摘要
本论文选用导电材料为掺杂剂,通过物理复合和化学复合的方法让之与聚合物基质进行复合,希望材料在较低的掺杂量的同时具有较高的介电常数并且具有良好的机械性能,本论文主要有以下三部分组成:(1)为了得到介电性能良好并且相分离现象不明显的复合材料,本部分从分子设计的角度入手,采用氧化偶联的聚合方法,通过化学键连接的方式把导电性能优异的苯胺齐聚物接到聚合物的主链中,分别制备了四种不同链柔性的电活性聚合物,对它们的结构和性质分别进行了研究,探索分子链柔性对介电性能等性能的影响。(2)为了得到介电常数更高的全有机低密度的复合材料,本部分首先采用有机低密度的聚苯胺纳米纤维为掺杂材料让其与聚偏氟乙烯复合;然后为了降低掺杂材料和聚合物之间相分离现象的发生,采用一种“类原位聚合”的方法制备侧链含有聚苯胺的全有机聚合物材料。通过调节两种单体的比例,可以得到一系列具有不同介电常数的聚合物材料。(3)为了降低介电损耗,采用溶液共混的方法制备二氧化钛包覆的多壁碳纳米管/聚偏氟乙烯复合材料,二氧化钛包覆层能起到钝化层的作用,得到了介电常数较高介电损耗较低的导电材料/聚合物复合的介电材料;为了使材料在较低掺杂量的同时具有较高的介电常数,我们采用具有电学性能更加优异、热传导系数高和比表面积大的石墨烯为掺杂材料,采用氧化石墨烯在聚偏氟乙烯溶液中的原位还原的方法制得石墨烯与聚偏氟乙烯的高频下高介电复合材料。
High-technology fields require new high-dielectric-permittivity materials. High-technology electronic devices require new high dielectric permittivity materials (known as high-K materials).With the advantages of good mechanical and dielectric performance, composite materials that consist of a flexible polymer loaded with ferroelectric high-K ceramic or conductive fillers have been widely studied, because of their potential applications in some fields such as high charge-storage capacitors, artificial muscles, smart skins, and apparatus used in high-speed integrated circuits. In addition, high-K materials reduce the size of microwave devices, since the wavelength that travels through the medium is inversely proportional to the square root of the permittivity, and it leads to a lower production cost.
Even though many ceramic materials that have a high dielectric permittivity and a low dielectric loss are presently used in electronic fields, they are generally brittle in nature, sinter at high temperature, and entail a complicated fabrication process. To overcome these disadvantages, ceramic/polymer composites are better alternatives, However, the dielectric permittivity of the common polymer is extraordinarily low (below 10). Thus, enhancing the dielectric permittivity of the polymer-based materials and keep their mechanical performance of the composites is necessary. Many researchers have been done on ceramic-polymer composite systems that adopt ceramics as fillers, e.g., BaTiO3, CaCuTi4O12, PZT, and PMN-PT. However, these composites have low dielectric permittivity even at a high loading of ceramics (>50 vol%) and the high loading will deteriorate the mechanical properties of the composites such as flexibility.
To dissolve the problem of ceramics/polymer composites, much effort has been done recently in the preparation of conductive filler/polymer composite based on the percolation threshold theory. So the MCNT@TiO2 graphene、polyaniline nanofibers、polyaniline and oligoaniline were chosen as conducting fillers to polymer matrix by physical mixing method or chemical bonding way. The work includes three parts.
Firstly, for the sake of obtaining outstanding dielectric properties, chemically bonding the filler to the backbone of the polymer matrix is meaningful objective for the improving compatibility between the filler and matrix. Herein, we use an oxidative coupling polymerization approach to introduce the conductive segments of oligoaniline into polymer main chain to prepare a new kind of electroactive alternant copolymer. We synthesize four different polymers with rigidity aromaticity group、crown ether、long flexible chain and polyethylene oxide in the main chain, respectively. The chemical structure of the electroactive copolymer was confirmed by Fourier-transform infrared spectra (FTIR), nuclear magnetic resonance spectra (NMR) spectroscopy measurements. Electrochemical activity of the copolymer are tested in H2SO4 aqueous solution. Moreover, the thermal properties of the copolymer were investigated by thermogravimetric analysis (TGA). With the solubility enhancement of the polymer, the dielectric constant is 6.4,13,58 and 1690 at 1 kHz, respectively.
