摘要
碳纳米管是一类长径比极大的中空管状结构材料。研究表明碳纳米管具有很高的轴向强度,优异的导电、导热、耐高温等物理性能,被认为是当前最理想的聚合物填料,可用于制备高性能、多功能性能新型聚合物复合材料。近年来,碳纳米管/聚合物复合材料的研究逐渐成为新材料领域研究工作者的热点。本文采用不同方法成功制备了聚氨酯/碳纳米管纳米复合材料,考察了聚氨酯/碳纳米管纳米复合材料的结构与性能,并对其性能作了系统的研究。
在论文的第一部分中,采用熔融共混法成功制备了高填充的碳纳米管/热塑性聚氨酯纳米复合材料,电镜观察结果说明,直接的熔融共混法制备的高填充的碳纳米管/热塑性聚氨酯纳米复合材料中,碳纳米管在双辊的强烈剪切力和高温作用下均匀分散在聚氨酯基体中,未处理的碳纳米管在聚氨酯基体中的分散呈纳米级分散状态。XRD和DSC分析结果表明,对于热塑性聚氨酯/碳纳米管复合体系,碳纳米管的加入只是稍微改变了聚氨酯的微相分离结构。通过力学性能、动态机械热分析、功能性能的测试,发现热塑性聚氨酯/碳纳米管纳米复合材料的力学性能与碳纳米管用量的关系与短纤维/橡胶复合材料的力学性能表现规律是相似的,碳纳米管的加入对聚氨酯在高温环境下(120℃)的力学性能是有增强作用的;碳纳米管的加入对复合材料的动态储能模量有明显的增强效果,特别是在橡胶态下,纳米复合材料的动态模量比纯聚氨酯大幅度提高,随着碳纳米管用量的增加,所得复合材料的模量逐渐提高,而且橡胶态到粘流态的转变温度升高,碳纳米管的加入改善了热塑性聚氨酯的耐热性;复合材料的导电性能提高,还具有摩擦系数降低,磨损性能提高以及一定的导热性能。当碳纳米管加入量为40 phr时,热塑性聚氨酯/碳纳米管复合材料的导电率为1.1S·m~(-1),复合材料的导电逾渗值在10 vol%MWNT左右。
在论文的第二部分,首先采用熔融共混法制备了热塑性聚氨酯/碳纳米管复合体系,然后通过退火热处理的方式对碳纳米管/热塑性聚氨酯复合体系进行了退火处理。主要研究了退火热处理对热塑性聚氨酯微观结构的影响以及热塑性聚氨酯/碳纳米管纳米复合材料导电性能的影响。结果表明,退火热处理过程改变了聚氨酯的微相分离结构;通过退火热处理方法降低了热塑性聚氨酯/碳纳米管纳米复合材料的导电逾渗值。复合材料熔融状态下热处理对于热塑性聚氨酯/碳纳米管复合体系,有利于碳纳米管聚集絮凝强化网络结构从而提高材料的导电性能,降低导电逾渗值。
论文的第三部分中,采用十二烷基磺酸钠表面活性剂,与碳纳米管、水性聚氨酯乳液超声共混制备了聚氨酯/碳纳米管稳定悬浮液,通过喷雾干燥法成功制备了聚氨酯/碳纳米管纳米复合材料。喷雾工艺条件为:进气温度190℃,进料率为20%。电镜观察结果表明未处理的碳纳米管在聚氨酯基体中分散均匀。X-射线衍射测试表明碳纳米管的加入对聚氨酯的微相结构影响较小。导电性能测试结果表明碳纳米管的加入提高了复合材料的导电性能。随着碳纳米管体积分数的增加,聚氨酯/碳纳米管纳米复合材料的电导率逐渐增大,填充碳纳米管的聚氨酯纳米复合材料的导电逾渗值约为5%。另外,该复合材料还表现出导热性能,是一种综合性能优异的纳米复合材料。
本文的最后通过静电纺丝技术制备了聚氨酯/碳纳米管复合纤维。聚氨酯/碳纳米管复合纤维的静电纺丝的适宜工艺条件:电压调至15kV,流速调至2ml/h,收集钢板到喷嘴的距离调至25cm。扫描电镜观察表明其复合纤维的直径均达到了纳米级别。透射电镜观察发现碳纳米管在复合纤维中呈一定的取向排列。XRD、DSC分析结果说明碳纳米管的加入基本没有影响聚氨酯的微观结构。随着碳纳米管用量的增加,复合材料的导电性能有一定的提高。
Carbon nanotubes have excellent mechanical strength, electrical and thermal conductivity and thermal stability, which is considered to be the optical filler for polymer materials. Carbon nanotubes is a hollow tubular material possessing high aspect ratio. Recently, many researches focus on the incorporation of carbon nanotubes in polymer materials. In this paper, polyurethane/multi-walled carbon nanotubes (PU/MWNT) nanocomposites were successfully fabricated through different compounding technology, the structure and properties of PU/MWNT nanocomposites were systematically investigated.
Firstly, a melt blending process has been employed to prepare nanocomposites based on thermoplastic polyurethane (TPU) and MWNT. The content of MWNT filled in TPU was increased till 40phr (parts per hundreds of rubber).The morphological, structural and mechanical properties of the resulting TPU nanocomposites were systematically investigated using scanning electron microscope (SEM), transmission electron microscope (TEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), dynamic mechanical thermal analysis (DMTA) and tensile testing. The results indicated that the unmodified MWNT were dispersed finely and uniformly in the TPU matrix beyond expectation, and the microphase separation structures of the TPU nanocomposites were slightly affected by the presence of MWNT. The mechanical properties of the TPU nanocomposites containing various amounts of MWNT at both room temperature and 120℃were studied, which demonstrated that the modulus of TPU were greatly increased and the high temperature tensile strength of TPU was also prominently improved when MWNT content is higher. Moreover, the TPU nanocomposites exhibited improved thermal and electrical conductivities that might mean the TPU/MWNT nanocomposites have potential application as multi-functional materials.
