聚合物納米復合材料聚合物納米復合材料復合體系組合分散相的尺度大小>1000nm(>1μm)100~1000nm(0.1~1μm)1~100nm(0.001~0.1μm,10~1000?)0.5~10nm(5~100?)（1）聚合物/低分子物低分子作增容劑低分子流變改性劑外部熱塑性聚合物（2）聚合物/聚合物宏觀相分離型聚合物摻混物微觀相分離型聚合物合金（1）分子復合物；（2）完全相容型聚合物合金（3）聚合物/填充物聚合物/填充物復合體系聚合物/填充物復合體系聚合物/超細粒子填充復合體系聚合物納米復合體系聚合物復合體系的分類第一節(jié)概述復合體系分散相的尺度大小>1000nm100~1000nm1納米概念的形成早期，石墨、炭黑中的顆粒1959年，美國物理學家RichardFeynman提出“whatwouldhappenifwecouldarrangetheatomsonebyonethewaywewantthem?”20世紀70年代康乃爾大學C.G.Granqvist&R.A.Buhrman小組氣相沉積制備納米20世紀80年代，原西德Gleiter首次制備金屬納米，提出納米材料及其應(yīng)用1981年，IBM發(fā)明AFM和STM，推動納米技術(shù)發(fā)展20世紀80年代末期，日本豐田研究中心制得PA6/粘土納米復合材料納米概念的形成早期，石墨、炭黑中的顆粒WhatnanocompositesareAnanocompositeisdefinedasacompositematerialwhereatleastoneofthedimensionsofoneofitsconstituentsisonthenanometresizescale.1.納米復合材料(nanocomposite)定義:WhatnanocompositesareAnanoc納米復合材料非聚合物納米復合材料金屬/金屬金屬/陶瓷陶瓷/陶瓷聚合物納米復合材料有機/無機納米復合材料聚合物/聚合物納米復合材料聚合物基無機物基分子復合原位復合微纖/基體Classificationofnanocomposite

納米復合材料非聚合物金屬/金屬聚合物有機/無機聚合物/聚合物Polymer/inorganicnanocomposites

Polymernanocompositesaregenerallydefinedasthecombinationofapolymermatrixresinandinorganicparticles(particles,layersorfibres)whichhaveatleastonedimension(i.e.length,width,orthickness)inthenanometersizerange.

2.聚合物/無機納米復合材料定義Polymer/inorganicnanocomposi

納米纖維(碳納米管、纖維素晶須、凹凸棒土)

層狀無機物(layeredsilicates)納米粒子(CaCO3、SiO2、TiO2、ZnO、Al2O3、Cr2O3)Schematicofnanoscalefillers第二節(jié).制備聚合物納米復合材料的無機物的種類納米纖維(碳納米管、纖維素晶須、凹凸棒土)Schema碳納米管碳納米管是由多個碳原子六方點陣的同軸圓柱面套構(gòu)而成的空心小管，其中石墨層可以因卷曲方式不同而具有手性。碳納米管的直徑一般為幾納米至幾十納米，長度為幾至幾十微米。碳納米管可以因直徑或手性的不同而呈現(xiàn)很好的金屬導電性或半導體性。

(Iijima1991)多壁碳納米管單壁碳納米管碳納米管碳納米管是由多個碳原子六方點陣的同軸圓Derivedfromexpandable2:1layeredsmectitefamilyofclaysIsomorphoussubstitutionofatomscreatesachargeimbalanceSodiumMontmorillonitePlateletStructureNa+SiOxideAl/Mg/Fe–Oxide/HydroxideSiOxideNa+

~50nm-300nm~1nmDerivedfromexpandable2:1lLayeredsilicates

AdvantagesoverconventionalfillersExpandablestructuresIndividualsilicatelayershaveatleastonedimensioninnanoscopicsizerangeLayershavehighaspectratios(length/thickness),extremelylargesurfaceareas,andhighmoduliLargepropertybenefitsachievableatverylowfillerlevelsascomparedtoconventionalreinforcingadditivesWeightsaving(2.5wt%nanoclayvs.25wt%talc)Betterprocessibility(fastercyclingtimesandquickerfill)Don’tneednewlinesoftools~1nmLayeredsilicates