Secondly, due to the high conductivity and low density, polyaniline is chosen as conducting filler to mix with polymer matrix to get a full organic material with high dielectric constant. First, PANI nanofibers are prepared by a rapidly mixed reaction method. PANI nanobibers/PVDF composites are got by solution mixed method. The max constant of composite achieves 359 at 1 MHz with the PANI nanofibers weight percentage of 20%. Then, A novel copolymer of poly (styrene-co-styrenesulfonate) with different content of styrenesulfonate doped PANI (SSPANI) was prepared by free-radical polymerization method. Through adjusting the weight ratio of SSPANI to styrene, SSPANI loading in the copolymer could be well regulated so that a series of copolymers with different dielectric constant were obtained. In contrast to the simple physical mixing approach, the chemical bonding method is an effective way to avoid phase separation. Due to the well dispersion of PANI, the copolymer exhibited a super high dielectric constant compared to common polymer (about 3) and by simple physical mixing method at high frequency at room temperature. When the content of SSPANI reached 35% (wt%) in the copolymer, the dielectric constant of the copolymer was approximately 1300 at 1000 Hz, which was about 400 times larger than that of common polymer. The high dielectric constant behavior originated from the Maxwell-Wagner-Sillars (MWS) theory.
Thirdly, for the purpose of reducing dielectric loss, we choose TiO2 coated carbon nanotubes as conducting fillers, and then we prepared MCNT@TiO2/PVDF composites materials by solution mixing method. For the contrast, the TiO2 layer worked as a passivation layer, The TiO2 dielectric shells not only act as interparticle barriers to prevent from direct connection of MCNT, but they also produce excellent compatibility between the fillers and the polymer matrix and ensure the dispersion of fillers in the matrix. The resultant high performance of such new polymer composites makes them particularly attractive for technological applications in flexible high-k components such as the PCB-embedded dielectric components. To get a lower percolation threshold and high dielectric constant material, we fabricate a novel composite with high dielectric permittivity containing PVDF and graphene nanosheet by an in-situ reduction approach. The mono- or a few layers graphene nanosheets were chosen as conductive filler due to their unusual properties, such as fascinating electrical property, high thermal conductivity, good mechanical property and large specific surface area. The graphene/PVDF composite film exhibited a dielectric constant of 148 at percolation threshold of 4.08 vol% at 1000 Hz, which was a lower value. The highest dielectric permittivity of the film with 12.5 vol% of graphene fillers achieved 2080 at 1000 Hz. The dielectric behavior could be endorsed to Maxwell-Wagner-Sillars (MWS) theory at percolation.
引文
[1]邵天奇,任天令,李春晓,朱钧.高介电常数材料在半导体存储器件中的应用.[J].固体电子学研究与进展,2002,22:312-7.
[2]党之敏,王海燕,王岚.新型高温高介电无机/有机功能复合材料[J].复合材料学报,2005,22:9-15.
[3]李杰,韦平,汪根林.高介电复合材料及其介电性能的研究[J].绝缘材料,2003,12:3-6.
[4]殷之文主编.电介质物理学(第二版).北京:[M].科学出版社,2003.
[5]BAI Y, CHENG Z Y, BHARTI V, et al. High-dielectric-constant ceramic-powder polymer composites [J]. Applied Physics Letters,2000,76(25):3804-6.
[6]HOMES C C, VOGT T, SHAPIRO S M, et al. Optical response of high-dielectric-constant perovskite-related oxide [J]. Science,2001,293(5530):673-6.