In addition flocculation method through annealing the nanocomposites at higher molding temperature has been adopted to improve the electrical conductivity of the nanocomposites. XRD experiment shows that the microphase separation structures of the TPU nanocomposites are affected by annealing heat treatment. Annealing heat treatment is in favor of increasing electrical conductivity of the nanocomposites and the percolation threshold value in electricity of the annealed TPU/MWNT nanocomposites is lower by contrast to the TPU/MWNT nanocomposites.
Secondly, a spray drying approach has been adopted to prepare polyurethane (PU)/MWNT nanocomposites. Through the SEM observation, the unmodified MWNT were dispersed finely and uniformly in the PU matrix. XRD experiment indicates that the microphase separation structures of the PU nanocomposites were slightly affected by the presence of MWNT. In the electrical conductivity test, the electrical conductivity of the nanocomposites is gradually improved with increasing MWNT content as expected. The percolation threshold of the PU nanocomposites filled with MWNT is about 5vol %.
In the final part, PU/MWNT composite fiber has been prepared by electrospinning, their structure and the electrical conductivity property have also been studied. SEM and TEM images show that the composite fibers have the diameter of nano scale and MWNT in the composite fibers have been aligned partly.
引文
[1]山西省化工研究所.聚氨酯弹性体手册[M].北京:化学工业出版社,2001,1-9
[2]Iijima S.Helical microtubules of graphitic carbon[J],Nature,1991,354(7),56-59
[3]Wang J.Carbon-nanotube based electrochemical biosensors:A review[J],Electroanalysis,2005,17(1),7-14
[4]Kaushik BK,Goel S,Rauthan G.Future VLSI interconnects:optical fiber or carbon nanotube-a review[J].Microelectronics International 2007;24(2):53-63
[5]Coleman JN,Khan U,Blau WJ,Gunko YK.Small but strong:A review of the mechanical properties of carbon nanotube-polymer composites[J].Carbon 2006;44(9):1624-52
[6]Breuer O,Sundararaj U.Big returns from small fibers:A review of polymer/carbon nanotube composites[J].Polymer Composites 2004;25(6):630-45
[7]Bokobza L.Multiwall carbon nanotube elastomeric composites:A review[J].Polymer 2007,48(17):4907-20
[8]Vincent H Crespi.Relations between global and local topology in multiple nanotube junctions[J].Phys Rev B,1998,58(19):12671-12672
[9]Valentin N Popov.Carbon nanotubes:properties and application[J].Materials Science and Engineering R 2004,43(3),61-102
[10]Li QW,Li Y,Zhang XF,Chikkannanavar SB,Zhao YH,Dangelewicz AM,et al.Structure-dependent electrical properties of carbon nanotube fibers[J].Advanced Materials 2007,19(20):3358-3363
[11]Liu K,Sun YH,Chen L,Feng C,Feng XF,Jiang KL,et al.Controlled growth of super-aligned carbon nanotube arrays for spinning continuous unidirectional sheets with tunable physical properties[J].Nano Letters 2008,8(2):700-705
[12]Oncel C,Yurum Y.Carbon nanotube synthesis via the catalytic CVD method:A review on the effect of reaction parameters[J].Fullerenes Nanotubes and Carbon Nanostructures 2006,14(1):17-37
[13]Shin YS,Yang JH,Park CY,Kwon MH,Yoo JB,Yang CW.Synthesis of crystalline carbon nanotube arrays on anodic aluminum oxide using catalyst reduction with low pressure thermal chemical vapor deposition[J].Japanese Journal of Applied Physics Part 1-Regular Papers Brief Communications &Review Papers 2006,45(3A):1869-72
[14]Turano SP,Ready J.Chemical vapor deposition synthesis of self-aligned carbon nanotube arrays[J].Journal of Electronic Materials 2006,35(2):192-94
[15]Malhotra SV.Synthesis of carbon nanotube gels with Ionic liquids[J].Abstracts of Papers of the American Chemical Society 2005,230:U2208-U2009
[16]Chuang CC,Liu WL,Chen WJ,Huang JH.The role of Ti interlayer in carbon nanotube growth[J].Surface &Coatings Technology 2008,202(10):2121-2125
[17]Chen J,Minett AI,Liu Y,Lynam C,Sherrell P,Wang C,et al.Direct growth of flexible carbon nanotube electrodes[J].Advanced Materials 2008,20(3):566-570
[18]Pal SK,Talapatra S,Kar S,Ci L,Vajtai R,Borca-Tasciuc T,et al.Time and temperature dependence of multi-walled carbon nanotube growth on Inconel 600[J].Nanotechnology 2008, 19(4): 45502-45508
[19] Yang Z, Chen XH, Nie HG, Zhang K, Li WH, Yi B, et al. Direct synthesis of ultra long carbon nanotube bundles by spray pyrolysis and investigation of growth mechanism [J]. Nanotechnology 2008;19(8): 85606
[20] Eceiza A, Martin MD, de la Caba K, Kortaberria G, Gabilondo N, Corcuera MA, et al. Thermoplastic polyurethane elastomers based on polycarbonate diols with different soft segment molecular weight and chemical structure: Mechanical and thermal properties [J].Polymer Engineering and Science,2008;48(2):297-306
[21] Wu J, Huang QW, Ma YF, Huang Y, Liu ZF, Yang XY, et al. Distortion of carbon nanotube array and its influence on carbon nanotube growth and termination [J] .Colloids and Surfaces a-Physicochemical and Engineering Aspects 2008,313:13-17
[22] Ding F, Bolton K, Rosen A. Structure and thermal properties of supported catalyst clusters for single-walled carbon nanotube growth [J]. Applied Surface Science 2006, 252(15):5254-58
[23] Lange H, Bystrzejewski M, Huczko A. Influence of carbon structure on carbon nanotube formation and carbon arc plasma [J] .Diamond and Related Materials 2006;15(4-8):1113-16
[24] Ebbesen TW, Lezec HJ, Hiura H,et al. Electrical conduvtivity of individual carbon nanotubes [J], Nature, 1996,382:54-56
[25] Odom TW, Huang JL, Kim P, et al. Atomic structure and electronic properties of single-walled carbon nanootubes [J]. Nature,1998, 391:62-64
[26] Berber S, Kwon YK, Tomanek D. Unusually high thermal conductivity of carbon nanotubes [J]. Phys Rev Lett, 2000,84(20):4613-4616
[27] Noya EG, Srivastava D, Chernozatonskii LA, Menon M. Thermal conductivity of carbon nanotube peapods [J].Physical Review B 2004;70(11)
[28] Nan CW,Liu G,Lin YH,Li M.Interface effect on thermal conductivity of carbon nanotube composites [J] .Applied Physics Letters 2004;85(16):3549-51.