AdvantagesCationicExchangeofSodiumMontmorillonite+SodiumMMT*Swollen“Organoclay”R1*R2R3CH3N+Cl-+NaClCationicSurfactant(e.g.,alkyl-ammoniumchloride)=Na=Alkylammonium蒙脫土族礦物具有離子交換性、吸水性、膨脹性、觸變性、黏結(jié)性、吸附性等特性。CationicExchangeofSodium插層劑的作用利用離子交換的原理進入蒙脫土片層之間；擴張片層間距；改善層間的微環(huán)境；使蒙脫土的內(nèi)外表面由親水性轉(zhuǎn)化為疏水性；增強蒙脫土片層與聚合物分子鏈之間的親和性；降低硅酸鹽材料的表面能。常用的插層劑有烷基銨鹽、季銨鹽、吡啶類衍生物和其他陽離子型表面活性劑插層劑的作用利用離子交換的原理進入蒙脫土片層之間；常用的插層第三節(jié).聚合物納米復合材料主要制備方法

溶膠-凝膠法(Sol-Gel):烷氧基金屬或金屬鹽等前驅(qū)物（水溶性鹽或油溶性醇鹽）溶于水或有機溶劑中形成均質(zhì)溶液，溶質(zhì)發(fā)生水解反應(yīng)生成納米級粒子并形成溶膠，溶膠經(jīng)蒸發(fā)干燥轉(zhuǎn)變?yōu)槟z。原位聚合法(in-situpolymerization):分散有納米粒子的單體聚合后形成復合體系共混法:聚合物與納米粒子共混插層法:將單體或聚合物插入層狀無機物層間形成納米復合結(jié)構(gòu)第三節(jié).聚合物納米復合材料主要制備方法溶膠-凝膠法(SolPreparationMethods原位插層(In-situintercalationpolymerization)

溶液插層(Polymerintercalationfromsolution)

熔體插層(Polymermeltintercalation)Polymer/Layeredsilicatenanpcomposites聚合物/層狀硅酸鹽納米復合材料制備方法(插層法)PreparationMethods原位插層(In-sitMorphologyoflayeredsilicateMorphologyoflayeredsilicate1.InsituPolymerization1.InsituPolymerization2.Polymerintercalationfromsolution2.Polymerintercalationfroms3.meltintercalation3.meltintercalationMechanicallyblendpolymer–organoclaymixturesabovethepolymer’sTm(i.e.,highsheartwinscrewextrusion)NanocompositeFormationTechnique

-MeltProcessing–(常規(guī)做法)hpMechanicallyblendpolymer–orgNaokiHasegawa,etal,Polymer44(2003)2933–2937anovelcompoundingprocessusingNa–montmorillonitewaterslurryforpreparingnovelnylon6/Na–montmorillonitenanocompositesSchematicfiguredepictingthecompoundingprocessforpreparingtheNCH-CSusingtheclayslurryNewmethod(加入層狀無機材料的懸浮液)NaokiHasegawa,etal,PolymerNaokiHasegawa,etal,Polymer44(2003)2933–2937SchematicfiguresdepictingdispersionoftheNa–montmorillonitesilicatelayersoftheslurryintonylon6duringcompoundingNaokiHasegawa,etal,PolymerKineticsofpolymermeltintercalationTwostepsfornanocompositeformation:Polymertransportedfromtheagglomerate-polymermeltinterfacetotheprimaryparticlesPolymermeltpenetratetotheedgesofthecrystallites

ThefirststepislimitingstepforpolymernanocompositesformationKineticsofpolymermeltinterThermodynamicanalysis△F=F(h)-F(h0)=△E-T△S

△F＜0indicatelayerseparationisfavorable△F＞0impliestheinitialunintercalatedstateisfavorable△S≈△Schain+△SpolymerThermodynamicanalysis第四節(jié)層狀納米復合材料結(jié)構(gòu)與性能1.結(jié)構(gòu)LayeredNanocompositestructure第四節(jié)層狀納米復合材料結(jié)構(gòu)與性能Schematicillustrationoftwodifferenttypesofthermodynamicallyachievablepolymer/layeredsilicatenanocomposites.SchematicillustrationoftwoSchematicdepictingtheXRDpatternsforvarioustypesofstructures不同插層結(jié)構(gòu)的表征(X射線衍射法)層狀有序結(jié)構(gòu)完全消失完全未解離插層結(jié)構(gòu)(層間距明顯增大)插層結(jié)構(gòu)均一插層結(jié)構(gòu)無序SchematicdepictingtheXRDpaX-raydiffractionpatternofPEO/Na+-MMThybridheatedto80℃for0,2,and6hVaiaRA,etal,Macromolecules1995,28:8080MMT片層結(jié)構(gòu)衍射峰X-raydiffractionpatternofPTemporalseriesofX-raydiffractionpatternsforaPS30/F18pelletannealedinsituat160℃invacuumVaiaRA,etal,AdvMater1995,7,154–156TemporalseriesofX-raydiffr

2.性能PropertiesofpolymerlayeredsilicatenanocompositesEfficientreinforcementwithminimallossofductilityandimpactstrengthIncreasethermalstabilityIncreaseflameretardant

