PVDFTiO2杂化超滤膜的制备与表征

PVDF/TiO2*姜海凤,马玉新,王铎,高从堦(,266100):钛酸丁酯(TBT)直接加入到铸膜液中,在相转化成膜的同时,膜液中的TBT发生水解反应,从而制备出有机-无机杂化膜实验中制备出不同TiO2含量的PVDF/TiO2杂化膜,研究了添加剂含量对杂化膜的水通量牛血清蛋白(BSA)截留率和接触角的影响,并通过SEMEDS和DSC对膜结构进行表征研究结果显示:杂化膜较未加入TBT的膜的性能有所改善,当TBT加入量为5.7%(质量分数)时,膜的水通量增加了1倍而截留率保持在90%以上;同时TBT对膜结构也有一定影响:杂化膜中海绵状孔减少,指状孔增多;TBT的水解产物部分存留在杂化膜中:PVDF/TiO2;;:TQ028:A:1001-9731(2009)04-0591-041,,-,,,[1]--[2~4][5~7][8,9]TiO2,,,TiO2,,,,-,(TBT),PVDF/TiO222.1(PVDF)1300,KUREHA;(PAN),;N,N-(DMAc),,;N-(NMP),,;TBT,,;,,;(BSA),Mw=67000,;,,UF,;DHG-9070A,;CH-1-ST,;UV-2450,;,;HH-W,;AL204,-();SPS202F,();RCTbasic,IKA;JEM-6700F,;STA409PC,;DSA100,KRUSS2.2NMP,TBT,L-S,PVDFPANTBTDMAc,,,40e2.32.3.1,4cm,UF,0.15MPa30min,0.1MPaJ=VS#t(1)J0.1MPa(L/(m2#h)),Vt(L),S(m2),t(h)2.3.2,10-4BSA,0.1MPa,UV-2450280mnR:591:PVDF/TiO2*:(973)(2009CB623402);(2007GG10005001):2008-10-13:2009-01-03::(1984-),,,,,R(%)=1-C1C2@100%(2)C1C22.3.3,JEM-6700F,,,,SEMEDS2.3.4DSCDSCSTA409PC:25~200e,10e/min,N22.3.5,DSA10033.1TBTTBT,,NMPTBT,,,TBT,NMPTBT,,NMPNTi)OHH,Ti)O,[10]pH,TBT,TBT,,,,[11]3.2EDS3.4%()TBTEDS(11),,Ti,TBT图1杂化膜的能谱图Fig1EDSimageofhybridmembrane1Table1Percentageofdifferentelements元素质量百分比原子百分比CK35.3346.67OK3.012.29FK59.449.6TiK2.260.75总量1003.32,TBT,TBT,,TBT,TBT,-,;,TBT[12],,,,,TBT图2不同添加剂膜的SEM图片Fig2SEMimagesofmembraneswithdifferentaddition3.43TBTTBT2.3%4.5%()3DSC,2,TBT0~4.5%2TBT,,TBTPVDF,,,,SEM59220094(40)图3TBT含量对膜熔点的影响Fig3EffectofcontentofTBTonmeltingpointofmembranes2Table2Themeltingpointandmeltenthalpyofdif-ferentmembanes膜样品熔点T(e)熔融焓$Hm(J/g)聚合物+3.6%LiCl174.630.18聚合物+3.6wt%LiCl+2.3wt%TBT175.030.15聚合物+3.6wt%LiCl+4.5wt%TBT175.234.493.5PVDF/TiO23.5.1Ti,TBT3,TBT,,,TBT2.86g,TBT,,TiO2,,,TBT,,;TBT,,TiO2,,,TBT3TBTTable3EffectofcontentofTBToncontactangleofmembranesTBT量(g)00.952.863.814.76接触角(b)70.4464.2760.4162.2762.253.5.2Ti4,TBT,,BSA,90%TBT,,,,TBT,TBT,,图4TBT含量对水通量和截留率的影响Fig4EffectofcontentofTBTonwaterfluxandre-jection4TBTPVDF/TiO2,:(1)TBT:,,BSA;(2)SEM,TBT;DSC,PVDF/TiO2,TBT;EDS,TiO,TBT:[1],,.[J].,2006,26(1):31-34.[2]NagaraleRK,ShahiVK.[J].JournalofMembraneSc-ience,2005,248(1):37-44.[3]ZhongShunhe,LiChuanfeng,XiaoXiufen.[J].JournalofMembraneScience,2002,199(1):53-58.[4]CorneliusC,HibshmanC,MarandE.[J].SeparationandPurificationTechnology,2001,25(1):181-193.[5]HuQ,MarandE.[J].Polymer.1999,40(17):4833-4843.[6]MauritzKA,PayneJT.[J].JournalofMembraneSc-ience,2000,168(1):39-51.[7]KimSH,KwakSY,SohnBH,etal.[J].JournalofMembraneScience,2003,211(1):157-165.[8],.[J].,2002,18(5):177-179.[9]YeowML,LiuYutie,LiK.[J].JournalofMembraneScience,2005,258(1):16-22.[10].-[M].:,2005.