[29] Foygel M, Morris RD, Anez D, French S, Sobolev VL. Theoretical and computational studies of carbon nanotube composites and suspensions: Electrical and thermal conductivity [J].Physical Review B 2005;71(10)
[30] Fujii M, Zhang X, Xie HQ, Ago H, Takahashi K, Ikuta T, et al. Measuring the thermal conductivity of a single carbon nanotube [J].Physical Review Letters 2005;95(6)
[31] Treacy M M, Ebbesen T W, Gibson J M, Exceptionally high young's modulus observed for individual carbon nanotubes [J], Nature, 1996, 381,678-680
[32] Pugno N M. On the strength of the carbon nanotube-based space elevator cable: from nanomechanics to mega mechanics [J]. Journal of Physics-Condensed Matter 2006, 18(33):S1971-S1990
[33] Goyal A, Wiegand DA, Owens FJ, Iqbal Z. Synthesis of carbide-free,high strength iron-carbonnanotube composite by in situ nanotube growth [J]. Chemical Physics Letters 2007,442(4-6):365-371
[34] Sun Y, Sun JR, Liu M, Chen QF. Mechanical strength of carbon nanotube-nickel nanocomposites [J]. Nanotechnology 2007,18(50): 5704-5710
[35] Dillon AC, Jones KM, Bekkedahl TA, et al., Storage of hydrogen in single-walled carbon Nanotubes [J],Nature, 1997, 386: 377-379
[36]detteer WA,Bonard JM,Fauth K,Chatelain A,Forro L,Ugarte D.Electron field emitters based on carbon nanotube films[J].Advanced Materials 1997;9(1):87-89
[37]Collins PG,Zettl A.Unique characteristics of cold cathode carbon-nanotube-matrix field emitters[J].Physical Review B 1997,55(15):9391-9399
[38]Boussaad S,Tao NJ,Zhang R,Hopson T,Nagahara LA.In situ detection of cytochrome c adsorption with single walled carbon nanotube device[J].Chemical Communications 2003(13):1502-03.
[39]Biswas SK,Vajtai R,Wei BQ,Meng GW,Schowalter L J,Ajayan PM.Vertically aligned conductive carbon nanotube junctions and arrays for device applications[J].Applied Physics Letters 2004;84(15):2889-2891
[40]Yu W,Cho YS,Choi GS,Kim DJ,Song YH,Lee JH.A stable high power carbon nanotube field-emitter device[J].Diamond and Related Materials 2004,13(4-8):1017-1021
[41]Ren JW,Liao SJ,Liu JM.MNi4.8Sn0.2(M=La,Nd)-supported multi-walled carbon nanotube composites as hydrogen storage materials[J].Chinese Science Bulletin 2007,52(12):1616-1622
[42]Cao DP,Wang WC.Storage of hydrogen in single-walled carbon nanotube bundles with optimized parameters:Effect of external surfaces[J].International Journal of Hydrogen Energy 2007,32(12):1939-1942
[43]Hsieh CT,Chu YW,Lin JY.Fabrication and electrochemical activity of Ni-attached carbon nanotube electrodes for hydrogen storage in alkali electrolyte[J].International Journal of Hydrogen Energy2007,32(15):3457-3464
[44]Reddy ALM,Ramaprabhu S.Design and fabrication of carbon nanotube-based mierofuel cell and fuel cell stack coupled with hydrogen storage device[J].International Journal of Hydrogen Energy2007,32(17):4272-4278
[45]马仁志,魏秉庆,徐才录,等.基于碳纳米管的超级电容器[J].中国科学(E 辑),2000,30(2):112
[46]Pugno NM.On the strength of the carbon nanotube-based space elevator cable:from nanomechanics to megamechanics[J].Joumal of Physics-Condensed Matter 2006;18(33):S1971-S1990
[47]Ajayan PM,Schadler LS,Giannaris C,Rubio A,Single-Walled Carbon Nanotube-Polymer Composites:Strength and Weakness[J],Advanced Materials,2000,12(10),750-753
[48]Barber AH,Cohen SR,Wagner HD.Measurement of carbon nanotube-polymer interfacial strength[J].Applied Physics Letters 2003,82(23):4140-4142
[49]Spinks GM,Mottaghitalab V,Bahrami-Saniani M,Whitten PG,Wallace GG.Carbon-nanotube-reinforced polyaniline fibers for high-strength artificial muscles [J].Advanced Materials 2006,18(5):637-640
[50]Mclntosh D,Khabashesku VN,Barrera EV.Benzoyl peroxide initiated in situ functionalization processing and mechanical properties of single-walled carbon nanotube-polypropylene composite fibers[J].Journal of Physical Chemistry C 2007,111(4):1592-600
[51]王铀,沈静铢.制备聚合物纳米复合材料展望[J].化工新型材料,1998,1:8-12
[52]刘祥萱,马卫华,扬绪杰.纳米粒子催化马来酰亚胺溶液聚合[J].高分子材料,1997, 4: 1-4
[53] Eduardo R H, Pilar A, Blanca C, Juan C G. Nanocomposite materials with controlled ion mobilityk [J]. Advanced Materials, 1995, 7(2): 180-184
