Effects

JournalofHarbinInstituteofTech.

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    ;WANGDongIbolFENGY~-jielTIANYah3HANLi—wei3

    ;王东波,冯玉杰,田言,韩俐伟

    ;SchofMunicipalandEn.-,ifnnmenEn咖

    eering,HarbinInstituteofTechnology,Harbin150090,China,E—mail:w121308@163?co

    rn;2Fm”Ionrne”tal

    ;scho01,Guaniuniversity,Nanning530004,Chin;3.InstituteofPetrochemicalofHeilongjiangProvince,Harbin150076,China)

    ;Abstract:SiO,nanoparticle,throughsurfacemodificationbysilicanecouplingagentKH_570,wassuccessfully

    ;即

    p1iedtomakenanoSiO2/PPcompositematerialbythemelt—outblendingprocesswithtwin

    —screwextrude?

    ;Effects0fnanoSiO,onthereinforcingandtougheningofPPwerestudiedbyanalyzingthematerialimpactbr0一

    ;kenfracture.thecrystelstructureandthediameterofSiO2/lanoparticleusingSEM,XRDandTEM,respec—

    ;tivelv.ResuhsshowedthattheimpactstrengthandthetensilestrengthofnaIloSiO2/PPcompositematerial

    ;weI?

    impmvedappaIlently;theimpactstrengthofPPwasfracturewasincreasedto67%whenthenanoSiO2

    ;c.ntent-Was4%;whi1ethenaJ1oSiO2partic1e

    叩.nsurfacetreatmentwillimp.se.bvi.usheterogeneousnuclea—

    ;tionfunctionoverPPcrysta1.

    ;Keywords:nano-silicaparticles;silicanecouplingagent;toughening;polypropylene ;CLCnumber:TQ327.8Documentcode:AArticleII):1005-9113(2008)05686JD4 ;Withmeritslikerichrawmaterialsource,low

    ;priceandlightdensityetc,polypropylene(PP)isone

    ;ofthecommonresinsextensivelyappliednowadays;

    ;however.thedisadvantagelikedistinguishedbrittleness

    ;andlowimpactstrengthatfractureetcrestrictitsfur-

    ;therapplication.Fillingpolymerwithinorganicnano’

    ;particlewasthehotspotinpolymermodification.

    ;Withthematurityandindustrializationofnanomaterial

    ;productionprocesslikenanoCaCO3,SiO2and ;TiO2etc,theplasticrigidityandtoughnesswouldbe ;enhancedatthesametimebothintheoreticalanalysis ;andinpracticaleffectincasethenanoparticledisplays ;sounddisperseinPP.However.itisdimculttorealize ;thenano一1eveldispersioninpolyolefinmatrixbecause ;thenanoparticlecouldformagglomerationeasilyf0rifs ;highsurfaceenergy[.

    -81 ;Thoughgreatbreakthrough【

    ;hasbeenobtainedbydomesticandforeignscholarsin ;termsofnanoparticle/compositemateria1thisproblem ;isstil】l】nsolved.

    ;Bymelt.outprocess,theauthormixednanoSiO2 ;uponsurfacetreatmentbysilicanecouplingagentKH一

    ;570togetherwithPP.thenextrudedwithtwin—screwex—

    ;truder.thusobtainedthenanoSiO,/PPcompositemate—

    ;ria1.Throughtheresearchonmechanicalperformanceof ;SiO/PPcompositematerialaswellasthefractureanal- ;ysisoverthematerialbyScanningElectronMicroscopic, ;togetherwiththePPcrystalbyXRD,theauthorfurther ;discussedtheeffectandtougheningmechanismofllano ;SiO2,uponthesurfacetreatmentbycouplingagent,O—

    ;verthemechanicalperformanceofPP.

    ;Received20o5—12—05

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    ;1Experiment

    ;1.1MainMaterial

    ;Isotacticpolypropylene(PP)homopolymerpow ;der.suppliedbyDaqingPertrochemicalIndustrial ;Co..China,wasusedasthematrixpolymer.Ithasa ;meltindex(MFI)of3.0g/10min(2.16kgat

    ;230oC).Theprecipitatednano—SiO2withanaverage

    ;primaryparticlesizeof16nmandaspecificsurfacear- ;eaof640m,譬wassuppliedbyZhoushanNanomateri—

    ;alsCo..Ltd.SilanecouplingagentKH.570waspur—

    ;chasedfromNa-jingShuguangchemicalplant. ;1.2Equipment

    ;Twin.screwextruder,TE一35,JiangsuNanjing

    ;KeyaCompany;fullhydraulicplasticinjectionmolding ;machine:JPH120,ShundeQinchuanHenliPlasticMa—

    ;chineCo..Ltd;SuspendedBeamImpactTestingMa—

    ;chine:XJU-2.75J,ChengdeTestingMachineCo., ;Ltd:MicroprocessorControlElectronicsTensileTester:

    ;WD00.ShenzhenKaiqiangMachineryCo.,Ltd; ;MultipleSampleMachine:ZHY—W,ChengdeTesting

    ;MachineCo.,Ltd.

    ;1.3PreparationofNanoSiO,/PPCompositeMa- ;terial

    ;Afterbeingdriedin110qcvacuumchamber.

     ;nanoSiO2particlewith100mLpureethanolwerevi—

    ;bratedbyultrasonicwavefor20min,thensilicane ;couplingagentKH一570wasaddedforsurfacewrapping ;treatment.Leavethesameforreactionuponnitrogen ;Journal0厂HarbinInstituteofTechnology(NewSeries),Vo1.!?0.!