[7]DIETZE M, ES-SOUNI M. Structural and functional properties of screen-printed PZT-PVDF-TrFE composites [J]. Sensors and Actuators a-Physical,2008,143(2): 329-34.
[8]LEI N, XIANG MING C. Dielectric relaxations and formation mechanism of giant dielectric constant step in CaCu3Ti4O12 ceramics [J]. Applied Physics Letters,2007, 91(12):122905.
[9]NI L, CHEN X M. Enhancement of Giant Dielectric Response in CaCu3Ti4O12 Ceramics by Zn Substitution [J]. Journal of the American Ceramic Society,93(1):184-9.
[10]BOCQUET J F, CHHOR K, POMMIER C. Barium titanate powders synthesis from solvothermal reaction and supercritical treatment [J]. Materials Chemistry and Physics, 1999,57(3):273-80.
[11]赵文元,赵文明,王亦军.聚合物材料的电学性能及应用.[M].北京:世界工业出版社,2006,
[12]ARBATTI M, SHAN X, CHENG Z Y. Ceramic-Polymer Composites with High Dielectric Constant [J]. Advanced Materials,2007,19(10):1369-72.
[13]AMARAL F, RUBINGER C P L, HENRY F, et al. Dielectric properties of polystyrene-CCTO composite [J]. Journal of Non-Crystalline Solids,2008,354(47-51): 5321-2.
[14]WANG F, ZHOU D, HU Y. Preparation and dielectric properties of CaCu3Ti4O12-polyethersulfone composites [J]. physica status solidi (a),2009,206(11): 2632-6.
[15]DANG Z M, WANG H Y, XU H P. Influence of silane coupling agent on morphology and dielectric property in BaTiO3/polyvinylidene fluoride composites [J]. Applied Physics Letters,2006,89(11):112902-4
[16]LU J X, MOON K S, KIM B K, et al. High dielectric constant polyaniline/epoxy composites via in situ polymerization for embedded capacitor applications [J]. Polymer, 2007,48(6):1510-6.
[17]KIM P, DOSS N M, TILLOTSON J P, et al. High Energy Density Nanocomposites Based on Surface-Modified BaTiO3 and a Ferroelectric Polymer [J]. ACS Nano,2009, 3(9):2581-92.
[18]NAN C W. PHYSICS OF INHOMOGENEOUS INORGANIC MATERIALS [J]. Progress in Materials Science,1993,37:1-116.
[19]NAN C W. Comment on Effective dielectric function of a random medium [J]. Physical Review B,2001,63(17):176201-3.
[20]PECHARROMAN C, ESTEBAN-BETEGON F, BARTOLOME J F, et al. New percolative BaTiO3-Ni composites with a high and frequency-independent dielectric constant (approximate to 80,000) [J]. Advanced Materials,2001,13(20):1541-4.
[21]PECHARROMAN C, MOYA J S. Experimental evidence of a giant capacitance in insulator-conductor composites at the percolation threshold [J]. Advanced Materials, 2000,12(4):294-7.
[22]WU J, MCLACHLAN D S. Percolation exponents and thresholds obtained from the nearly ideal continuum percolation system graphite-boron nitride [J]. Physical Review B, 1997,56(3):1236-48.
[23]WU J, MCLACHLAN D S. Scaling behavior of the complex conductivity of graphite-boron nitride percolation systems [J]. Physical Review B,1998,58(22): 14880-87.
[24]YANG R, WONG C P. Novel ultra-high dielectric constant polymer based composite for embedded capacitor application; proceedings of the Polymers and Adhesives in Microelectronics and Photonics,2002 POLYTRONIC 2002 2nd International IEEE Conference on, F,2002 [C].
[25]QI L, LEE B, CHEN S, et al. High-Dielectric-Constant Silver-Epoxy Composites as Embedded Dielectrics [J]. Advanced Materials,2005,17(14):1777-81.