[54] Safadi B, Andrews R, E. Grulke A, Multiwalled Carbon Nanotube Polymer Composites: Synthesis and Characterization of Thin Films [J]. J Appl Polym Sci, 2002, 84, 2660-2669
[55] Song YS, Youn JR, Influence of dispersion states of carbon nanotubes on physical properties of epoxy nanocomposites [J], Carbon, 2005, 43, 1378-1385
[56] Manchado MAL, Valentini L, Biagiotti J, Kenny J M, Thermal and mechanical properties of single-walled carbon nanotubes-polypropylene composites prepared by melt processing [J] ,Carbon, 43 (2005) 1499-1505
[57] Zhang W D, Shen L, Phang I Y, Liu T, Carbon nanotubes reinforced nylon-6 composite prepared by simple melt-compounding [J]. Macromolecules, 2004,37: 256-259
[58] Zhang Zh N, Zhang J, Chen P, Zhang BQ, He J S, Hu G H, Enhanced interactions between multi-walled carbon nanotubes and polystyrene induced by melt mixing [J], Carbon, 44 (2006) 692-698
[59] Gao J, Itkis M E, Yu A, Bekyarova E, Zhao B, Haddon R C, Continous spinning of a single-walled carbon nanotube-nylon composite fiber [J], Journal of American Chemical Society, 2005,127 :3847-3854
[60] Park C, Ounaies Z, Watson K A, Crooks R E, Smith J J, Lowther S E, Connell JW, Siochi E J, Harrison J S, St. Clair T L, Dispersion of single wall carbon nanotubes by in situ polymerization under sonication [J], Chemical Physics Letters, 2002,364: 303-308
[61] Deng J, Ding X, Zhang W, Peng H, Wang J, Long X, Li P, Chan A S C, Carbon nanotube -polyaniline hybrid materials[J], European Polymer Journal, 2002,38:2497-2501
[62] Xia H Sh, Song M, Preparation and characterization of polyurethane carbon nanotube composites [J], Soft Matter, 2005,1:386-394
[63] Jia ZJ, Wang ZY, Xu CL, Liang J, Wei BQ, Wu DH, Zhu SW, Study on poly(methyl methacrylate)/carbon nanotube composites [J], Material Science Engineering: A Structural Materials: Properties, Microstructure and Processing, 1999,271:395-400
[64] Zhang B., Dong X. M., Fu R. W., Zhao B., Zhang M. Q., The sensibility of the composites fabricated from polystyrene filling multi-walled carbon nanotubes for mixed vapors, Composites Science Technology, 2008,68,1357-1362
[65] Badaire S, Poulin P,MaugeyM, et al. In situ measurements of nanotube dimensions in suspensions by depolarized dynamic light scattering [J]. Langmuir, 2004, 20: 10367- 10370
[66] Islam M F, Rojas E,BergeyD M, et al. High weight fraction surfactant solubilization of single-wall carbon nanotubes in water [J]. Nano Letters, 2003,2: 269 - 273
[67] BryningM B,Milkie D E, Islam M F, et al. Thermal conductivity and interfacial resistance in single-wall carbon nanotube epoxy composites [J]. Appl Phys Lett, 2005,87 : 161909/1 - 161909/3
[68] Sundararajan P R, Singh S,MoniruzzamanM. Surfactant-induced crystallization of polycarbonate [J].Macromolecules, 2004, 37: 10208 -10211
[69] Singh S, Pei Y,Miller R, et al. Entangled carbon nanotube networks in polycarbonate [J]. Advanced Functional Material, 2003, 13: 868 - 872
[70] Du F, Fischer John E, Winey K I. Coagulation method for preparing single-walled carbon nanotube /poly(methyl methacrylate) composites and their modulus, electrical conductivity, and thermal stability [J]. J Polym Sci, Part B: Polym Phys, 2003,41: 3333 - 3338
[71] L iu T, Phang I Y, Shen L, et al. Morphology and mechanical properties of multi-walled carbon nanotubes reinforced nylon-6 composites [J]. Macromolecules, 2004, 37: 7214 - 7222
[72] Zhang W D, Shen L, Phang I Y, et al. Carbon nanotubes reinforced nylon-6 composite prepared by simple melt-compounding[J]. Macromolecules, 2004, 37: 256 - 259
[73] Bhattacharyya A R, Sreekumar T V, Smalley R E, et al. Crystallization and orientation studies in polypropylene /single wall carbon nanotube composite[J]. Polymer,2003,44 :2373 - 2377
[74] Siochi E J,Working D C, Park C, et al. Melt p rocessing of SWCNT-polyimide nanocomposite fibers[J]. Composites (PartB) : Engineering, 2004,35 : 439 - 446
