9 191,,, *, ( 青岛科技大学橡塑材料与工程教育部重点实验室 / 山东省橡塑材料与工程重点实验室, 青岛 266042) : (TrG) (MWNTs) 3%(wt) 14, 20 47, 2%(wt), 1 10-5 S/cm TrG MWNTs, TrG MWNTs : [1~3], [1~6] 20, :(1) (2) sp 2, [7,8],, PMMA [9] PC [10] PVDF [11] PU [12] PA [13,14] PP [15] Nobile [16] (PE )/MWNTs, MWNTs PE Lv [17] PMMA/TrG [18,19], :2013-06-14 :2013-07-09 : (20944004) (ZR2012EMM003) (12-1-4-3-(7)- jch) (201010009) :,(1988-), *,,E-mail:hhq@qust.edu.cn.
192 2013 9, : (MVQ), OH (BR) π-π, 1 1.1 (MVQ), 110-2 BR9000 (MWNTs), MC5,-COOH 1.23%(wt), KH550, ( 25, ), SGN-102,,2,2,4- -1,2- ( RD),N- -N - ( 4010), ( TT),N- -2- ( CZ) XK-160, KQ2200DE, S212 DF-101S, JY92-2D GT-M2000-A,, 1.2 (MVQ) (THF), ( ), 1h, 150w ( ), 30min, 90w 50, tc 90, 160, 200 4h 1.3 :BR 100, 5, 2, RD 1, 4010 1, CZ 1, TT 0.5, 1.4, ( ), 70, 10min, 8h, 40~50, 3min, 1mm 2.5mm, 151, tc 90 1.4 GB/T528-1992 GB/T531-1999 : <10-6 S/cm, PC68, >10-6 S/cm, (MODELSZT-2000), (SEM,JSM-6700F), (TEM,JEM-2100), (EMFC7), (AI-700M ), (CSPM3000 ) 2 2.1 (TrG) (TEM) (AFM) TrG,TEM AFM 1 1a TrG TEM,TrG,, sp 2 sp 3
9 193 Figure1 1 TEM AFM (a) TEM (b) AFM (c)b (a)temimageofgraphene(b)afmimageofgraphene(c)heightofthepositionmarkedbythebluecross 1b 1c TrG AFM 1b 1c, 1nm, 0.5~0.8nm [20] 2.2 2 (SEM) SEM ( 2a) 2b MWNTs 5 SEM, MWNTs, 1~6μm MWNTs, 2 SEM (a) / (3phr) SEM (b) / (5phr) SEM (c) / (5phr) SEM (d) / (10phr) SEM Figure2 SEMimagesofrubbercomposites (a)semimageofmvq/trg(3phr)composities(b)semimageofmvq/mwnts(5phr)composities (c)semimageofbr/trg(5phr)composites(d)semimageofbr/mwnts(10phr)composites BR, TrG MWNTs BR,,TrG ( 2c),MWNTs BR ( 2d),TrG BR MWNTs
194 2013 9,,, ( O Si O ) O OH BR ( C C C C ) C H,BR π-π /, π-π 2.3 3 (MWNTs) (TrG) 3%(wt) 14, 0.22MPa 3.04MPa, 20 47, MWNTs 10%(wt) 4, 0.22MPa 0.94MPa, 20 27 3 (a)mwnts (b)trg (c)mwnts (d)trg Figure3 Themechanicalpropertiesofrubberwithdiferentfiler (a)themechanicalpropertiesofsiliconrubberwith MWNTs(b)themechanicalpropertiesofsilicon rubberwithtrg(c)themechanicalpropertiesofbutadienerubberwith MWNTs (d)themechanicalpropertiesofbutadienerubberwithtrg, 7%, 1.21MPa 8.22MPa, 50 72, MWNTs 10%,
9 195 0.22MPa 2.23MPa, 50 59 2.4 4 4a, /TrG 2%(wt), 1 10-5 S/cm, /TrG 7%(wt) 5.56 10-7 S/cm /MWNTs 5%(wt) 2.38 10-7 S/cm, /MWNTs 15%(wt), 3.33 10-5 S/cm, MWNTs,, MWNTs,,,,, 4 (a)mwnts TrG (b)mwnts TrG Figure4 Theconductivityofrubberwithdiferentfiler (a)theconductivityofrubberwith MWNTsandTrG(b)theconductivityofrubberwith MWNTsandTrG 3, 3%(wt) 14, 2%(wt), : (20944004), (ZR2012EMM003), (12-1-4-3-(7)- jch) (201010009) : [1] NovoselovKS,Geim A K,MorozovS V,JiangD,ZhangY,DubonosS V,GrigorievaIV,FirsovA A.Science,2004,306 (5956):666~669. [2] IijimaS.Nature,1991,354(6348):56~58. [3] Geim A K,NovoselovKS.NatMater,2007,6(3):183~191. [4] DuJ,ChengH M.MacromolChem Phys,2012,213:1060~1077. [5] SunY,ShiG.JPolymSciPolPhys,2013,51(4):231~253. [6] KuilaT,BhadraS,YaoD,Kim N H,BoseS,LeeJH.ProgPolymSci,2010,35(11):1350~1375. [7] BaoC,GuoY,SongL,KanY,QianX,Yuan H.JMaterChem,2011,21:13290~13298. [8] YangSY,Lin W N,HuangY L,Tien H W,WangJY,MaCC,WangYS.Carbon,2011,49(3):793~803.