[26]ZHENG W, LU X F, WANG W, et al. Fabrication of novel Ag nanowires/poly(vinylidene fluoride) nanocomposite film with high dielectric constant [J]. Physica Status Solidi a-Applications and Materials Science,207(8):1870-3.
[27]DANG Z M, PENG B, XIE D, et al. High dielectric permittivity silver/polyimide composite films with excellent thermal stability [J]. Applied Physics Letters,2008, 92(11):112910-2.
[28]DANG Z M, LIN Y H, NAN C W. Novel ferroelectric polymer composites with high dielectric constants [J]. Advanced Materials,2003,15(19):1625-29.
[29]WANG C C, SONG J F, BAO H M, et al. Enhancement of electrical properties of ferroelectric polymers by polyaniline nanofibers with controllable conductivities [J]. Advanced Functional Materials,2008,18(8):1299-306.
[30]HO C H, LIU C D, HSIEH C H, et al. High dielectric constant polyaniline/poly(acrylic acid) composites prepared by in situ polymerization [J]. Synthetic Metals,2008,158(15): 630-7.
[31]RUBINGER C P L, FAEZ R, COSTA L C, et al. Dielectric properties of PANI/PSS blends obtained by in situ polymerization technique [J]. Polymer Bulletin,2008,60(2-3): 379-86.
[32]LIANG S W, CLAUDE J, XU K, et al. Synthesis of dumbbell-shaped triblock structures containing ferroelectric polymers and oligoanilines with high dielectric constants [J]. Macromolecules,2008,41(17):6265-8.
[33]PANWAR V, KANG B, PARK J-O, et al. Study of dielectric properties of styrene-acrylonitrile graphite sheets composites in low and high frequency region [J]. European Polymer Journal,2009,45(6):1777-84.
[34]HE F, LAU S, CHAN H L, et al. High Dielectric Permittivity and Low Percolation Threshold in Nanocomposites Based on Poly(vinylidene fluoride) and Exfoliated Graphite Nanoplates [J]. Advanced Materials,2009,21(6):710-5.
[35]DANG Z M, WANG L, YIN Y, et al. Giant dielectric permittivities in functionalized carbon-nanotube/electroactive-polymer nanocomposites [J]. Advanced Materials,2007, 19(6):852-7.
[36]DANG Z M, SHEN Y, FAN L Z, et al. Dielectric properties of carbon fiber filled low-density polyethylene [J]. Journal of Applied Physics,2003,93(9):5543-5.
[37]DONG L, XIONG C, QUAN H, et al. Polyvinyl-butyral/lead zirconate titanates composites with high dielectric constant and low dielectric loss [J]. Scripta Materialia, 2006,55(9):835-7.
[38]ZHANG Q M, LI H F, POH M, et al. An all-organic composite actuator material with a high dielectric constant [J]. Nature,2002,419(6904):284-7.
[39]POPIELARZ R, CHIANG C K, NOZAKI R, et al. Dielectric Properties of Polymer/Ferroelectric Ceramic Composites from 100 Hz to 10 GHz [J]. Macromolecules, 2001,34(17):5910-5.
[40]HUANG C, ZHANG Q M. Fully functionalized high-dielectric-constant nanophase polymers with high electromechanical response [J]. Advanced Materials,2005,17(9): 1153-58.
[41]WANG J W, SHEN Q D, YANG C Z, et al. High dielectric constant composite of P(VDF-TrFE) with grafted copper phthalocyanine oligomer [J]. Macromolecules,2004, 37(6):2294-8.
[42]MOORE G E. Progress in digital integrated electronics. [J]. EEE IEDM Tech Dig,1975, 11.
[43]关振铎,张中太,焦金生.无机材料物理性能(第一版).[M].北京:清华大学出版社,1992.
[44]XU JW W C. Effects of the Low Loss Polymers on the Dielectrie Behavior of Novel Aluminum-filled High-K Nano-composites. [J].9th Int'l Symposium onAdvanced Packaging Materials,2004,158-70.