[75] Jin Z, Pramoda KP, Xu G, Goh SH. Dynamic mechanical behavior of melt-processed multi-walled carbon nanotube/poly(methyl methacrylate) composites. Chem Phys Lett 2001,337:43-47
[76] Shaffer M S P, Windle A H. Fabrication and characterization of carbon nanotube /poly (vinylalcohol) composites. Adv Mater. 1999. 11.937
[77] Xu Hangxun, Wang Xingbo, Zhang Yanfeng, et al. Single-step in situ preparation of polymer-grafted multi-walled carbon nanotube composites under 60Coγ2ray irradiation [J]. Chem Mater, 2006 (18): 2929 - 2934
[78] Ma Yf, Ali S R, Dodoo A S, et al. Enhanced sensitivity for biosensors: multiple functions of DNA-wrapped single-walled carbon nanotubes in self-doped polyaniline nanocomposites [J]. J Phys Chem B, 2006,110 : 16359 - 16365
[79] Kong H, Gao C, Yan D Y. Controlled functionalization of multi-walled carbon nanotubes by in situ atom transfer radical polymerization [J]. Journal of the American Chemical Society, 2004,126: 412 - 413
[80] Master WK, Benito AM, Callejas MA, Seeger T, et al. Synthesis and characterization of new polyaniline/nanotube composites [J], Materials Science & Engineering 2003, C23:87-91
[81] Haggenmueller R, Fischer J E, Winey K I. Single wall carbon nanotube /polyethylene nanocomposites: nucleating and templating polyethylene crystallites [J]. Macromolecules, 2006,39 : 2964 - 2971
[82] Gao Junbao, ItkisM E, Yu Aiping, et al. Continuous spinning of a single-walled carbon nanotube-nylon composite fiber [J]. J Am Chem Soc, 2005, 127: 3847 - 3854
[83] Ajayan PM, Schadler LS, Giannaris C, Rubio A, Single-Walled Carbon Nanotube-Polymer Composites: Strength and Weakness [J], Advanced Materials, 2000, 12 (10) :750-753
[84] Einarsson E, Shiozawa H, Kramberger C, Rummeli MH, Gruneis A, Pichler T, et al. Revealing the small-bundle internal structure of vertically aligned single-walled carbon nanotube films [J]. Journal of Physical Chemistry C 2007,111(48):17861-17864
[85] Andrei N K, David A B, Andrew D B. Molecules in carbon nanotubes[J], Acc Chem Res,2005,38(12):901-09.
[86] Baowan D, Thamwattana N, Hill JM. Encapsulation of C-60 fullerenes into single-walled carbon nanotubes:Fundamental mechanical principles and conventional applied mathematical modeling[J].Physical Review B 2007,76(15),155411.1-155411.8
[87]Kaneko T,Okada T,Hatakeyama R.DNA encapsulation inside carbon nanotubes using micro electrolyte plasmas[J].Contributions to Plasma Physics 2007;47(1-2):57-63
[88]Christ KV,Sadeghpour HR.Energy dispersion in graphene and carbon nanotubes and molecular encapsulation in nanotubes[J].Physical Review B 2007,75(19):195418
[89]Qian D,Dickey EC.Load transfer and deformation mechanisms in carbon nanotube polystyrene composites[J].Applied Physics Letters,2002,20:2868-2870
[90]Wagner H D,Lourie O,Feldman Y,Tenne R.Stress induced fragmentation of multiwall carbon nanotubes in a polymer matrix[J].Applied Physics Letters,1998,72(2):1882-1901
[91]Andrews R,Jacques D,Rao AM,Rantell T.et al.Nanotube composite carbon fibers[J].Applied Physics Letters 1999,75(9),1329-1331
[92]Salvetat JP,Briggs GD,Bonard JM,et al.Elastic and shear moduli of single-walled carbon nanotube ropes[J].Phys.Rev.Lett.,1999,82(5):944-947
[93]贾志杰,王正元,徐才录等.原位法制取碳纳米管/尼龙-6复合材料[J].清华大学学报(自然科学版),2000,40(4),14-16
[94]Gong X,Liu J,Baskran S,et al.Surfactant-assisted Processing of Carbon Nanotube/Polymer Composites[J].Chemistry of Materials,2000,12(4):1049-1052
[95]Lordi V,Yao N.Molecular mechanics of binding in carbon-nanotube polymer composites[J].Journal of Materials Research,2000,15(12):2770-2779
[96]Bower C,Roseb R,Jin L,et al.Deformation of carbon nanotubes in nanotube-polymer composites.Applied Physics Letters,1999,74(22):3317-3319.
[97]李宏健,彭景翠,陈小华等.填充碳纳米管/石墨的有机导电膜[J],半导体学报,2000,21(6):586-590
[98]Raquel Sainz,William R Small,NigelA Young,et al.Synthesis and properties of optically active polyaniline carbon nanotube composites[J].Macromolecules,2006,39:7324-7332
[99]Baughman Ray H,Zakhidov AnvarA,de HeerWaltA.Carbon nanotubes—the route toward applications[J].Science,2002,297:787-92.