ImprovedgasbarrierpropertiesImprovedionicconductivityReducedthermalexpansioncoefficientAlteredelectronicandopticalproperties2.性能PropertiesofpolymerlayPropertiesofNylon-6layeredsilicatenanocompositesPropertyNanocompositesNylon-6TensileModulus(GPa)TensileStrength(MPa)HeatDistortionTemp(℃)ImpactStrength(KJ/m2)WaterAdsorption(%)CoefficientThermalExpansion(x,y)2.11071602.80.516.3×10-51.169652.30.8713×10-5最有價值的性能變化PropertiesofNylon-6layeredComparisonoftheYoung’smodulusofclay/nylon-6nanocompositesandglassfiberreinforcednylon-6compositeswithlowfillerloadingFenggeGao,materialstoday,2004,50-55Inthelowfillerloadingrange,clay/polymernanocompositeshavethepotentialtoreplacetraditionalfiberreinforcedcomposites.ComparisonoftheYoung’smoduModulusincreasebylayeredsilicatereinforcementofPA66L.A.GOETTLER,PolymerReviews,47:291–317,2007普通層狀填料玻纖增強Modulusincreasebylayeredsi(a)Organoclay(OMSFM)(wt%)dependenceofHDTofneatPLAandvariousPLACNs.(b)LoaddependenceofHDTofneatPLAandPLACN7ThermalpropertiesSuprakasSinhaRay,etal,Chem.Mater.2003,15,1456-1465(a)Organoclay(OMSFM)(wt%)TGAanalysisofPDMS(solidline).andPDMSnanocomposite(dashedline)(massfraction10%mica-type-silicate,MTS).Lineswereaddedtoindicate50%massloss.Burnside,S.D.,Giannelis,E.P.,Chem.Mater.1995.

7,1597TGAanalysisofPDMS(solidlinComparisonoftheHeatReleaseRateHRR.plotfornylon-6,nylon-6silicate-nanocomposite(massfraction5%)at35kW/m2heatflux,showinga63%reductioninHRRforthenanocomposite.flameretardantJeffreyW.Gilman,AppliedClayScience,15,1999.31–49放熱速率顯著下降ComparisonoftheHeatReleasePP及其納米復合材料的熱釋放速率對比（熱通量=35kW/m2)PP及其納米復合材料的熱釋放速率對比Flammabilityperformancefornylon-6nanocompositesnanocompositeworkswithotherflameretardantsinasynergisticorcooperativemannertolowerthepolymerflammability(heatreleaserate)ComparisonbetweennanocompositesandconventionalflameretardantsAlexanderB.Morgan,Polym.Adv.Technol.2006;17:206–217工業(yè)上評價材料阻燃性能的檢測標準FlammabilityperformancefornBeyer,G.,2002NanocompositePowerCableKabelwerkEupenBeyer,G.,2002NanocompositeSelectedvideoimagesat100,200,and400sinnitrogenat50kW/m2.TakashiKashiwagi,Polymer45(2004)881–891Mechanism:Thesilicate-richcharactsasanexcellentinsulatorandmasstransportbarrier,therebyreducingtheheatreleaseratemandslowingdowntheescapeofvolatileproductsreleasedasthepolymerdecomposes.阻燃機理:硅酸鹽作為隔絕火焰,熱量和物質(zhì)的材料減緩了聚合物分解時揮發(fā)份的釋出Selectedvideoimagesat100,Proposedmodelforthetorturouszigzagdiffusionpathinanexfoliatedpolymer-claynanocompositewhenusedasagasbarriergasbarrierpropertiesProposedmodelforthetorturoMontmorillonitecontentdependenceofpermeabilitycoefficientofwatervaporinpolyimide-clayhybrid.MontmorillonitecontentdependenceofpermeabilitycoefficientofO2inpolyimide-clayhybridKAZUHISAYANO,etal,JournalofPolymerScience:PartAPolymerChemistry,Vol.31,2493-2498(1993)應(yīng)用價值:食品保鮮MontmorillonitecontentdependStarch-claynanocompositebagmadebyfilmblowingtechnology.Thisbaghasbeenstoredfilledwithwaterdidnotshowanyreleasenorfailureafter3weeksStarch-claynanocompositebag(a)RealpictureofbiodegradabilityofneatPLAandPLACN4recoveredfromcompostwithtime.Initialshapeofthecrystallizedsampleswas3*10*0.1cm3.SuprakasSinhaRay,etal,NanoLetters,2002,2(10),1093-1096biodegradability可降解性提高(a)Realpictureofbiodegradab(b)Timedependenceofresidualweight,Rw(%)andchangeofmatrixMwofneatPLAandPLACN4.SuprakasSinhaRay,etal,NanoLetters,2002,2(10),1093-1096殘留率由60%幾乎下降為0(b)TimedependenceofresiduaDegreeofbiodegradation(i.e.,CO2evolution)ofneatPLAandPLACN4undercompostat58±2℃.(b)TimedependencechangeofmatrixMwofneatPLAandPLACN4undercompostat58±2℃SuprakasSinhaRay,etal,Chem.Mater.2003,15,1456-1465降解速度加快Degreeofbiodegradation(i.e.Montmorillonitecontentdependenceofthermalexpansioncoefficientofpolyimide-clayhybridat:(a)150℃,(b)200℃,(c)250℃,and(d)295℃.KAZUHISAYANO,etal,JournalofPolymerScience:PartAPolymerChemistry,Vol.31,2493-2498(1993)thermalexpansioncoefficient熱膨脹系數(shù)降低Montmorillonitecontentdepend制備聚合物/層狀硅酸鹽納米復合材料遇到的主要問題無機相分布不規(guī)則；無機相形態(tài)難控制；存在界面問題；分散方法需改進。制備聚合物/層狀硅酸鹽納米復合材料遇到的主要問題無機相分布不InfluencefactorsofpolymerintercalationOriginalpropertiesofsilicatePolymerarchitectureinteractionbetweensurfaceandpolymera.Organicallymodifiedlayeredsilicatessurfaceb.AddingafractionoffunctionalizedpolymersProcesscondition第五節(jié)影響聚合物插層效果的主要因素InfluencefactorsofpolymeriWAXDpatternsoforganicallymodifiedclay:(a)smectiteclaymodifiedwithC8,C12,andC16phosphoniumsalt;(b)smectite,MMT,andmicaclaymodifiedwithC16phosphoniumsaltOriginalpropertiesofsilicateWAXDpatternsoforganicallymComparisonofPCandNylon6NanocompositesWideAngleX-RayScattering(HE)2M1T1T(C18)N+CH3CH2CH2OHCH2CH2OHPolymerarchitecturePA6可以充分剝離層狀結(jié)構(gòu),PC不能ComparisonofPCandNylon6NSchematicillustrationofOMLSdispersionprocessinPP-g-MAmatrixinteractionbetweensurfaceandpolymer聚烯烴接枝上極性基團有助于MMT的解離和插層SchematicillustrationofOMLS

