超高分子量聚乙烯凝胶结晶膜中链缠结的Raman研究

/RamanXXX(,230026):,m·400,,,NMR,RamanNMR:;/;;;:O63:A:1004-9843(1999)01-0049-05(UHMWPE)(PE)12,34,5,()5-7,,PE,(1)8-12,PE,,(P2cos)(P4cos)12LAM(LongitudinalAcousticalModes)PE118-10Table1AssignmentsoftheramanbandsforPEFrequency(cm-1)PhaseModeSymmetryFrequency(cm-1)PhaseModeSymmetry1060C(A)(C-C)B2g+B3g1370C(CH2)B2g+B3g1080A(C-C)/1416C(CH2)Ag1130C(A)(C-C)Ag+B1g1440?FermiAg+B1g?1170C(A)(CH2)Ag+B1g2resonance1293C(CH2)B2g+B3g1460?+OverAg+B1g?1303A(CH2)/tones?C:Crystalline;A:Amorphous;:Stretching;:rocking;:twisting;:bending;:wagging1,1416cm-1CH2Ag,CH2(c),1303cm-1(CH21080cm-1(C-C))(a);CH2(1270cm-11320cm-1)ITPE,:c=I1416/0.46IT(1)a=I1303/ITora=I1080/0.79IT(2)Vol.1219993JournalofFunctionalPolymersNo.1Mar.1999XXX(29874031):1998-09-03a+b+c=1(3),abc,0.460.791416cm-11080cm-19UHMWPE/,NMRUHMWPE/11.11.1.1/UHMWPE,M=5.210613,,0.45g/100mLUHMWPE/,100m1.1.2//(6mm25mm),3min,71.1.3/,1290.5,,,1.21.2.1DSCPerkin-ElmerDSC-2C,20/min,(285.9J/g),1.2.2BrukerIFS66,(532nm)(A,200mW,90,4cm-1,15022.1UHMWPE/Fig.1TypicalramanspectraofUHMWPEgel/crystallinefilm(drawn,=5)051UHMWPE10001500cm-1,(1),C-C1130cm-1,1170cm-11060cm-1Table2CrystallinitiesofannealedUHMWPEgel/crystallinefilmsmeasuredbyramanspectrameter,IRandDSCAnn.Temp.(/3min)Xc(%)(IR)#Xc(%)(DSC)c(%)(Raman)b(%)(Raman)a(%)(Raman)untreated87.367.271.417.111.56286.167.572.518.29.310088.2////12090.1////12990.969.773.718.87.513289.971.574.320.15.613589.172.173.819.07.213881.168.470.015.414.614073.9////14560.250.548.615.336.1#:Abstractedfromreference5Table3CrystallinitiesofdrawnUHMWPEgel/crystallinefilmsdeterminedbyDSC,NMR3andramanspectraDrawRatioXc(%)(DSC)c(%)(Raman)(NMR)b(%)(Raman)(NMR)c(%)(Raman)(NMR)167.271.480.517.119.211.50373.674.9/18.2/6.9/576.778.885.315.014.76.207/81.7/12.5/5.8/1079.482.8/11.6/5.6/5083.0/95.5/2.5/03:Thesesampleswerepreparedaccordingtotwo-stagedrawingmethod.1450cm-1,CH2Fermi15,,CH215UHMWPE/,,,1080cm-11293cm-11303cm-11416cm-1,(1)(3)cba,232.2UHMWPE/2.2.1,(),,,5,16,UHMWPE/5,62,c,129132DSCXc(DSC)Xc(IR)cXc(DSC)c,Porter8,(ReactorPowder)UHMWPE;Xc(IR)c,(c+b),IR1894cm-1,CH2(all-transsequences,ttt)17,;DSC,,,MutterUHMWPECH2182ba,:b,135;a,135,14536.1%,15/Raman19Mutter18,,b,,UHMWPE/,,5UHMWPE/12913221,,,,,132135,,,,UHMWPE/2.2.2,UHMWPE8,,203,,cba,,:(b),,;,,Pigeon12,,(5),ba,NMRWAXD6,=5,,,;,(crystallite-bridges)(tie-molecules),=150,,,,,,,UHMWPE/3(),,,(139)130135,,,,RamanNMR,,Flory:45(),,,,,,132135,,,,,,,,,Bruker25:[1]PeterlinA.ColloidPolymSci,1987,265:359..[2]ZhouGuien,ZhuQingren,GaoJianfeng,etal.JChinaUnivSci&Tech,1992,22:425.[3]KanamotoT,TsurutaT,TakedaK,etal.Macromolecules,1988,21:470.[4]SawatariC,OkumuraT,MatsuoM,etal.PolymJ,1986,18:741.[5]ZhuQingren,QiRongrong,HongKunlun,etal.ActaPolymSinica,1994,(5):552.[6]OgitaT,YamamotoR,SuzukiN,etal.Polymer,1991,32:822.[7]OgitaT,KawaharaY,NakamuraR,etal.Macromolecules,1993,26:4646.[8]WangLH,PorterRS,StidhamHD,etal.Macromolecules,1991,24:5535.[9]StroblGR,HagedronW.JPolymSci,PolymPhysEd,1978,16:1181.[10]GlotinM,MandelkernL.ColloidPolymSci,1982,260:182.[11]WangYK,WaldmanDA,SteinRS,etal.ApplPhys,1982,53:6591.[12]PigeonM,PrudhommeRE,PezoletM.Macromolecules,1991,24:5687.[13]LemstraPJ,vanAerleNAJM,BastiaansenCWM.PolymJ,1987,19:85.[14]HendraPJ,JobicHR,MarsdenEP,etal.SpectrochimActa,1977,33A:445.[15]SpellsSJ,HillMJ.Polymer,1991,32:2716.[16]WedgewoodAR,SeferisJC.Pure&ApplChem,1983,55:873.[17]MutterR,StilleW,StribG.JPolymSci,PolymPhysEd,1993,31:99.[18]ZhuQingren,HongKunlun,QiRongrong,etal.ScienceinChina,B,1995,25(4):350.[19]VanAerleNAJM,BraamAWM.JMaterSci,1988,23:4429.[20],,,1993,(4):193.StudyontheInterfaceofUHMWPEGel-FilmsbyRamanSpectroscopyPangWenminQiRongrongFengNingFanChenggaoZhuQingren(StructureResearchLaboratory,UniversityofScience&TechnologyofChina,Hefei230026,China)Abstract:Theeffectofannealinganddrawingonthephasestructureofultrahighmolecularweightpolyethylene(UHMWPE)gel-filmswasstudiedbyRamanspectroscopy.Ourattentionfocusedmainlyonthemassfractionchangesofinterfacephase.TheresultswerealsocomparedwithdataobtainedfromIR,DSCand13C-NMRmethods.Therelationshipbetweenthemassfractionchangesofinterfacephaseandchainentanglementswasdiscussed.Keywords:ramanspectroscopy;UHMWPEgel/crystallinefilms;chainentanglement;drawinganneal2ing35/Raman