[100]贾志杰,王正元,梁吉,等.碳纳米管的加入对PMMA强度和导电性能的影响[J],材料开发与应用,1998,13(6),22-26
[101]李宏建,彭景翠,陈小华,等.填充碳纳米管/石墨的复合型电磁波屏蔽膜[J].化学物理学报,2001,14(2):211-215
[102]Grimes CA,Mungle C,Kouzoudis D,et al.The 500 MHz to 5.50 GHz complex permittivity spectra of single-wall carbon nanotube-loaded polymer composites[J].Chem.Phys.Lett.,2000,319:460-464
[103]胡平,范守善.碳纳米管/UHMW-PE复合材料的研究[J].工程塑料应用.1998,26(1):1-3
[104]Paul C P Watts,Wen Kuang Hsu,George Z Chen,et al.A low resistance boron-doped carbon nanotube-polystyrene composite[J].J Mater Chem,2001,11:2482-2488
[105]Schadler L S,Gianngaris S C,Ajayan PM.Load transfer in carbon nanotube epoxy composites[J].Applied Physics Letters,1998,73(26):38422-38441
[106]Sandler J KW,Kirk J E,Kinloch IA,et al.Ultra-low electrical percolation threshold in carbon nanotube-epoxy composites [J]. Polymer, 2003, 44: 5893 - 5899
[107] Bryning M B, Islam M F, Kikkawa J M, et al. Very low Conductivity threshold in bulk isotrop ic single-walled carbon nanotube-epoxy composites [J]. Advanced Material, 2005,17:1186-1191
[108] BiercukM J, L lagunoM C, Radosavljevic M, et al. Carbon nanotube composites for thermal management [J]. Applied Physics Letters, 2002, 80: 2767 - 2769
[109] Choi E S, Brooks J S, Eaton D L, et al. Enhancement of thermal and electrical properties of carbon nanotube polymer composites by magnetic field processing[J]. J Appl Phys, 2003, 94: 6034 - 6039
[110] Huang H, Liu C, Wu Y, Fan S. Aligned carbon nanotube composite films for thermal management[ J]. Adv Mater, 2005 (17): 1652 - 1656
[111] Huxtable S T, CahillD G, Shenogin S, et al. Interfacial heat flow in carbon nanotube suspensions [J]. Nature Mater, 2003, 2: 731 - 734
[112] Ge Jason J, Hou H, Li Q, et al. Assembly of well-aligned multi walled carbon nanotubes in confined polyacrylonitrile environments: electrospun composite nanofiber sheets [J]. J Am Chem Soc, 2004, 126: 15754 - 15761
[113] Beyer G. Short communication: carbon nanotubes as flame retardants for polymers [J]. Fire Mater, 2002, 26 : 291- 293
[114] Kashiwagi T,Du F,Winey K I, et al. Flammability properties of polymer nanocomposites with single-walled carbon nanotubes: Effects of nanotube dispersion and concentration [J]. Polymer, 2005,46: 471-481
[115] Shaffer MSP, Windle AH. Fabrication and characterization of carbon nanotube /poly(vinyl alcohol) composites[J], Advanced Materials, 1999, 11: 937-941
[116] Tang B Z, Xu X Y. Preparation, Alignment, and Optical Properties of Soluble Poly(phenylacetylene)-Wrapped Carbon Nanotubes[J], Macromolecules 1999, 32, 2569-2576
[117] Jin Zhaoxia, Sun Xuan, Xu Guoqin, et al. Nonlinear optical properties of some polymer/ multi-walled carbon nanotube composites [J]. Chem Phys Lett, 2000 ,318 :505 - 510
[118] Wu Wei, Li Junxin , Liu Luqi ,et al. The photo conductivity of PVK-carbon nanotube blends [J]. Chem Phys Lett, 2002 ,364 :196 -199
[119] Curran S, Ajayan P M, lau WB, et al. Composite from PPV and carbon nanotubes: a novel material for molecular optoelectronics [J].Advanced Materials, 1998, 10:1091
[120] Sun X, Yu R Q , Xu GQ , et al. Broadband optical limiting with multiwalled carbon nanotubes[J], Appl. Phys. Lett ., 1998 , 73 :3632-3637
[121] G.厄特尔.聚氨酯手册[M].中国石化出版社, 1992
[122] Estes G M, Cooper SL, Tobolsky A V.J Macromol Sci Rev Macromol Chem, 1970, 4:313
[123] Foks J, Janik H, Russo R, et al. Eur Polym J, 1989, 25:31
[124] Cooper S L, Toboolsky A V. JAppl Polym Sci.1966, 19:1037
[125] Arnold C.J Elastomers Plastics, 1974, 6:238
[126] Paik Sung C S and Schneider N S. Macromol. 1975, 8:68
[127] Legass R R. JAppl Polym Sci.1977, 27:2489
[128] KeveiTK, et al. JAppl Polym Sci.1982, 27:2891
[129] Heprum. Polyurethane Elastomors. Applied Sci Publishers. London and New York. 1982
[130] Chough S B, Sehneider N S, King A O, J Macromol Sci, 1968, B2:611
[131] koutsky JA, Hien NV, J.Polyln.Sci.Polym.Letter, 1970, 8:353
[132] Legasse RR, J.APPI..Polym.Sci., 1977, 21:2891
[133] Russo RT, Thomas EL, J.Polym.Sci-Phys., 1983, B22(4):553
[134] Leung LM, Koberstein JT, J.Polym.Sci., Polym.Phys.Eb., 1985, 23:1883
[135] SkriehatraPimuk VW, Cooper SL, J. Macromol. Sci., 1978, B15(2):267
[136] Hu CB,et al, J.Appl.Polym.Sci., 1982, 27:2167
[137] Huh DS, Cooper SL, Polym.Eng.Sci., 1971, 11:369
[138] Samuels SL, Wilkes GL, J.Polym.Sci., Polym.Symp., 1973, 43:149
[139] Chough SB, Sehneider NS and King AO, J.Macromol.Sci., 1968, B2:611
[140] C.海普本.聚氨酯弹性体 [M]. 辽宁科学技术出版社, 1985
[141] Eceiza A, Martin MD, de la Caba K, Kortaberria G, Gabilondo N,Corcuera MA,et al.Thermoplastic polyurethane elastomers based on polycarbonate diols with different soft segment molecular weight and chemical structure:Mechanical and thermal properties [J]. Polymer Engineering and Science, 2008;48(2):297-306
[142] Chuang FS. Analysis of thermal degradation of diacetylene-containing polyurethane copolymers [J] .Polymer Degradation and Stability 2007;92(7):1393-1407
[143] Vlad S, Oprea S.Chain extender and diisocyanate amount effects on the thermal,mechanical and wettability properties of some polyurethane elastomers [J].E-Polymers 2008
[144] Li WL,Liu JL,Hao CW ,Jiang K,Xu DF,Wang DJ.Interaction of thermoplastic polyurethane with polyamide 1212 and its influence on the thermal and mechanical properties of TPU/PA1212 blends[J]. Polymer Engineering and Science 2008;48(2):249-256
[145] Kim YH,Choi SJ,Kim AM,Han MS,Kim WN,Bang KT.Effects of organoclay on the thermal insulating properties of rigid polyurethane foams blown by environmentally friendly blowing agents[J]. Macromolecular Research 2007;15(7):676-681
[146] Thirumal M, Khastgir D, Singha NK, Manjunath BS, Naik YP. Mechanical, morphological and thermal properties of rigid polyurethane foam: Effect of the fillers[J].Cellular Polymers 2007;26(4):245-259
[147] Chen W, Tao X, Liu Y. Carbon nanotube-reinforced polyurethane composite fibers [J]. Composites Science and Technology, 2006, 66: 3029-3034.