LLDPE

M2(HT)2

LLDPE-g-MA接枝上極性基團后MMT在LLDPE中得以充分解離和分散LLDPEEffectofmaleationonstructureofnanocomposite隨接枝率上升,LLDPE插層后的MMT層間結(jié)構(gòu)趨于消失Effectofmaleationonstructu8μmParticle>3000PlateletsChemistryChemistry/ProcessingProcessingDispersionDispersionTactoids/IntercalantsPartialDispersionTactoids/IntercalantsTactoids/IntercalantsTactoids/IntercalantsPaul分散機理ProcessconditionThreecasesinvolvingtheinterplayduringmeltprocessing8μmParticleChemistryPlateletExfoliationMechanismDuringExtrusionPlateletspeelapartbycombineddiffusion/shearprocessShearOrganoclayparticle(~8m)StacksofsilicateplateletsortactoidsShearingofplateletstacksleadstosmallertactoidsShearStress=ShearDiffusionPlateletExfoliationMechanism

Thekeyoftheformationofnanocompositesis:

thereareenoughinteractionbetweenpolymerandlayersilicatessothattheintercalationandexfoliationcanoccurThekeyoftheformationofCoRotating,LowShear15A/PA6SingleScrewCoRotating,MediumShear剪切場對改性clay分散狀態(tài)的影響CoRotating,LowShear15A/PA6NetworkiniPP/claynanocompositesRheologybehaviorNetworkiniPP/claynanocomposSelectedApplicationsAutomotive(EnhancedModulusandDimensionalStability，HigherHeat-DistortionTemperature，ImprovedScratchandMarResistance)Packaging(PermeationBarrier)FlameRetardancy聚合物/層狀硅酸鹽復合材料的應(yīng)用SelectedApplicationsAutomotiv上世紀80年代，日本豐田中央研究院在最早用于豐田車內(nèi)部件的尼龍6納米復合材料，但是由于價格的原因很快被放棄了。通用汽車公司在其2002年的兩款新車GMCSafari和ChevroletAstro上采用了一種全新的材料—聚丙烯/膨潤土納米復合材料制備的腳踏板（step-assist），這項技術(shù)創(chuàng)新獲得了國際塑料工程師協(xié)會的大獎，對整個高分子納米復合材料的發(fā)展有里程碑的意義。汽車的應(yīng)用上世紀80年代，日本豐田中央研究院在最早用于豐田車內(nèi)部件的尼ToyotoNylon6-ClayHybrid(NCH)1986InsitupolymerizationprocessInjectionmoldedtimingbeltcoverseeM.Kawasumi,J.Polym.Sci.PartA:Polym.Chem.,42,819(2004)ToyotoNylon6-ClayHybrid(NC1stCommercialLaunch

