聚合物混改性原理纳米复合材料课件

聚合物共混改性原理

————聚合物纳米复合材料张琴

聚合物共混改性原理

————聚合物纳米复合材料张琴1复合体系组合分散相的尺度大小>1000nm(>1μm)100~1000nm(0.1~1μm)1~100nm(0.001~0.1μm,10~1000Å)0.5~10nm(5~100Å)（1）聚合物/低分子物低分子作增容剂低分子流变改性剂外部热塑性聚合物（2）聚合物/聚合物宏观相分离型聚合物掺混物微观相分离型聚合物合金（1）分子复合物；（2）完全相容型聚合物合金（3）聚合物/填充物聚合物/填充物复合体系聚合物/填充物复合体系聚合物/超细粒子填充复合体系聚合物纳米复合体系聚合物复合体系的分类复合体系分散相的尺度大小>1000nm100~1000nm12纳米概念的形成早期，石墨、炭黑中的颗粒1959年，美国物理学家RichardFeynman提出“whatwouldhappenifwecouldarrangetheatomsonebyonethewaywewantthem?”20世纪70年代康乃尔大学C.G.Granqvist&R.A.Buhrman小组气相沉积制备纳米20世纪80年代，原西德Gleiter首次制备金属纳米，提出纳米材料及其应用1981年，IBM发明AFM和STM，推动纳米技术发展20世纪80年代末期，日本丰田研究中心制得PA6/粘土纳米复合材料纳米概念的形成早期，石墨、炭黑中的颗粒3WhatnanocompositesareNanocompositesaremadebymixingtwoormorephase,suchasparticles,layersorfibres,whereatleastoneofthephasesisinthenanometresizerange.Becausethebuildingblocksmakingupthenanocompositesarethereforesoclosetothemolecularscale,confinementandquantumeffectsresultfromthewaythattheblocksinteract.Nanocompositesshowpropertiesnotfoundinbulkmaterials,differentiatingthemfromtypicalcompositesorfilled-polymersystems.WhatnanocompositesareNanocom4纳米复合材料非聚合物纳米复合材料金属/金属金属/陶瓷陶瓷/陶瓷聚合物纳米复合材料有机/无机纳米复合材料聚合物/聚合物纳米复合材料聚合物基无机物基分子复合原位复合微纤/基体Classificationofnanocomposite

纳米复合材料非聚合物金属/金属聚合物有机/无机聚合物/聚合物5Polymer/inorganicnanocomposites

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

Polymer/inorganicnanocomposi6制备聚合物纳米复合材料的无机物的种类

纳米粒子(CaCO3、SiO2、TiO2、ZnO、Al2O3、Cr2O3)纳米纤维(碳纳米管、纤维素晶须、凹凸棒土)层状无机物

制备聚合物纳米复合材料的无机物的种类纳米粒子(CaCO37LayeredhostcrystalssusceptibletointercalationbyapolymerLayeredhostcrystalssuscepti8蒙脱土的化学通式：Nax(H2O)4{(AL2~xMgx)[Si4O10](OH)2}

分类：钠基蒙脱土（碱性土）钙基蒙脱土（碱土性土）天然漂白土（酸性土）蒙脱土的化学通式：分类：9蒙脱土的改性方法人工钠化改型（悬浮液法、堆场钠化法、挤压法）酸活化方法（干法活化工艺、湿法活化工艺）蒙脱土的改性方法人工钠化改型（悬浮液法、堆场钠化法、挤压法）10湿法生产工艺：包装原土破碎制浆提纯改型活化有机覆盖过滤干燥粉碎覆盖剂干法生产工艺：包装原土制浆提纯1提纯2改型活化精细钠土加热混合干燥粉碎覆盖剂湿法生产工艺：包装原土破碎制浆提纯改型活化有机覆盖过滤干燥粉11Structureof2:1layeredsilicates蒙脱土的结构特征---天然的纳米结构Structureof2:1layeredsilic12Cation-exchangereactionbetweenthesilicateandthealkylammoniumsalt蒙脱土族矿物具有离子交换性、吸水性、膨胀性、触变性、黏结性、吸附性等特性Cation-exchangereactionbetwe13插层剂的作用利用离子交换的原理进入蒙脱土片层之间；扩张片层间距；改善层间的微环境；使蒙脱土的内外表面由亲水性转化为疏水性；增强蒙脱土片层与聚合物分子链之间的亲和性；降低硅酸盐材料的表面能。常用的插层剂有烷基铵盐、季铵盐、吡啶类衍生物和其他阳离子型表面活性剂插层剂的作用利用离子交换的原理进入蒙脱土片层之间；常用的插层14聚合物混改性原理纳米复合材料课件15聚合物/层状硅酸盐纳米复合材料特点需要填料体积分数少；具有优良的热稳定性及尺寸稳定性；性价比高。聚合物/层状硅酸盐纳米复合材料特点需要填料体积分数少；16PolymerlayeredNanocompositespreparationIn-situintercalationpolymerization

