外文翻译水溶性粘结剂高弯曲模注塑粉.doc
附录Water-solublebinderwithhighflexuralmodulusforpowderinjectionmoldingMINSEOKSONG,MINSOOPARK,JINKONKIMNationalCreativeResearchInitiativeCenterforBlockCopolymerSelf-AssemblyandDepartmentofChemicalEngineering,ElectronicandComputerEngineeringDivisions,PohangUniversityofScienceandTechnology,Kyungbuk790-784,KoreaILBUMCHO,KYUNGHOKIM,HWANJINSUNG,SANGHOAHNResearchInstituteofScienceandTechnology,Pohang,Kyungbuk790-784,KoreaE-mail:jkkimpostech.ac.krAnewbindersystem,containingternarypolymerblendsofpoly(methylmethacrylate)(PMMA),celluloseacetatebutyrate(CAB)andpolyethyleneglycol(PEG),wasintroducedforthepowderinjectionmoldingofstainlesssteelpowders.TheweightfractionofPEGinthebinderwasmaintainedtobe0.65.WhentheweightfractionofPMMAinthebinderwas0.10.25(thustheweightfractionofCABwas0.10.25),thefeedstockswith56vol%ofsteelpowdersweresuccessfullyinjectionmoldedwithoutshowinganyjetting.Furthermore,thefeedstockshavemuchhigherflexuralmoduluscomparedwiththosepreparedbyabinderconsistingonly35/65(wt/wt)CAB/PEGblend.Threebinaryblends,PMMA/CAB,PMMA/PEG,andCAB/PEG,werecompletelymiscibleataninjectionmoldingtemperatureof130C.Theextractionprocessemployedinthisstudybecomesenvironmentallyfavorableduetothemajorcomponent(PEG)ofthebinderwhichiseasilyextractedbyasolventofwaterorethanol.Also,theshapemaintenanceduringthesolventextractionwasexcellent,andfinalsinteredpartshadexcellentdimensionalstability.Duetohighflexuralmodulusoffeedstocks,thisbindersystemcanbeemployedforpreparinglargesizedinjection-moldarticles._C2005SpringerScience+BusinessMedia,Inc.1.IntroductionPowderinjectionmolding(PIM)processingofmetalsorceramicshasbeenemployedtodeveloptinyandsophisticatedmetalorceramicparts,anditisaveryeconomicprocesscomparedwithacastingandamachining1,2.AmongthemanystepsinthePIM,thesuitablechoiceofabinderbecomescrucialtodeterminethemechanicalpropertiesofthefinalproduct.Wax-basedbinderscontainingabackbonematerialofpolyethyleneorapoly(ethylene-ran-vinylacetate)havebeenwidelyusedinthepowderinjectionmoldingindustries3,4.However,organicsolventsuchashexaneandheptane,whichisnotanenvironmentallyfavorablesolvent,shouldbeusedtoextractthewax.Toavoidusinghexaneorheptaneduringtheextraction,effortshavebeenfocusedonfindingnewtypesofbindersthatwouldberemovedbyanenvironmentallyfavoredsolventsuchaswater511.Daviesandcoworkers7,8introducedapoly(methylmethacrylate)/poly(ethyleneglycol)PMMA/PEGbindersystemforstainlesssteelpowders.Althoughaveryhighmolecularweight(1,000,000)ofPMMAwasused,thebinderwasmixedwithsteelpowderinthepresenceofwater,becausewaterisasolventoflowermolecularweight(<1500)PEGandanemulsionmediumofPMMA.However,withoutusingemulsioncontainingwaterforPMMAparticles,abinderconsistingofPMMAandPEGmightnotbemixedeffectivelywithsteelpowders.Previously,weintroducedawater-solublebinderconsistingofcelluloseacetatebutyrate(CAB)andvariousmolecularweightsofPEG.WefoundthatthecrystallizationofPEGdependinguponthemolecularweightaffectedprofoundlytheshapemaintenanceduringsolventextraction12,13.Namely,whenthemolecularweightofPEGwaslargerthan3400,crackswerefoundingreenpartsafterthesolventextraction.AlthoughbindersofCAB/PEGwithmolecularweightlessthan2000couldbeinjectionmolded,jettingresultingfromlowviscosityofPEGwassometimesobserved.Also,mechanicalpropertiessuchasflexuralstrengthofgreenpartsarepoor,whichrestrictsonetomakinglargesizedinjection-moldedarticles.Inordertoovercomethesedisadvantages,weaddedPMMAtoCABasthebackbonematerial.TherationalbehindchoosingPMMAisthat(i)PMMAismisciblewithbothCABandPEGataprocessingtemperatureof130C;(ii)itshowsgoodadhesionwithmetalpowderduetohavingapolargroup,whichpreventsbinderseparationduringinjectionmolding;and(iii)itprovidesgoodmechanicalpropertiesofgreenparts.WecouldusehighermolecularweightofPEGupto8,000whenPMMAwasemployed.AbinderconsistingofPMMA/CAB/PEGternaryblendsexhibitedhigherflexuralmodulusandsuitablerheologicalpropertiesforinjectionmolding;thusalargesizedinjectionmoldedarticlewassuccessfullyprepared.Also,weobservedthattheshapemaintenanceduringtheextractionwasexcellent,andfinalsinteredpartshadexcellentdimensionalstability.2.Experimental2.1.MaterialsPMMAwasalsokindlysuppliedbyLGMMACo,andthemolecularweightandpolydispersityofPMMAweredeterminedbyusinggelpermeationchromatography(WatersCo.)withPMMAstandards.CABwith54mol%butyratesidegroupwaspurchasedfromAcrosCo.andPEGwithdifferentmolecularweightswaskindlysuppliedbyKoreaPolyolCo.(Korea).ThemolecularcharacteristicsofthesematerialsaregiveninTableI.CABandPMMAareamorphousmaterialswithaglasstransitiontemperatureof94Cand100C,respectively,measuredbyDSC(Perkin-ElmerDSC7series)ataheatingrateof20C/min.Themetallicpowderwasstainlesssteel(17-4PH,MitsubishiSteelMFGCo.)havingirregularshapeandamedianparticlesizeof8.86m.2.2.SamplepreparationandrheologicalpropertiesThefeedstock,amixtureofthebinderandmetallicpowder,wasfirstpreparedbymixingat130Cfor1hbyusingtheKneadingBladeTypeMixer(IKAVISCCo.);thenitwasshapedintoarectangularbar70.22×7.12×3.57mm(L×W×T)byusinga180tonprecisioninjectionmoldingmachine(SodickPlustechCo.;Japan)at130Candmoldtemperatureof25C.AnAdvancedRheometricsExpansionSystem(ARES)usingthedynamicoscillatorymodewithparallelplatefixture(25mmdiameter)wasusedtomeasuretheviscosityofthebinderitself.Thestrainamplitudewas5%,whichliesinlinearviscoelasticityrange.TABLEIMolecularcharacteristicsofblendcomponentsemployedinthisstudyMnPolydispersityindexTgorTm(C)PMMA63.0001.47Tg=100CAB11,0002.3Tg=94PEG-11,5001.15Tm=43PEG-22,0001.10Tm=50PEG-33,3501.14Tm=54PEG-88,0001.16Tm=562.3.TurbidityexperimentofPMMA/CABblendVariousblendcompositionsofPMMAandCABforturbiditytemperature(Tb)measurementwerepreparedbydissolvingapredeterminedamountofthemixtureintoluene(10wt%)andslowlyevaporatingthesolventover8hatroomtemperature.Thesamplethicknesswas10m.Eachspecimenwasannealedinthehomogeneousstate(120C)for4h.TheTbofeachcompositionwasmeasuredfromthesuddenincreaseinlightscatteringintensityatascatteringangleof30uponheatingthemixturefrom120Catarateof0.1C/min.OncetheTbofaspecimenwasestimated,theexactTbwasdeterminedbythenakedeyeuponatemperatureincrementby0.5Cnearthetemperatureofinterest.Thespecimenwasheldateachtemperaturefor1h.ThemaximumerrorinthevaluesofTbdeterminedwas±0.5C.2.4.DebindingandsinteringTwostepsofdebindingofgreenpartswereconducted.ThefirststepwastoextractPEGoutofgreenpartsbydistilledwateratroomtemperaturefor24h.Thesecondstepwasreferredtoasthethermaldebinding,wherethebackbonescomposedofPMMAandCABwerecompletelyremovedandpre-sinteringofmetalpowdersoccurred.Finallythesinteringofmetalpowderswascarriedout.Thermaldebindingandsinteringwerecarriedoutinatube-typefurnace(LentonThermalDesignLtd.)underhydrogenatmospherebyusingthesamethermalhistoryasref.12.3.Resultsanddiscussion3.1.MiscibilitybetweenbindercomponentsThebinderemployedinPIMhasamulti-componentsystem:(a)abackbonepolymerthatprovidesshapemaintenanceduringsolventextraction;(b)anextractablepolymerthatisremovedduringthefirststepofthedebindingprocess,and(c)asurfactanttobridgebetweenthebinderandpowder1.Itisnecessarythatallcomponentsshouldbemiscibleatprocessingtemperatures.Otherwise,thebindercomponentsbecomemacrophase-separated.Previously,weshowedthatabinaryblendofCAB/PEGhavingamolecularweight(M)of35000showedlowercriticalsolutiontemperature(LCST)of168C13.SinceMofPEGemployedinthisstudyislessthan8000,wefoundthattheCAB/PEGmixturedoesnotbecomephase-separatedupto250C.ThePMMA/PEGblendbecomescompletelymiscibleattemperaturesgreaterthanthemeltingtemperatureofPEG14.Fig.1givesthephasebehaviorofthePMMA/CABblend,fromwhichtheLCSTwas142Cat20/80(w/w)PMMA/CABcomposition.Thus,weconcludethatMacrophaseseparationamongallthreebinaryblends(PMMA/PEG,CAB/PEG,andPMMA/CABblends)doesnotoccurataprocessingtemperatureof130C,whichisthemixingandinjectionmoldingtemperatures.Also,whentheamountofPMMAwaschangedfrom15to25wt%atafixedamountofPEG(65wt%),noturbiditywasdetectedupto200C.Figure1PhasediagramsofPMMA/CABblend.3.2.RheologicalpropertiesItisknownthatfeedstocksshouldhavealowenoughviscositytobeprocessedbyinjectionmolding.However,whentheviscositybecomestoosmall,jettingoccursduringtheinjectionmoldingprocess;thustheexactshapeofmoldedarticleisimpossible.Fig.2givesthecomplexviscosity(*)asafunctionoffrequencyforthebinderscomposedofvariouscompositionsofPMMA/CAB/PEGswithtwodifferentmolecularweightsofPEGs.ItshowsthatasthecontentofPMMAandMofPEGincrease,theviscositybecomeslarger.WhenthebindersdonotcontainCAB,abinderconsistingof35/65(wt/wt)PMMA/PEGhaszero-shearviscosity(o)of100Pa·s,regardlessofmolecularweightsofPEG.Itisknownthatwhenoofabinderislargerthan20Pa·s,thefeedstocksincludinghighvolumeofpowderscouldnotbemoldedbyinjectionmolding1.Therefore,itisconsideredthatfeedstocksconsistingof15/20/65and25/10/65(wt/wt/wt)PMMA/CAB/PEG-8binderand56vol%ofsteelpowderscouldbeinjectionmolded.