StepAssistonAstroandSafariVan1stCommercialLaunch

StepAssHUMMERH2SUT:MostRecentNanocompositeApplicationHUMMERH2SUT:MostRecentNa包裝材料

Honeywell公司：含2%和4%納米膨潤土的尼龍6，作為中等阻隔材料對氧氣敏感產(chǎn)品的包裝，其對氧氣的阻隔性與尼龍6相比分別提高了3倍和6倍，同時還增加了膜的剛度、耐熱性和透明度。Honeywell公司：以納米膨潤土作為透過層，以特定尼龍作為氧氣捕捉活性層的納米復合材料。納米膨潤土的作用是保護氧氣捕捉層以免其過早耗盡。用于三層結(jié)構(gòu)的PET瓶。Nanocor公司與三菱瓦斯：納米膨潤土加入到無定形的MDX6尼龍中，納米復合材料的的氧氣阻隔性為PET的100倍，作為三層PET瓶中的中間層，據(jù)稱作為啤酒瓶的貨架期可達到200天。Bayer公司：Nanocor的納米膨潤土用于尼龍6的澆注膜，用于多層包裝、保護膜和藥品的包裝等。Ube公司：納米膨潤土加入到尼龍6/66的共混物中，作為汽車的燃油系統(tǒng)，2%納米膨潤土含量的尼龍6與未改性的尼龍6相比，對甲醇的阻隔性提高了5倍。包裝材料Honeywell公司：含2%和4%納米膨潤土的尼InsertthatfitsintotheshoeNanocompositePouchfilledwithHeliumConverseBasketballShoe

PouchbyTritonSystemsInc.InsertthatfitsintotheshoeWilson

DoubleCoreTennisBall

CoatingAirDefensebyInMatTMButylRubberNanocompositeCoreWilsonDoubleCoreTennisBal部分高分子納米復合材料的提供廠商部分高分子納米復合材料的提供廠商聚合物納米復合材料聚合物納米復合材料復合體系組合分散相的尺度大小>1000nm(>1μm)100~1000nm(0.1~1μm)1~100nm(0.001~0.1μm,10~1000?)0.5~10nm(5~100?)（1）聚合物/低分子物低分子作增容劑低分子流變改性劑外部熱塑性聚合物（2）聚合物/聚合物宏觀相分離型聚合物摻混物微觀相分離型聚合物合金（1）分子復合物；（2）完全相容型聚合物合金（3）聚合物/填充物聚合物/填充物復合體系聚合物/填充物復合體系聚合物/超細粒子填充復合體系聚合物納米復合體系聚合物復合體系的分類第一節(jié)概述復合體系分散相的尺度大小>1000nm100~1000nm1納米概念的形成早期，石墨、炭黑中的顆粒1959年，美國物理學家RichardFeynman提出“whatwouldhappenifwecouldarrangetheatomsonebyonethewaywewantthem?”20世紀70年代康乃爾大學C.G.Granqvist&R.A.Buhrman小組氣相沉積制備納米20世紀80年代，原西德Gleiter首次制備金屬納米，提出納米材料及其應(yīng)用1981年，IBM發(fā)明AFM和STM，推動納米技術(shù)發(fā)展20世紀80年代末期，日本豐田研究中心制得PA6/粘土納米復合材料納米概念的形成早期，石墨、炭黑中的顆粒WhatnanocompositesareAnanocompositeisdefinedasacompositematerialwhereatleastoneofthedimensionsofoneofitsconstituentsisonthenanometresizescale.1.納米復合材料(nanocomposite)定義:WhatnanocompositesareAnanoc納米復合材料非聚合物納米復合材料金屬/金屬金屬/陶瓷陶瓷/陶瓷聚合物納米復合材料有機/無機納米復合材料聚合物/聚合物納米復合材料聚合物基無機物基分子復合原位復合微纖/基體Classificationofnanocomposite

納米復合材料非聚合物金屬/金屬聚合物有機/無機聚合物/聚合物Polymer/inorganicnanocomposites

Polymernanocompositesaregenerallydefinedasthecombinationofapolymermatrixresinandinorganicparticles(particles,layersorfibres)whichhaveatleastonedimension(i.e.length,width,orthickness)inthenanometersizerange.