    ;protectionunderroomtemperaturefor24h,separate ;thesamebycentrifugalmethod,andthenmixtheSiO2 ;particlethusobtainedwithPPpowderevenly,extrude ;withtwin—screwextruder,thusobtainingparticleand ;makingitintostandardsamplebygoingthroughinjec- ;tionmoldingfortesting.

    ;1.4MaterialCharacterization

    ;XRDtest:Recordedbyscanningcontinuously ;withD/maxtypewide—angleX—raydiffractometer,Cu-

    ;Karadiation,blackleadsolidcolordevicefilter,scan- ;ningspeedas4.o/min,scanningscopeis5.0—

    ;60.0..ScanningelectronmicroscopeS-4700(HI—

    ;TACHL):analysisonfractureappearanceofthesee—

    ;tionofimpactsampleandbrittlebreakingbothtreated ;bygiltsprayingwasmadeunderroomtemperature; ;transmissionelectronmicroscopeJem.1200Ex:upon ;dispersingnanoSiO2particleinpureethanolbyultra—

    ;sonicwave,observethedispe”singstatusofnanoparti-

    ;clebyfilming.

    ;2Resuit&Discussion

    ;2.1AppearanceAnalysisbefore&afterSurface ;TreatmentofNanoSiO,Particle

    ;TheTEMfigureofnanoSiO,beforeandaftersur—

    ;facetreatmentwasshowninFig.1.Fromwhich.it ;couldbeseenthatthediameterofnanosiO.withoutsur. ;facetreatment(Fig.1(a))wasfromdozenstohundreds ;nmandevenbigger,AsshowninFig.1(b),thediame—

    ;terofnanoSiO2goingthroughsurfacetreatmentbysili—

    ;canecouplingagentKH-570rangedfrom50to10onm ;andthedisperseofnanoSiO,wasobviouslyimproved. ;ThestructureandagglomerationstatusofnanoSiO,had ;displayedapparentchangeswithaveragediameterless ;than100nm.evenwiththeexistenceofagglomeration.

;2.2MechanicalPerformanceofNanoSiO,/PP

    ;CompositeMaterial

    ;Fig.2depictedtherelationshipcurveofthemate. ;rialfractureimpactstrengthofnanoSiO/PPcomposite ;withnanoSiOparticlecontent.Withtheincreaseof ;nanoSiO2particlecontent,thefractureimpacts~ength ;ofPPenhancedgraduallyandreachedanapexvalueas ;67%whenthecontentofnanosi0.was4%.While ;theimpactstrengthofPPdeclinedinalinearwayas ;thenanoSiO,contentincreasedcontinuallyuntil10%. ;whenitwaslowerthanthatofpurePP:Fig.3showed ;theeffectofnanoSiO,contentovertensilestrengthof ;SiO,/PPcomposite.Itcouldbeobservedthatithad ;thesamevariationtrendwiththatinFig.2indicated ;thatnanoSiO,contributedmoretoPPimpactstrength ;andtensilestrengthwhenitscontentwasrelativelylow—

    ;er(4%);whileformorefillingamount,thenano ;SiO.particleshowedpoordispersioneffectandformed ;biggeragglomeration,inducingthedefectofmaterial ;andobviousdecreaseofmechanicalperformanceofthe ;matrix.

    ;吕

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    ;葛

    ;昌.

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    ;(b)SiO2一KH570compositeparticle

    ;Fig.1TEMmicrographs

    ;ThecontentofSiO2/%

    ;Fig.2IzodnotchimpactstrengthofPPasaFunctionof ;SiO2content

    ;2.3ScanningElectronMicroscopeAnalysisfor ;theFractureImpactSectionofComposite

    ;Material

    ;ThefracturesectionSEMfigureofPP..basedcom.. ;positematerialwasshowninFig.4,Fig.4(a)showed ;thatthesectionofpurePPwassmooth.whichcouldbe ;classifiedasobviousbrittlefracture.Whilethesection ;scanningpictureofnanoSiO2/PP(4/96)upontreat—

    ;mentbycouplingagentdisplayed(Fig.4(b))evident ;plasticdeformation.andthecrackspreadsinthefclrln ;ofdimpleandshowedapparentbrittle—ductiletransition.

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    ;performanceanddemonstratedthatthePPcrystal ;structurechangedwhenthenanoSiO2particleupon ;surfacetreatmentwasfilled,namelythatnanoSiO2 ;particlewouldinducetheformationof一PP,thusrein-

    ;forcingandtougheningPP.

    ;3Conclusions

    ;1)Thefractureimpactstrengthandtensile

    ;strengthofnanoSiO2/PPcompositeuponsurfacetreat- ;mentwouldincreaseobviouslywhenthenanoSiO,was ;filledatlowercontent(4%).whilethemechanical ;performanceofwhichwoulddeclineapparentlyasthe ;contentofnanosi0exceeded6%.

    ;2)TougheningmechanismanalysisofnanoSiO2/ ;PPcompositeshowedthatthenanoSiO2upontreatment ;bycouplingagentwouldinducePPmatrixresininto ;theheterogeneousnucleatiorandenhancetheforlTla. ;tion0f一PPcrystal,thusrealizingthereinforcingand ;tougheningofPP.Byanalyzingfromfractureaction ;mechanism,whennanoSiO2/PPcompositewas

    ;shockedbytheoutsideforce,thesoundlydispersed ;nanoSiO.wouldeffectivelydispersethestressandab. ;sorbimpactenergy,thuspreventingsmallcrackfrom ;expandingintobiggeroneandenhancingthetoughness ;ofmatrixresin

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