[11],,.[J].,2005(3):417-423.[12].Si(Ti)/PVDF[D].:,2007.593:PVDF/TiO2Preparationandcharacterizationofpolymer/TiO2hybridmembraneJIANGHa-ifeng,MAYu-xin,WANGDuo,GAOCong-jie(CollegeofChemistryandChemicalEngineering,OceanUniversityofChina,Qingdao266100,China)Abstract:Tetra-n-butyltitanate(TBT)wasaddedintothecastingsolutionandhydrolyzedsimultaneouslyintheprocessofmembraneformationofL-Sphaseinversiontopreparetheorganic-inorganichybridmembrane.Dif-ferentsampleswithdifferentcontentofTiO2werepreparedintheexperiment.TheeffectofTBTadditiononpurewaterflux,rejectionofbovineserumalbumin(BSA)andcontactanglewasstudied.Inaddition,thestructureandpropertiesofpolymer/TiO2hybridmembranewerestudiedbytensilestrength,differentialscan-ningcalorimetry(DSC),scanningelectronmicroscope(SEM)andenergydispersivespectroscopy(EDS).Itwasfoundthatthepropertiesofthehybridmembranewerebetterthanthepolymermembrane.WhenthemassfractionofTBTis5.8%,thepurewaterfluxofmembranewasnearlydoubledwhiletherejectionofBSAwasstillmorethan90%.ThestructureofmembranehadbeenchangedwiththeaddtionofTBT,andthesponge-typestructurewasreducedandthefinger-typestructurewasincreased.TitaniumwasdetectedinthemembranebytheEDS.Keywords:PVDF/TiO2hybridmembrane;ultrafiltrationmembrane;preparation(587)[16]YuanHJ,XieSS,LiuDF,etal.[J].ChemPhysLett,2003,371:337-341.[17]ZhangXianghui,ZhangYe,SongYipu,etal.[J].PhysE,2005,28:1-6.[18]HeZhaoyuan,SuYong,ChenYiqing,etal.[J].MaterResBull,2005,40:1308-1313.[19]LinMing,SudhiranjanT,BoothroydC,etal.[J].ChemPhysLett,2004,400:175-178.[20]ZhouXT,KimPSG,ShamTK,etal.[J].JApplPhys,2005,98:024312-1-024312-5.[21]QadriSB,SkeltonEF,HsuD,etal.[J].PhysRevB,1999,60:9191-9193.[22]MengZhaoyu,PengYiya,XuLiqiang,etal.[J].MaterLett,2002,53:165-167.[23]WeiFeng,LiGuicun,ZhangZhikun.[J].MaterResBull,2005,40:1402-1407.[24]MengXM,LiuJ,JiangY,etal.[J].ChemPhysLett,2003,382:434-438.[25]ManzoorK,AdityaV,VaderaSR,etal.[J].SolidStateComm,2005,135:16-20.[26]BeckerWG,BardAJ.[J].PhysChem,1983,87:4888-4893.[27]YangYong,ZhangWeijun.[J].MaterLett,2004,58:3836-3838.ThesynthesisandcharacterizationofZnSnanowireswithzincblendestructureDUYuan-yuan,JIEWan-qi,LIHuan-yong(SchoolofMaterialsandEngineering,NorthwesternPolytechnicalUniversity,Xi.an700072,China)Abstract:ZnSsingle-crystalnanowiresweresuccessfullysynthesizedonasiliconsubstratewiththeassistanceofNiSnanoparticlesviaasimpleCVDmethod.Theas-synthesizedZnSnanowireswere200nminaveragediame-terand25Lminlength,withzincblendestructuregrowingalongtheorientationof31114.WithPLspectrum,astrongemiss