientationmustbelockedintoplacen nEffectsfinalmechanicalpropertiesofC.F.sEffectsfinalmechanicalpropertiesofC.F.s5PAN precursor fiber process6Considerat
7、ions of PANn nWetspinningn nRequiresexcessivesolventn nNecessitatesremovalfromfiber,solventrecoveryNecessitatesremovalfromfiber,solventrecoveryn nTraceimpuritieslimitfinalC.F.propertiesTraceimpuritieslimitfinalC.F.propertiesn nBASFpseudo-meltalternativen nAcrylonitrilecopolymerpolymerizedinaq.Soln.A
8、crylonitrilecopolymerpolymerizedinaq.Soln.n nPurified,dewatered,pelletizedPurified,dewatered,pelletizedn nHomogenousmeltbelowdegradationtemp.Homogenousmeltbelowdegradationtemp.n nEliminatesneedforexpensivesolventEliminatesneedforexpensivesolventn nLowerwastewaterrequirementsLowerwastewaterrequiremen
9、ts7BASF PAN pseudo-melt8Production of Carbon Fiber from PANn nHeating/Stretchingn nPre-carbonizationn nCarbonizationn nSurfaceTreatment9Chemistry of carbon fiber production10Heating/Stretchingn nStretching(500-1300%)n n220-270220-270o oCfor30minto7hrsCfor30minto7hrsn nTemp./Timedependentoncompositio
10、n/diameterofPrecursorTemp./Timedependentoncomposition/diameterofPrecursorn nChemicalchangesChemicalchangesn nCyclizationofnitrilegroupsCyclizationofnitrilegroupsn nDehydrationofsaturatedC-CbondsDehydrationofsaturatedC-Cbondsn nOxidationOxidationn nGeneratesCOGeneratesCO2 2andHCNandHCNn nLargefurnace
11、+DriverollersLargefurnace+Driverollersn nControlledtensionessentialforalignmentControlledtensionessentialforalignmentn nPANcarboncontent:54%PANcarboncontent:54%11Pre-carbonizationn nHeatingupto1100oCn nNon-Carbonelementsdrivenoffn nInitiallylargermoleculesInitiallylargermoleculesn nCHCH4 4HH2 2ONHON
12、H3 3NN2 2HCNCOHCNCO2 2COCOn nSlowerheatingrate12Carbonizationn n1100oC2800OCn nOnlysmalldiatomicmoleculesn nH H2 2NN2 2n nFasterheatingratepossibleFasterheatingratepossiblen nGraphitizationabove1800oCn nFinalCcontent:80%to99%n nTemp.dependentTemp.dependentn nOverallYield:40-45%OverallYield:40-45%13S
13、urface Treatmentn nImprovesbondingwithpolymericmatrixmaterialsn nIncreasesoxygenatedgroupsatsurfacen nGassingatelevatedtemps.Gassingatelevatedtemps.n nSodiumhypochloritesolutionSodiumhypochloritesolutionn nNitricAcidNitricAcid14C.F.s from PAN precursor Fibers15PAN and Pitch processing16Rayon (cellul
14、ose) precursor fibersn nTypicallylowmodulus(4x10Typicallylowmodulus(4x106 6psi)psi)n nFiberheatedto400Fiberheatedto400o oC,pyrolizationofcelluloseC,pyrolizationofcellulosen nCarbonizationat1000Carbonizationat1000o oC Cn nGraphitizedat2000Graphitizedat2000o oC Cn nHighmodulusobtainedbystretchingatfin
15、alheatHighmodulusobtainedbystretchingatfinalheattreatmentstagetreatmentstage17Mesophase Pitch Precursorsn nSamegeneralprocessasPANSamegeneralprocessasPANn nLowtensilestrengthofprecursorfibersLowtensilestrengthofprecursorfibersn nMelt-spinisusedMelt-spinisusedn nDonotrequirestretchingprocesstomaintai
16、nDonotrequirestretchingprocesstomaintainpreferredalignmentpreferredalignment18Final Carbon Fibersn nWoven,Braided,orWoundn nUnidirectionallay-upsUnidirectionallay-upsn nMulti-directionalweavesMulti-directionalweavesn nStrengthlimitingfactorsn nPurityofprecursorPurityofprecursorn nPrecursorvoidconten
17、tPrecursorvoidcontentn nTemperatureTemperaturen nTensionTension19C.F.s from differing processes20Carbon vs. SteelMaterialMaterial TensileTensileStrengthStrength(GPa)(GPa)TensileTensileModulusModulus(GPa)(GPa)DensityDensity(g/ccm)(g/ccm)SpecificSpecificStrengthStrength(GPa)(GPa)StandardGradeStandardG
18、radeCarbonFiberCarbonFiber3.53.5230.0230.01.751.752.002.00HighTensileSteelHighTensileSteel1.31.3210.0210.07.877.870.170.1721Modulus Classificationsn nUltrahighelasticmodulustype(UHM)n nHighelasticmodulustype(HM)n nIntermediateelasticmodulustype(IM)n nStandardelasticmodulustype(HT)n nLowelasticmodulu
19、stype(LM)22Carbon Fiber Modulushttp:/www.carbonfiber.gr.jp/english/index.htmlhttp:/www.carbonfiber.gr.jp/english/index.html23Composite uses of carbon fibersn nPolymer-MatrixCompositesn nMetal-MatrixCompositesn nCarbon-MatrixCompositesn nCeramic-MatrixCompositesn nHybridcomposites24Carbon-Carbon Comp
20、ositesn nCarbonsubstrateinCarbonaceousMatrixn nSameelementdoesnotsimplifycompositebehaviorn neachconstituenthasawiderangeofformsn nCarbonfiberscontinuousandwovenn nDisadvantagesn nHighfabricationcostn nPooroxidationresistancen nPoorinter-laminarproperties25Fabrication of C-C Compositesn nLiquidphase
21、impregnation(LPI)n nHotisostaticpressureimpregnationcarbonization(HIPIC)n nHotpressingn nChemicalVaporInfiltration(CVI)26Applications of C-C Compositesn nAircraftBrakesAircraftBrakesn nHeatPipesHeatPipesn nReentryvehiclesReentryvehiclesn nRocketmotornozzlesRocketmotornozzlesn nHipreplacementsHiprepl
22、acementsn nBiomedicalimplantsBiomedicalimplantsn nToolsanddiesToolsanddiesn nEnginepistonsEnginepistonsn nElectronicheatsinksElectronicheatsinksn nAutomotiveandmotorcyclebodiesAutomotiveandmotorcyclebodiesn nBicyclesBicycles27n nBuckley,JohnD.andDan.D.Edie,eds.Buckley,JohnD.andDan.D.Edie,eds.Carbon-
23、Carbon-CarbonMaterialsandCompositesCarbonMaterialsandCompositesNoyesNoyesPublications:ParkRidge,NJ1993Publications:ParkRidge,NJ1993n nChung,Deborah.Chung,Deborah.CarbonFiberCompositesCarbonFiberComposites. .Butterworth-Heinemann,Boston1994Butterworth-Heinemann,Boston1994n nJapanCarbonFiberManufacturersAssociationJapanCarbonFiberManufacturersAssociation http:/www.carbonfiber.gr.jp/english/index.htmlhttp:/www.carbonfiber.gr.jp/english/index.htmlFurther Reading28