[148] Jung Y C, Sahoo N G, Cho J W. Polymeric nanocomposites of polyurethane block copolymers and functionalized multi-walled carbon nanotubes as crosslinkers [J]. Macromolecular Rapid Communications, 2006, 27: 126-131
[149] Xiong Jiawen, Zhou Dongsheng, Zheng Zhen, et al. Fabrication and distribution characteristics of polyurethane / single-walled carbon nanotube composite with anisotrop ic structure [J]. Polymer, 2006,47: 1763-1766
[150] Kuan H C, Ma C C M, Chang W P et al. Synthesis, thermal, mechanical and rheological properties of multiwall carbon nanotube /waterborne polyurethane nanocomposite [J]. Composites Science and Technology, 2005, 65: 1703-1710
[151] Mondal S, Hu J L. A novel approach to excellent UV protecting cotton fabric with functionalized MWNT containing water vapor permeable PU coating [J]. Journal of Applied Polymer Science, 2007, 103: 3370-3376.
[152]Nanda Gopal Sahoo,Yong Chae Jung,Hye Jin Yoo,et al.Influence of carbon nanotubes and polypyrrole on the thermal,mechanical and electroactive shape memory properties of polyurethane nanocomposites[J].Composites Science and Technology,2007,67(9):1920-1929
[153]Xia Hesheng,Song Mo,Jin Jie,et al.Poly(propylene glycol)-grafted multi-walled carbon nanotube polyurethane[J].Macromolecular Chemistry and Physics.2006,207(21):1945-1952
[154]Kwon J Y,Kim H D.Comparison of the properties of waterbome polyurethane/multiwalled carbon nanotube and acid-treated multiwalled carbon nanotube composites prepared by in situ polymerization[J].Journal of Polymer Science,A:Polymer Chemistry,2005,43(17)::3973-3985
[155]喻光辉,曾繁涤.聚氨酯/碳纳米管复合材料力学及电性能研究[J].工程塑料应用,2005,33(6):11-14
[156]Sahoo GN,Jung CY,Yoo JH,Cho WJ.Effects of functionalized carbon nanotubes on molecular interaction and properties of polyurethane composites[J].Macromol.Chem.Phys.,2006,207(19):1773-1780
[157]Zunfeng Liu,Gang Bai,Yi Huang,et al.Reflection and absorption contributions to the electromagnetic interference shielding of single-walled carbon nanotube/polyurethane composites[J].Carbon,2007,45(4):821-827
[158]Min Xu,Tao Zhang,Bing Gu,et al.Synthesis and properties of novel polyurethane-urea /multiwalled carbon nanotube composites[J].Macromolecules,2006,39(10):3540-3545
[159][Meng J,Kong H,Xu H Y,et al.Imp roving the blood compatibility of polyurethane using carbon nanotubes as fillers and its implications to cardiovascular surgery[J].Journal of Biomedical Materials Research Part A,2005,74A(2):208-214.