[45]何曼君,陈维孝,懂西侠.高分子物理[M].[J].北京:清华大学出版社,1988.
[46]况延香.集成化是无源元件发展的必然趋势[J].世界产品与技术,2003,5:30-3.
[47]LI G C, PANG S P, PENG H R, et al. Templateless and surfactantless route to the synthesis of polyaniline nanofibers [J]. Journal of Polymer Science Part a-Polymer Chemistry,2005,43(17):4012-5.
[48]PANWAR V, KANG B, PARK J O, et al. Study of dielectric properties of styrene-acrylonitrile graphite sheets composites in low and high frequency region [J]. European Polymer Journal,2009,45(6):1777-84.
[49]苑金凯,党智敏.全有机电活性复合材料的研究进展[J].绝缘材料,2007,40:(22-6.
[50]SINGH V, KULKARNI A R, MOHAN T R R. Dielectric properties of aluminum-epoxy composites [J]. Journal of Applied Polymer Science,2003,90(13):3602-8.
[51]晁单明.电活性聚合物的分子设计、合成及性质研究[D].长春:吉林大学化学学院,2008.
[52]DANILINA L I, TELESHOV E N, PRAVEDNIKOV A N. The thermal degradation of aromatic polysulphones [J]. Polymer Science USSR,1974,16(3):672-80.
[53]MATHEWS R G, SCHWARTZ R D, PEAFFENBERGER C D, et al. Polyphenyl ether sulfones:Thermally stable polar phases for gas chromatography [J]. Journal of Chromatography A,1974,99:51-61.
[54]CUDBY M E A, FEASEY R G, JENNINGS B E, et al. Synthesis of poly(arylene sulphones) by polycondensation of arylsulphonyl chlorides under friedel-crafts conditions [J]. Polymer,1965,6(11):589-601.
[55]PIERACCI J, CRIVELLO J V, BELFORT G. UV-assisted graft polymerization of N-vinyl-2-pyrrolidinone onto poly(ether sulfone) ultrafiltration membranes using selective UV wavelengths [J]. Chemistry of Materials,2002,14(1):256-65.
[56]SON W K, YOO H J, HWANG T S, et al. Synthesis and characteristics of aminated poly(arylene ether sulfone) as thermostable anion exchanger [J]. Polymer-Korea,2002, 26(1):1-8.
[57]HASIOTIS C, QINGFEND L, DEIMEDE V, et al. Development and characterization of acid-doped polybenzimidazole/sulfonated polysulfone blend polymer electrolytes for fuel cells [J]. Journal of the Electrochemical Society,2001,148(5):A513-A9.
[58]SEKKAK N, MAS A, BERRADA M, et al. Polysulfone membranes and modified polysulfones for the deshydration of ethanol by pervaporation [J]. European Polymer Journal,2001,37(8):1543-51.
[59]WANG Z G, CHEN T L, XU J P. Gas and water vapor transport through a series of novel poly(aryl ether sulfone) membranes [J]. Macromolecules,2001,34(26):9015-22.
[60]POUGET J P, LARIDJANI M, JOZEFOWICZ M E, et al. Structural aspects of the polyaniline family of electronic polymers [J]. Synthetic Metals,1992,51(1-3):95-101.
[61]POUGET J P, JOZEFOWICZ M E, EPSTEIN A J, et al. X-ray structure of polyaniline [J]. Macromolecules,1991,24(3):779-89.
[62]LIU H K, SHIH C C, WANG G P, et al. EPR studies of blends of polyaniline with poly(methyl methacrylate-co-glycidyl methacrylate iminodiacetic acid) [J]. Synthetic Metals,2005,151(3):256-60.
[63]MACDIARMID A G, MU S-L, SOMASIRI N L D, et al. Electrochemical Characteristics of polyaniline Cathodes and Anodes in Aqueous Electrolytes [J]. Molecular Crystals and Liquid Crystals,1985,121:187-90.
