碳纳米管对聚苯乙烯分子运动的影响
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摘要
利用DSC、流变仪和能量损耗仪等测试仪器,系统研究了碳纳米管加入到聚苯乙烯基体中后对不同长度聚苯乙烯分子链运动的影响.结果表明,碳纳米管加入到聚苯乙烯中后对聚苯乙烯的玻璃转变和液-液转变都产生了影响.碳纳米管的加入引起自由体积的增加只在一个很小的范围内影响了分子链段的运动,当质量分数为0.1%的碳纳米管加入时,链段运动速度增加,玻璃转变温度明显向低温方向移动;而由于范德华力的存在,高分子链会在碳纳米管表面选择吸附,从而使得整链运动时,参与运动的链单元尺寸降低,所以造成了整链运动时链间的耦合降低了.
In this paper,the dynamics of polystyrene chain was studied by DSC,rheology and energy dissipation spectrum.It was shown that both the glass transiton and the liquid-liquid transition all changed for the appearance of MWNT in MWNT/PS composites.The appearance of free volume aroused by MWNT fillers influenced the mobility of segments in a small area and the speed of segment mobility increased leading to the decrease of glass transition temperature when 0.1wt%added into polystyrene matrix.For the existence of van der Waals forces,the polymer chains adsorped selectively on the surface of nanotube which decreased the length of polymer chain that took part in the mobility of whole chain,i.e.,the intermolecular coupling decreased.
In this paper,the dynamics of polystyrene chain was studied by DSC,rheology and energy dissipation spectrum.It was shown that both the glass transiton and the liquid-liquid transition all changed for the appearance of MWNT in MWNT/PS composites.The appearance of free volume aroused by MWNT fillers influenced the mobility of segments in a small area and the speed of segment mobility increased leading to the decrease of glass transition temperature when 0.1wt%added into polystyrene matrix.For the existence of van der Waals forces,the polymer chains adsorped selectively on the surface of nanotube which decreased the length of polymer chain that took part in the mobility of whole chain,i.e.,the intermolecular coupling decreased.
引文
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[2]BILOTTI E,ZHANG H,DENG H,et al.Controlling the dynamic percolation of Carbon nanotube based conductive polymer composites by addition of secondary nanofillers:The effect on electrical conductivity and tuneable sensing behaviour[J].Composites Science and Technology,2013,74:85-90.
[3]GAVRILOV A A,CHERTOVICH A V,KHALATUR P G,et al.Effect of nanotube size on the mechanical properties of elastomeric composites[J].Soft Matter,2013,9(15):4067-4072.
[4]QI Y N,XU F,SUN L X.Thermal stability and glass transition behavior of PANI/MWNT composites[J].Journal of Thermal Analysis and Calorimetry,2008,94(1):137-141.
[5]JEE M H,LEE J S,LEE J Y,et al.Poly(ethylene 2,6-naphthalate)/MWNT nanocomposites prepared by in situ polymerization:Rheological and mechanical properties[J].Fibers and Polymers,2010,11(1):1-7.
[6]Pham J Q,Mitchell C A,Bahr J L,et al.Glass transition of polymer/single-walled carbon nanotube composite films[J].Journal of Polymer Science Part B:Polymer Physics,2003,41:3339-3345.
[7]Sreekumar T V,Liu T,Mih B G,et al.Polyacrylonitrile single-walled carbon nanotube composite fibers[J].Advanced Materials,2004,16:58-61.
[8]XIONG Jia-wen,ZHENG Zhen,QIN Xiu-min,et al.The thermal and mechanical properties of a polyurethane/multi-walled Carbon nanotube composite[J].Carbon,2006,44(13):2701-2707.
[9]Barrau S,Demont P,Maraval C,et al.Glass transition temperature depression at the percolation threshold in carbon nanotube-epoxy resin and polypyrrole-epoxy resin composites[J].Macromolecules Rapid Communacation,2005,26:390-394.
[10]Grady B P,Paul A,Peters J E,et al.Glass transition behavior of single-walled carbon nanotube polystyrene composites[J].Macromolecules,2009,42:6152-6158.
[11]WANG Xiao-hong,LIU He-wen,QIU Long-zhen.Cationic polymerization of tetrahydrofuran from multiple-walled Carbon nanotubes:Preparation and glass transition kinetics[J].Materials Letters,2007,61(11/12):2350-2353.
[12]Wei C,Srivastava D,Cho K.Thermal expansion and diffusion coefficients of carbon nanotube-polymer composites[J].Nano Letters,2002,2:647-650.
[13]Baur M E,Stockmayer W H.Dielectric relaxation in liquid polypropylene oxides[J].Journal of Chemical Physics,1965,43:4319-4324.
[14]Stockmayer W H.Dielectric dispersion in solutions of flexible polymers[J].Pure and Applied Chemistry,1967,15:539-554.
[15]LEE H K,PEJANOVI S,MONDRAGON I,et al.Dynamics of single-walled Carbon nanotube(SWNT)/polyisoprene(PI)nanocomposites in electric and mechanical fields[J].Polymer,2007,48(25):7345-7355.
[16]ZHOU Wei,WANG Jun-jun,GONG Zhen-li,et al.Investigation of interfacial interaction and structural transition for epoxy/nanotube composites by positron annihilation lifetime spectroscopy[J].Applied Physics Letters,2009,94(2):021904.
[17]YAN Xiao-li,GONG Zhen-li,GONG Jing,et al.Investigation of the glass transition and viscoelastic properties of polycarbonate/multiwalled Carbon nanotube composites by positron annihilation lifetime spectroscopy[J].Polymer,2013,54(2):798-804.
[18]WENG D,LEE H K,LEVON K,et al.The influence of Buckminsterfullerenes and their derivatives on polymer properties[J].European Polymer Journal,1999,35(5):867-878.
[19]SHANG Shuying,ZHU Zhenguang,LU Zaijun,et al.Liquid-to-liquid relaxation of polystyrene melts investigated by low-frequency anelastic spectroscopy[J].Journal of Physics-Condensed Matter,2007,19(41):416107.
[20]NGAI K L,WRIGHT G B.Relaxation and diffusion in Complex Systems[M].Washington:Springer,1984.
[21]Plazek N.Correlation of polymer segmental chain dynamics with temperature-dependent time-scale shifts[J].Macromolecules,1991,24:1222-1224.