[160]Jiawen Xiong,Zhen Zheng,Xiumin Qin,et al.The thermal and mechanical properties of a polyurethane/multi-walled carbon nanotube composite[J].Carbon,2006,44(13):2701-2707
[1]周湘文,王敬东,朱跃峰,梁吉.添加碳纳米管丁苯粉末橡胶的制备[J].碳素技术.2005,24(3):4-8
[2]朱跃峰,梁吉,王敬东,周湘文.一种碳纳米管改性粉末天然橡胶[P].中国专利,200510058999.6.2007-04-25
[3]Bielifiski D,Slusarski L.Physical modification of elastomers to improve their tribological properties[J].Wear,1993,169:257-263
[4]Ito K,Oki Y,Hirata M.Performance of a New NBR Rubber for Sliding Wear Applications [J].NTN Technical Review,2000,68:90-95
[1]Iijima S,Helical microtubules of graphitic carbon[J],Nature,1991,354:56-59
[2]Treacy M M,Ebbesen T W,Gibson J M,Exceptionally high young's modulus observed for individual carbon nanotubes[J],Nature,1996,381:678-680
[3]Ebbesen T W,Carbon nanotubes[J],Phys.Today,1996,49(6):26-32
[4]Cadek M,Colemen J N,Ryan K P,Nicolos V,Bister G,Fonseca A,Reinforcement of polymers with carbon nanotubes:The role of nanotube surface area[J],Nano Letters,2004,4:353-356
[5]Wei C,Srivastava D,Cho K,Thermal expansion and diffusion coefficients of carbon nanotube-polymer composites[J],Nano Letters,2002,2:647-650
[6]Lisunova MO,Mamunya Ye P,Et al,Percolation behaviour of ultrahigh molecular weight polyethylene/multi-walled carbon nanotubes composites[J],European Polymer Journal,2007,43:949-958
[7]Liu TX,Phang IY,Shen L,Chow SY,Zhang WD,Morphology and mechanical properties of multiwalled carbon nanotubes reinforced nylon-6 composites[J],Macromolecules,2004,37:7214-7222
[8]Pegel S,Potschke P,Petzold G,Alig I,Dudkin S M,Lellinger D,Dispersion,agglomeration,and network formation of multiwalled carbon nanotubes in polycarbonate melts[J],Polymer,2008,49:974-984
[9]Hill DE,Lin Y,Rao AM,Allard LF,Sun Y P,Functionalization of carbon nanotubes with polystyrene[J],Macromolecules,2002,35:9466-9471
[10]Lopez Manchado MA,Valentini L,Biagiotti J,Kenny JM,Thermal and mechanical properties of single-walled carbon nanotubespolypropylene composites prepared by melt processing[J],Carbon,2005,43:1499-1505
[11]DU F M,FISCHER JE,WINEY K I,Coagulation method for preparing single-walled carbon nanotube/poly(methyl methacrylate) composites and their modulus,electrical conductivity,and thermal stability[J],Journal of Polymer Science:Part B:Polymer Physics,2003,41:3333-3338
[12]Yue DM,Liu YF,Shen ZM,Zhang LQ,Study on preparation and properties of carbon nanotubes/rubber composites[J],J MATER SCI,2006,41:2541-2544
[13]Sreekumar TV,Liu T,Min BG,Guo H,Kumar S,Smalley RE,Polyacrlonitrile single-walled carbon nanotube composite fibers[J],Adv Mater,2004,16:58-61
[14]Payne A R,Whittaker RE,Low strain dynamic properties of filled rubbers[J],Rubber Chemistry and Technology,1994,44,440-478
[15]张立群,金日光,耿海萍,陈松,周彦豪.短纤维橡胶复合材料强度的理论研究Ⅰ纵度的理论预测[J].复合材料学报,1998,15,89-96
[16]卢金荣,吴大军,陈国华,聚合物基导电复合材料几种导电理论的评述[J],塑料,2004,33(5),43-47
[17]贾向明,杨其,李光宪,填充型导电高分子复合材料的逾渗理论进展,中国塑料,2003,17(6):9-14
[18]Potschke P,Bhattacharyya A R,Janke A,Carbon nanotube-filled polycarbonate composites produced by melt mixing and their use in blends with polyethylene[J],Carbon,2004,42:965-969
[19]Kodgire PV,Bhattacharyya A R,Bose S,Gupta N,Kulkarni A R,Misra A,Control of multiwall carbon nanotubes dispersion in polyamide6 matrix:An assessment through electrical conductivity[J],Chemical Physics Letters,2006,432:480-485
[20]大原利一郎.摩擦の理论.日本..エム协会志,1995,68(9):587
[21]Hanhi K,Stellberg B.Friction and the Dynamic Mechanical and Thermal Properties of Polyurethane Elastomers.1.Solid Polyurethanes[J],Cellular Polymers,1993,12(6):461
[1]Georg GA Bohm,My N Nguyen.Flocculation of carbonblack in filled rubber compounds.I.Flocculation occurring in unvulcanized compounds during annealing at elevated temperatures[J].J Appl Polym Sci,1995,55:1041-1050
[2]林桂,吴有平,,钱燕超,贾清秀,张立群,纳米填料/橡胶体系在贮存中的结构形态变化Ⅰ.填料与橡胶及填料与填料的相互作用[J],合成橡胶工业,2004,27(5):324-329
[3]林桂,吴有平,张秀娟,钱燕超,贾清秀,张立群,纳米填料/橡胶体系在贮存中的结构形态变化Ⅱ.结构变化的影响因素及其对性能的影响[J],合成橡胶工业,2005,28(1):1-7
[4]Payne A R,Whittaker RE,Low strain dynamic properties of filled rubbers[J],Rubber Chemistry and Technology,1994,44,440-478
[1]Bandyopadhyaya R,Nativ-Roth E,Regev O,Yerushalmi-Rozen R,Stabilization of individual carbon nanotubes in aqueous solutions[J],Nano Lett,2002,2:25-28.
[2]周湘文,王敬东,朱跃峰,梁吉.添加碳纳米管丁苯粉末橡胶的制备[J].碳素技术.2005,24(3):4-8
[3]朱跃峰,梁吉,王敬东,周湘文.一种碳纳米管改性粉末天然橡胶[P].中国专利,2005 10058999.6.2007-04-25
[4]Payne A.R.,Whittaker R.E.,Low strain dynamic properties of filled rubbers[J],Rubber Chemistry and Technology,1994,44,440-478.
[5]张立群,金日光,耿海萍,陈松,周彦豪.短纤维橡胶复合材料强度的理论研究Ⅰ纵向拉伸强度的理论预测[J].复合材料学报,1998,15,89-96.
[1]Hohman MM,Shin M,Rutledge G,Brenner MP,Electrospinning and electrically forced jets.I.Stability theory[J],Physics of Fluids,2001,13(8):2201-2236
[2]Pakula T,Grebrowicz J,Kryszewski M,Polym,Bull.1980,2,799-804
[3]Dror Y,Salalha W,Khalfin RL,Cohen Y,Yarin AL,Zussman E,Carbon nanotubes embedded in oriented polymer nanofibers by electrospinning[J],Langmuir 2003,19:7012-7020
[4] Yao Z, Postma H W C, Balents L, et al. Carbon nanotube intramolecular juctions [J]. Nature, 1999,402 : 273