tointercalatethemonomerandthentakeadvantageofthehost’soxidisingpropertiestoinducepolymerizationPolymerintercalationfromsolution

Polymermeltintercalation

tomixthepolymerandlayeredsilicatetogetherandthenheatthemixtureabovetheglasstransitiontemperature(softeningpoint)ofthepolymerExfoliation-adsorptionTemplatesynthesisPolymerlayeredNanocomposites17InsituPolymerizationInsituPolymerization18Schematicrepresentationofin-situpolymerizationSchematicrepresentationofin19聚合物大分子溶液插层工艺示意图聚合物大分子溶液插层工艺示意图20SchematicrepresentationofmeltintercalationSchematicrepresentationofme21聚合物混改性原理纳米复合材料课件22制备方法的改进利用共聚物制纳米复合材料（PS、PMMA）；利用聚合物催化剂制纳米复合材料（PS、PET）；利用相容剂制纳米复合材料（PP）；利用环状低聚物的开环聚合制纳米复合材料（PC）；硬质环氧树脂纳米复合材料的制备（硬质环氧树脂）。制备方法的改进利用共聚物制纳米复合材料（PS、PMMA）；23NaokiHasegawa,etal,Polymer44(2003)2933–2937anovelcompoundingprocessusingNa–montmorillonitewaterslurryforpreparingnovelnylon6/Na–montmorillonitenanocompositesNaokiHasegawa,etal,Polymer24NaokiHasegawa,etal,Polymer44(2003)2933–2937NaokiHasegawa,etal,Polymer25LayeredNanocompositestructureLayeredNanocompositestructur26聚合物混改性原理纳米复合材料课件27PLS纳米复合材料微观结构的分类表PLS纳米复合材料微观结构的分类表28SchematicdepictingtheXRDpatternsforvarioustypesofstructuresSchematicdepictingtheXRDpa29聚合物混改性原理纳米复合材料课件30聚合物混改性原理纳米复合材料课件31ThenewpropertiesofnanocompositesEfficientreinforcementwithminimallossofductilityandimpactstrengthIncreasethermalstabilityIncreaseflameretardantImprovedgasbarrierpropertiesImprovedionicconductivityReducedthermalexpansioncoefficientAlteredelectronicandopticalpropertiesThenewpropertiesofnanocomp32PropertiesofNylon-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

PropertiesofNylon-6layered33聚合物混改性原理纳米复合材料课件34聚合物混改性原理纳米复合材料课件35Organoclay(wt%)dependenceofHDTofneatPLAandvariousPLACNs.(b)LoaddependenceofHDTofneatPLAandPLACN7Organoclay(wt%)dependenceof36TGAcurvesforpolystyrene,PSandthenanocompositesTGAcurvesforpolystyrene,PS37Proposedmodelforthetorturouszigzagdiffusionpathinanexfoliatedpolymer–clay

nanocompositewhenusedasagasbarrierProposedmodelforthetorturo38ComparisonofcombustionofNylon6,6andNylon6,6nanocompositewithclayfractionof5wt.-%(Cloisite15A)atexternalfluxof35Kw/m2ComparisonofcombustionofNy39PP及其纳米复合材料的热释放速率对比（热通量=35kW/m2)PP及其纳米复合材料的热释放速率对比40RealpictureofbiodegradabilityofneatPLAandPLACN4recoveredfromcompostwithtime.Initialshapeofthecrystallizedsampleswas3*10*0.1cm3.Realpictureofbiodegradabili41Degreeofbiodegradation(i.e.CO2evolution),and(b)time-dependentchangeofmatrixMwofneatPLAandPLACN4(MEEclay=4wt%)undercompostat(58+