196 2013 9 [9] AlizadehT,SoltaniL H.JHazard Mater,2013,248:401~406. [10] GedlerG,AntunesM,RealinhoV,VelascoJI.MatSciEng,2012,31(1):012008. [11] FanP,WangL,YangJ,ChenF,Zhong M.Nanotechnol,2012,23(36):365702. [12] ChenZ,Lu H.JMaterChem,2012,22(25):12479~12490. [13] ZhengD,TangG,ZhangH B,YuZZ,YavariF,KoratkarN.ComposSciTechnol,2012,72(2):284~289. [14] ChiuFC,KaoGF.ComposPartA-ApplSci,2012,43(1):208~218. [15],,.,2013,1:7~12. [16] NobileM R,SimonGP,ValentinoO,Morcom M.MacromolSymp,2007,247(1):78~87. [17] LvC,XueQ,XiaD,MaM,XieJ,Chen H.JPhysChem C,2010,114(14):6588~6594. [18] Hu H,ZhaoL,LiuJ,ChengJ,LuoJ,LiangY,ZhaoJ.Polymer2012,53(15):3378~3385. [19] Hu H,LiuY,WangQ,ZhaoJ,LiangY.MaterLet2011,65(17):2582~2584. [20],,,.,2011,26(1):26~30. StudyontheDispersionofGrapheneandCarbonNanotubes inrubbercomposites YAN Lu-yao,ZHOU Bao-zhen,QUShun-zhi,ZHAOLi,HU Hai-qing *,LIU Guang-ye (Key Laboratoryof Rubber-Plastics Ministryof Education/Shandong Provincial Key Laboratory of Rubber-plastics,Qingdao Universityof Scienceand Technology,Qingdao266042,China) Abstract:Graphene(TrG)andmulti-waledcarbonnanotubes(MWNTs)wereusedtomodifythemechanicalproperties ofsiliconerubber(mvq)and butadienerubber(br).thetensilestrength of TrG /siliconerubbercomposites was improvedabout14timesandtheshoreahardnesswasincreasedfrom20to47with3wt% oftrg.thesepropertieswere muchhigherthan rubbers which wereimproved with MWNTs.Percolationthreshold ofsiliconerubberconductive compositesfiledwithtrg was2wt%,theconductivityofwhichwas1 10-5 S/cm.MWNTs/siliconerubbercomposites werepreparedbysolutionmethod,whilepercolationthresholdwas5 wt%,theconductivitywas2.38 10-7 S/cm.The sametendencyhadbeenobservedintrgand MWNTs/BRsystem.ThediferentdispersionbehaviorofTrGand MWNTs couldbecontributedtothediferenceintheirinteractionwithpolymermatrixduetotheirvariousgeometryandtopology. BasedonSEMandTEManalysis,thedispersionofMWNTsinsiliconerubbermatrixwasextremelydificultincomparison withtrg,althoughbothofthempossessthesamechemicalstructure.bothplanesofgraphenecouldinteractwithpolymer chains,enlargethecontactareaofgraphene with matrix,whichleadtothestronginteractionbetweengrapheneand rubber.thedispersionofgrapheneinrubbercouldbeobtainedevenintheweakinteractionsystemsuchastrg/butadiene rubbersystem. Keywords:GrapheneCarbonnanotubeSiliconerubberButadienerubberVanderWaalsforce