2.聚合物/無機納米復合材料定義Polymer/inorganicnanocomposi

納米纖維(碳納米管、纖維素晶須、凹凸棒土)

層狀無機物(layeredsilicates)納米粒子(CaCO3、SiO2、TiO2、ZnO、Al2O3、Cr2O3)Schematicofnanoscalefillers第二節(jié).制備聚合物納米復合材料的無機物的種類納米纖維(碳納米管、纖維素晶須、凹凸棒土)Schema碳納米管碳納米管是由多個碳原子六方點陣的同軸圓柱面套構(gòu)而成的空心小管，其中石墨層可以因卷曲方式不同而具有手性。碳納米管的直徑一般為幾納米至幾十納米，長度為幾至幾十微米。碳納米管可以因直徑或手性的不同而呈現(xiàn)很好的金屬導電性或半導體性。

(Iijima1991)多壁碳納米管單壁碳納米管碳納米管碳納米管是由多個碳原子六方點陣的同軸圓Derivedfromexpandable2:1layeredsmectitefamilyofclaysIsomorphoussubstitutionofatomscreatesachargeimbalanceSodiumMontmorillonitePlateletStructureNa+SiOxideAl/Mg/Fe–Oxide/HydroxideSiOxideNa+

~50nm-300nm~1nmDerivedfromexpandable2:1lLayeredsilicates

AdvantagesoverconventionalfillersExpandablestructuresIndividualsilicatelayershaveatleastonedimensioninnanoscopicsizerangeLayershavehighaspectratios(length/thickness),extremelylargesurfaceareas,andhighmoduliLargepropertybenefitsachievableatverylowfillerlevelsascomparedtoconventionalreinforcingadditivesWeightsaving(2.5wt%nanoclayvs.25wt%talc)Betterprocessibility(fastercyclingtimesandquickerfill)Don’tneednewlinesoftools~1nmLayeredsilicates

AdvantagesCationicExchangeofSodiumMontmorillonite+SodiumMMT*Swollen“Organoclay”R1*R2R3CH3N+Cl-+NaClCationicSurfactant(e.g.,alkyl-ammoniumchloride)=Na=Alkylammonium蒙脫土族礦物具有離子交換性、吸水性、膨脹性、觸變性、黏結(jié)性、吸附性等特性。CationicExchangeofSodium插層劑的作用利用離子交換的原理進入蒙脫土片層之間；擴張片層間距；改善層間的微環(huán)境；使蒙脫土的內(nèi)外表面由親水性轉(zhuǎn)化為疏水性；增強蒙脫土片層與聚合物分子鏈之間的親和性；降低硅酸鹽材料的表面能。常用的插層劑有烷基銨鹽、季銨鹽、吡啶類衍生物和其他陽離子型表面活性劑插層劑的作用利用離子交換的原理進入蒙脫土片層之間；常用的插層第三節(jié).聚合物納米復合材料主要制備方法

溶膠-凝膠法(Sol-Gel):烷氧基金屬或金屬鹽等前驅(qū)物（水溶性鹽或油溶性醇鹽）溶于水或有機溶劑中形成均質(zhì)溶液，溶質(zhì)發(fā)生水解反應(yīng)生成納米級粒子并形成溶膠，溶膠經(jīng)蒸發(fā)干燥轉(zhuǎn)變?yōu)槟z。原位聚合法(in-situpolymerization):分散有納米粒子的單體聚合后形成復合體系共混法:聚合物與納米粒子共混插層法:將單體或聚合物插入層狀無機物層間形成納米復合結(jié)構(gòu)第三節(jié).聚合物納米復合材料主要制備方法溶膠-凝膠法(SolPreparationMethods原位插層(In-situintercalationpolymerization)

溶液插層(Polymerintercalationfromsolution)

熔體插層(Polymermeltintercalation)Polymer/Layeredsilicatenanpcomposites聚合物/層狀硅酸鹽納米復合材料制備方法(插層法)PreparationMethods原位插層(In-sitMorphologyoflayeredsilicateMorphologyoflayeredsilicate1.InsituPolymerization1.InsituPolymerization2.Polymerintercalationfromsolution2.Polymerintercalationfroms3.meltintercalation3.meltintercalationMechanicallyblendpolymer–organoclaymixturesabovethepolymer’sTm(i.e.,highsheartwinscrewextrusion)NanocompositeFormationTechnique