2)ºCDegreeofbiodegradation(i.e.42聚合物混改性原理纳米复合材料课件43聚合物纳米复合材料的问题无机相分布不规则；无机相形态难控制；存在界面问题；分散方法需改进。聚合物纳米复合材料的问题无机相分布不规则；44MorphologyoflayeredsilicateMorphologyoflayeredsilicate45KineticsofpolymermeltintercalationTwostepsfornanocompositeformation:Polymertransportedfromtheagglomerate-polymermeltinterfacetotheprimaryparticlesPolymermeltpenetratetotheedgesofthecrystallites

ThefirststepislimitingstepforpolymernanocompositesformationKineticsofpolymermeltinter46Thermodynamicanalysis△F=F(h)-F(h0)=△E-T△S

△F＜0indicatelayerseparationisfavorable△F＞0impliestheinitialunintercalatedstateisfavorable△S≈△Schain+△SpolymerThermodynamicanalysis47InfluencefactorsofpolymerintercalationOriginalpropertiesofsilicatePolymerarchitectureinteractionbetweensurfaceandpolymera.Organicallymodifiedlayeredsilicatessurfaceb.AddingafractionoffunctionalizedpolymersProcessconditionInfluencefactorsofpolymeri48WAXDpatternsoforganicallymodifiedclay:(a)smectiteclaymodifiedwithC8,C12,andC16phosphoniumsalt;(b)smectite,MMT,andmicaclaymodifiedwithC16phosphoniumsaltWAXDpatternsoforganicallym49BrightfieldTEMimagesofmeltcompoundednanocompositescontaining,3wt%MMTbasedon(a)HMW,(b)MMW,and(c)LMWN6BrightfieldTEMimagesofmel50SchematicillustrationofOMLSdispersionprocessinPP-g-MAmatrixSchematicillustrationofOMLS51ThreecasesinvolvingtheinterplayduringmeltprocessingProcessconditionH.R.Dennisetal./Polymer42(2001)9513–9522Threecasesinvolvingtheinte52IllustratesschematicallyhowplateletspeelapartundertheactionofshearH.R.Dennisetal./Polymer42(2001)9513–9522Illustratesschematicallyhow53Thekeyoftheformationofnanocompositesis:

thereareenoughinteractionbetweenpolymerandlayersilicatessothattheintercalationandexfoliationcanoccurThekeyoftheformationof54X-raydiffractionscansfor(a)nylon6;(b)nylon6/untreatedmont.(c)Nylon6/treatedmont.(10wt%mont.)CrystallizationbehaviorX-raydiffractionscansfor(a55聚合物混改性原理纳米复合材料课件56SteadyshearviscosityasafunctionofshearrateforaseriesofhybridsofPDMS/MMTRheologybehaviordelaminatedintercalatedSteadyshearviscosityasafu57TemperaturedependenceofG′;G″andtandforN6matrixandvariousN6CNs.TemperaturedependenceofG′;58P.J.Yoonetal./Polymer43(2002)6727–6741P.J.Yoonetal./59纳米复合材料的表征方法X-射线衍射法：测定层状化合物或层状硅酸盐材料的层间距激光光散射方法：测定超细颗粒的（或纳米粒子）的分布曲线TEM方法AFM方法（AtomicForceMicrostropy)SEM与图像分析仪纳米复合材料的表征方法X-射线衍射法：测定层状化合物或层状硅60利用X射线衍射测量蒙脱土层间距的原理图Bragg方程：

λ=2dsinθ利用X射线衍射测量蒙脱土层间距的原理图Bragg方程：61聚合物/无机纳米复合材料的应用

——聚酰胺/层状硅酸盐纳米复合材料聚合物/无机纳米复合材料的应用

—62有机粘土层间距与ω-氨基酸碳链长度的关系1：ω-氨基酸插层粘土2：ε-己内酰胺插层有机粘土（25℃）3：ε-己内酰胺插层有机粘土（100℃）

有机粘土的制备有机粘土层间距与ω-氨基酸碳链长度的关系有机粘土的制备63Alkylchainaggregationinlayeredsilicates:(a)lateralmonolayer;(b)lateralbilayer;(c)paraffin-typemonolayerand(d)paraffin-typebilayer

Alkylchainaggregationinlay64原位聚合制备PA6/粘土纳米复合材料ε-己内酰胺水解聚合反应示意图图中Pn表示生成的聚合物分子链的聚合度

原位聚合制备PA6/粘土纳米复合材料ε-己内酰胺水解聚合反应65合成粘土及PA6/粘土纳米复合材料的X射线衍射图谱

合成粘土及PA6/粘土纳米复合材料的X射线衍射图谱66PA6/粘土纳米复合材料的TEM照片

PA6/粘土纳米复合材料的TEM照片67聚合物混改性原理纳米复合材料课件68普通PA6与PA6/合成粘土的WAXD谱线

普通PA6与PA6/合成粘土的WAXD谱线69普通PA6与PA6/合成粘土的DSC曲线普通PA6与PA6/合成粘土的DSC曲线70普通PA6与n-PA6（4%）的流变曲线普通PA6与n-PA6（4%）的流变曲线71普通PA6与n-PA6的性能对比普通PA6与n-PA6的性能对比72不同填充材料填充PA6时复合材料的弯曲模量对比不同填充材料填充PA6时复合材料的弯曲模量对比73

PA6与n-PA6材料薄膜对水、氧气的阻隔性能比较（1atm=101325Pa）PA6与n-PA6材料薄膜对水、氧气的阻隔性能比较（1at74应用应用75熔融插层制备PA6/层状硅酸盐纳米复合材料

无机粘土插层剂有机粘土PA6树脂螺杆挤出PLS纳米复合材料聚合物熔体插层制备PA6/粘土纳米复合材料的流程图熔融插层制备PA6/层状硅酸盐纳米复合材料无机粘土插层剂有76

PA6及其纳米复合材料的X射线衍射谱线1：PA6；2：PA6/粘土纳米复合材料PA6及其纳米复合材料的X射线衍射谱线77PA6及其纳米复合材料的DSC升温曲线PA6/粘土纳米复合材料的DSC降温曲线PA6及其纳米复合材料的DSC升温曲线PA6/粘土纳米复合材78蒙脱土填充量对PA6结晶度与过冷度的影响蒙脱土填充量对PA6结晶度与过冷度的影响79蒙脱土的含量对n-PA6材料杨氏模量的影响蒙脱土的含量对n-PA6材料弯曲性能的影响蒙脱土的含量对n-PA6材料杨氏模量的影响蒙脱土的含量对n-80蒙脱土的含量对n-PA6材料冲击性能的影响蒙脱土的含量对n-PA6材料热变形温度的影响蒙脱土的含量对n-PA6材料冲击性能的影响蒙脱土的含量对n-81熔体插层PP纳米复合材料熔体插层PP纳米复合材料82TEMphotographofPP/MMTnanocomposite(5wt%MMTcontent)

TEMphotographofPP/MMTnanoc83TEMphotographsofPP/MMTtraditionalcomposites

(a)PP-A(b)PP-B

TEMphotographsofPP/MMTtrad84SEMimagesoffracturedsurfaceatdifferentmixingtime

1min3min5min

8min12min20minSEMimagesoffracturedsurfac85TheWAXDprofileschangeswiththeincreaseofmixingtime（PP:MI=8.0g/10min）

TheWAXDprofileschangeswith86shearshearPrimaryparticlesagglomeratescrystallite

（a）particlesbecamesmallerundershear

Schematicoftheformationofnanocompositeviameltintercalation

（b）polymerchainsdispersion(c)intercalationandexfoliationoccurshearshearPrimaryparticlesagg87Schematicofmorphologicaldevelopmentduring

blending

t=0t=1mint=5mint=20minorSchematicofmorphologicaldev88(a)static(b)dynamic

TEMphotographsofPP/MMTnanocomposites(MMTcontent:5wt%)

(a)static89Sheardirection2d-WAXDdiagramsofpurePPandPP/MMTnanocomposites(5wt%MMT)preparedatTmelt=220℃,f=0.2Hz