-MeltProcessing–(常規(guī)做法)hpMechanicallyblendpolymer–orgNaokiHasegawa,etal,Polymer44(2003)2933–2937anovelcompoundingprocessusingNa–montmorillonitewaterslurryforpreparingnovelnylon6/Na–montmorillonitenanocompositesSchematicfiguredepictingthecompoundingprocessforpreparingtheNCH-CSusingtheclayslurryNewmethod(加入層狀無機材料的懸浮液)NaokiHasegawa,etal,PolymerNaokiHasegawa,etal,Polymer44(2003)2933–2937SchematicfiguresdepictingdispersionoftheNa–montmorillonitesilicatelayersoftheslurryintonylon6duringcompoundingNaokiHasegawa,etal,PolymerKineticsofpolymermeltintercalationTwostepsfornanocompositeformation:Polymertransportedfromtheagglomerate-polymermeltinterfacetotheprimaryparticlesPolymermeltpenetratetotheedgesofthecrystallites

ThefirststepislimitingstepforpolymernanocompositesformationKineticsofpolymermeltinterThermodynamicanalysis△F=F(h)-F(h0)=△E-T△S

△F＜0indicatelayerseparationisfavorable△F＞0impliestheinitialunintercalatedstateisfavorable△S≈△Schain+△SpolymerThermodynamicanalysis第四節(jié)層狀納米復合材料結(jié)構(gòu)與性能1.結(jié)構(gòu)LayeredNanocompositestructure第四節(jié)層狀納米復合材料結(jié)構(gòu)與性能Schematicillustrationoftwodifferenttypesofthermodynamicallyachievablepolymer/layeredsilicatenanocomposites.SchematicillustrationoftwoSchematicdepictingtheXRDpatternsforvarioustypesofstructures不同插層結(jié)構(gòu)的表征(X射線衍射法)層狀有序結(jié)構(gòu)完全消失完全未解離插層結(jié)構(gòu)(層間距明顯增大)插層結(jié)構(gòu)均一插層結(jié)構(gòu)無序SchematicdepictingtheXRDpaX-raydiffractionpatternofPEO/Na+-MMThybridheatedto80℃for0,2,and6hVaiaRA,etal,Macromolecules1995,28:8080MMT片層結(jié)構(gòu)衍射峰X-raydiffractionpatternofPTemporalseriesofX-raydiffractionpatternsforaPS30/F18pelletannealedinsituat160℃invacuumVaiaRA,etal,AdvMater1995,7,154–156TemporalseriesofX-raydiffr

2.性能PropertiesofpolymerlayeredsilicatenanocompositesEfficientreinforcementwithminimallossofductilityandimpactstrengthIncreasethermalstabilityIncreaseflameretardant

ImprovedgasbarrierpropertiesImprovedionicconductivityReducedthermalexpansioncoefficientAlteredelectronicandopticalproperties2.性能PropertiesofpolymerlayPropertiesofNylon-6layeredsilicatenanocompositesPropertyNanocompositesNylon-6TensileModulus(GPa)TensileStrength(MPa)HeatDistortionTemp(℃)ImpactStrength(KJ/m2)WaterAdsorption(%)CoefficientThermalExpansion(x,y)2.11071602.80.516.3×10-51.169652.30.8713×10-5最有價值的性能變化PropertiesofNylon-6layeredComparisonoftheYoung’smodulusofclay/nylon-6nanocompositesandglassfiberreinforcednylon-6compositeswithlowfillerloadingFenggeGao,materialstoday,2004,50-55Inthelowfillerloadingrange,clay/polymernanocompositeshavethepotentialtoreplacetraditionalfiberreinforcedcomposites.ComparisonoftheYoung’smoduModulusincreasebylayeredsilicatereinforcementofPA66L.A.GOETTLER,PolymerReviews,47:291–317,2007普通層狀填料玻纖增強Modulusincreasebylayeredsi(a)Organoclay(OMSFM)(wt%)dependenceofHDTofneatPLAandvariousPLACNs.(b)LoaddependenceofHDTofneatPLAandPLACN7ThermalpropertiesSuprakasSinhaRay,etal,Chem.Mater.2003,15,1456-1465(a)Organoclay(OMSFM)(wt%)TGAanalysisofPDMS(solidline).andPDMSnanocomposite(dashedline)(massfraction10%mica-type-silicate,MTS).Lineswereaddedtoindicate50%massloss.Burnside,S.D.,Giannelis,E.P.,Chem.Mater.1995.

7,1597TGAanalysisofPDMS(solidlinComparisonoftheHeatReleaseRateHRR.plotfornylon-6,nylon-6silicate-nanocomposite(massfraction5%)at35kW/m2heatflux,showinga63%reductioninHRRforthenanocomposite.flameretardantJeffreyW.Gilman,AppliedClayScience,15,1999.31–49放熱速率顯著下降ComparisonoftheHeatReleasePP及其納米復合材料的熱釋放速率對比（熱通量=35kW/m2)PP及其納米復合材料的熱釋放速率對比Flammabilityperformancefornylon-6nanocompositesnanocompositeworkswithotherflameretardantsinasynergisticorcooperativemannertolowerthepolymerflammability(heatreleaserate)ComparisonbetweennanocompositesandconventionalflameretardantsAlexanderB.Morgan,Polym.Adv.Technol.2006;17:206–217工業(yè)上評價材料阻燃性能的檢測標準FlammabilityperformancefornBeyer,G.,2002NanocompositePowerCableKabelwerkEupenBeyer,G.,2002NanocompositeSelectedvideoimagesat100,200,and400sinnitrogenat50kW/m2.TakashiKashiwagi,Polymer45(2004)881–891Mechanism:Thesilicate-richcharactsasanexcellentinsulatorandmasstransportbarrier,therebyreducingtheheatreleaseratemandslowingdowntheescapeofvolatileproductsreleasedasthepolymerdecomposes.阻燃機理:硅酸鹽作為隔絕火焰,熱量和物質(zhì)的材料減緩了聚合物分解時揮發(fā)份的釋出Selectedvideoimagesat100,Proposedmodelforthetorturouszigzagdiffusionpathinanexfoliatedpolymer-claynanocompositewhenusedasagasbarriergasbarrierpropertiesProposedmodelforthetorturoMontmorillonitecontentdependenceofpermeabilitycoefficientofwatervaporinpolyimide-clayhybrid.MontmorillonitecontentdependenceofpermeabilitycoefficientofO2inpolyimide-clayhybridKAZUHISAYANO,etal,JournalofPolymerScience:PartAPolymerChemistry,Vol.31,2493-2498(1993)應(yīng)用價值:食品保鮮MontmorillonitecontentdependStarch-claynanocompositebagmadebyfilmblowingtechnology.Thisbaghasbeenstoredfilledwithwaterdidnotshowanyreleasenorfailureafter3weeksStarch-claynanocompositebag(a)RealpictureofbiodegradabilityofneatPLAandPLACN4recoveredfromcompostwithtime.Initialshapeofthecrystallizedsampleswas3*10*0.1cm3.SuprakasSinhaRay,etal,NanoLetters,2002,2(10),1093-1096biodegradability可降解性提高(a)Realpictureofbiodegradab(b)Timedependenceofresidualweight,Rw(%)andchangeofmatrixMwofneatPLAandPLACN4.SuprakasSinhaRay,etal,NanoLetters,2002,2(10),1093-1096殘留率由60%幾乎下降為0(b)TimedependenceofresiduaDegreeofbiodegradation(i.e.,CO2evolution)ofneatPLAandPLACN4undercompostat58±2℃.(b)TimedependencechangeofmatrixMwofneatPLAandPLACN4undercompostat58±2℃SuprakasSinhaRay,etal,Chem.Mater.2003,15,1456-1465降解速度加快Degreeofbiodegradation(i.e.Montmorillonitecontentdependenceofthermalexpansioncoefficientofpolyimide-clayhybridat:(a)150℃,(b)200℃,(c)250℃,and(d)295℃.KAZUHISAYANO,etal,JournalofPolymerScience:PartAPolymerChemistry,Vol.31,2493-2498(1993)thermalexpansioncoefficient熱膨脹系數(shù)降低Montmorillonitecontentdepend制備聚合物/層狀硅酸鹽納米復合材料遇到的主要問題無機相分布不規(guī)則；無機相形態(tài)難控制；存在界面問題；分散方法需改進。制備聚合物/層狀硅酸鹽納米復合材料遇到的主要問題無機相分布不InfluencefactorsofpolymerintercalationOriginalpropertiesofsilicatePolymerarchitectureinteractionbetweensurfaceandpolymera.Organicallymodifiedlayeredsilicatessurfaceb.AddingafractionoffunctionalizedpolymersProcesscondition第五節(jié)影響聚合物插層效果的主要因素InfluencefactorsofpolymeriWAXDpatternsoforganicallymodifiedclay:(a)smectiteclaymodifiedwithC8,C12,andC16phosphoniumsalt;(b)smectite,MMT,andmicaclaymodifiedwithC16phosphoniumsaltOriginalpropertiesofsilicateWAXDpatternsoforganicallymComparisonofPCandNylon6NanocompositesWideAngleX-RayScattering(HE)2M1T1T(C18)N+CH3CH2CH2OHCH2CH2OHPolymerarchitecturePA6可以充分剝離層狀結(jié)構(gòu),PC不能ComparisonofPCandNylon6NSchematicillustrationofOMLSdispersionprocessinPP-g-MAmatrixinteractionbetweensurfaceandpolymer聚烯烴接枝上極性基團有助于MMT的解離和插層SchematicillustrationofOMLS