(a-1)PP,static(a-2)PP,dynamic(b-1)PP-5,static(b-2)PP-5,dynamic

Sheardirection2d-WAXDdiagram90Halpin-Tsai‘continuum’Equations

Halpin-Tsai‘continuum’Equati91

ThetheoreticaltensilemodulusatdifferentNtogetherwithexperimentaldatainthePP/MMTnanocompositesThetheoreticaltensilemodul92stress-straincurvesofPP/MMTnanocomposites

Engineeringstress-straincurvesstress-straincurvesofPP/MM93truestress-straincurvesstress-straincurvesofPP/MMTnanocompositestruestress-straincurvesstres942d-WAXDdiagramsofPP/MMTnanocomposites(3wt%MMTcontent)measuredforindicatedstrainduringstretchingunderload(a)εt=0(b)εt=0.6(c)εt=1.2

2d-WAXDdiagramsofPP/MMTnan95PPPP-1PP-3PLMmicrographsofthedifferentsamplescrystallizationat130℃

PP96

DifferentcrystallitedataofthesamplesfromSAXSSampledc(nm)L(nm)da(nm)Xc(%)PP3.414.511.123.4PP-12.513.911.418.0PP-32.513.611.118.4PP-52.513.410.918.7PP-A3.114.211.121.8

Differentcrystallitedataof97

tpofthesamplesatdifferentcrystallizationtemperature

tpofthesamplesatdifferen98TheDSCthermogramsofsamples

heatingscancoolingscanTheDSCthermogramsofsamples99ThevariouscrystallizationparametersofthesamplesfromDSCSampleTc(℃)Tm(℃)△Hc(J/g)△Hf(J/g)Xc(%)PP111.3166.1-85.861.729.5PP-1123.0164.5-84.856.527.3PP-3119.3166.8-88.758.528.8PP-5119.7166.4-85.965.533.0

Thevariouscrystallizationpa100ApplicationofPPnanocompositesPPthinfilmforfoodpackageEngineeringPPplasticsforAutobumperandsafetyhelmetApplicationofPPnanocomposit101ApplicationofPETSyntheticfibersFilmsBottlesEngineeringplasticsPETnanocompositesApplicationofPETSyntheticfi102

PETnanocompositesforbeerpackaging1.HugemarketofbeerpackagingTherewere305billion(305,000,000,000)beercontainersallovertheworldin2001.Andtheamountsareincreasingstablyeveryyear.Ithadreachednearly20milliontonbeerinChinain2002whichwilloverruntheU.S.Aandbecomethetoponewhosebeerproductionarrangedintheworld.

Everydevelopedcountryarestudyingplasticbeerbottletooccupythishugemarket.PETnanocompositesforbeerp103Sortsofbeerbottlesecuritytransparencyweightyprice(bottle)GlassbottleNo(easytoexplode)transparentHeavy(670ml,bottleweight540g)cheapMetallictinYesopaqueMiddle(250ml,bottleweight35g)expensivePlasticbottleYestransparentLight(670ml,bottleweight50g)wellsituated2.NecessityofdevelopingplasticbeerbottleSortsofbeerbottlepriceGl1043.StatusofPETbeerpackagingbottle

AdvantageofPETpackaging:

☺lightweight(easytotransport)☺unbreakable(hardtobreakup)

☺transparent(youcanseetheinnerobject)☺nontoxic,odorless☺cheap

ThemarketofPETpackagingmaterialisboomingupinrecentyear.3.StatusofPETbeerpackagin105

limitsofPETforbeerpackaging:

notenoughoxygen-barriercapability(oxygengastransmissionrateofPETisabout2.1x10-5cm3.mm/cm2.hr.atm,asthebeerbottleit’sORTmustlowerthan3.8x10-6cm3.mm/cm2.hr.atm

)

lowheat-resistant(Bassterilizationofbeerat80℃)PETpackagingmaterialsmadeofgeneralPETresincannottocontainoxygen-sensitiveproducts.ButmodifiedPETcanbeusedinbeerbottle,itisthemostimportanttoimprovetheoxygen-barriercapability.limitsofPETforbeerp106PropertiesofPETlayeredsilicatenanocompositesPropertyNanocompositesPETTensileModulus(GPa)TensileStrength(MPa)Flexural