[64]YANG J S, SWAGER T M. Porous Shape Persistent Fluorescent Polymer Films:as An Approach to TNT Sensory Materials [J]. Journal of the American Chemical Society, 1998,120(21):5321-2.
[65]YANG J S, SWAGER T M. Fluorescent Porous Polymer Films as TNT Chemosensors: Electronic and Structural Effects [J]. Journal of the American Chemical Society,1998, 120(46):11864-73.
[66]SWAGER T M. The Molecular Wire Approach to Sensory Signal Amplification [J]. Accounts of Chemical Research,1998,31(5):201-7.
[67]MARSELLA M J, NEWLAND R J, CARROLL P J, et al. lonoresistivity as a highly sensitive sensory probe:investigations of polythiophenes functionalized with calix[4]arene-based ion receptors [J]. Journal of the American Chemical Society,1995, 117(39):9842-8.
[68]LECLERC M. Optical and Electrochemical Transducers Based on Functionalized Conjugated Polymers [J]. Advanced Materials,1999,11(18):1491-8.
[69]CRAWFORD K B, GOLDFINGER M B, SWAGER T M. Na+ Specific Emission Changes in an Ionophoric Conjugated Polymer [J]. Journal of the American Chemical Society,1998,120(21):5187-92.
[70]BOLDEA A, LEVESQUE I, LECLERC M. Controlled ionochromism with polythiophenes bearing crown ether side chains [J]. Journal of Materials Chemistry,1999, 9(9):2133-8.
[71]YAMAUCHI A, HAYASHITA T, NISHIZAWA S, et al. Benzo-15-crown-5 Fluoroionophore/y-Cyclodextrin Complex with Remarkably High Potassium Ion Sensitivity and Selectivity in Water [J]. Journal of the American Chemical Society,1999, 121(10):2319-20.
[72]XIA W-S, SCHMEHL R H, LI C-J. A Highly Selective Fluorescent Chemosensor for K+ from a Bis-15-Crown-5 Derivative [J]. Journal of the American Chemical Society,1999, 121(23):5599-600.
[73]KAYNAK A, UNSWORTH J, CLOUT R, et al. A study of microwave transmission, reflection, absorption, and shielding effectiveness of conducting polypyrrole films [J]. Journal of Applied Polymer Science,1994,54(3):269-78.
[74]FURUKAWA Y, UEDA F, HYODO Y, et al. Vibrational spectra and structure of polyaniline [J]. Macromolecules,1988,21(5):1297-305.
[75]CHAO D M, MA X B, LU X F, et al. Design, synthesis and characterization of novel electroactive polyamide with amine-capped aniline pentamer in the main chain via oxidative coupling polymerization [J]. Journal of Applied Polymer Science,2007,104(3): 1603-8.
[76]CHAO D M, LU X F, CHEN J Y, et al. New method of synthesis of electroactive polyamide with amine-capped aniline pentamer in the main chain [J]. Journal of Polymer Science Part a-Polymer Chemistry,2006,44(1):477-82.
[77]DUST J M, FANG Z H, HARRIS J M. Proton NMR characterization of poly(ethylene glycols) and derivatives [J]. Macromolecules,1990,23(16):3742-6.
[78]HOOPER K A, KOHN J. Diphenolic Monomers Derived from the Natural Amino Acid α-L-Tyrosine:An Evaluation of Peptide Coupling Techniques [J]. Journal of Bioactive and Compatible Polymers,1995,10(4):327-40.
[79]CHAO D M, LU X F, CHEN J Y, et al. Synthesis and characterization of electroactive polyamide with amine-capped aniline pentamer and ferrocene in the main chain by oxidative coupling polymerization [J]. Polymer,2006,47(8):2643-8.
[80]CHAO D M, MA X B, LIU Q H, et al. Synthesis and characterization of electroactive copolymer with phenyl-capped aniline tetramer in the main chain by oxidative coupling polymerization [J]. European Polymer Journal,2006,42(11):3078-84.
[81]CHRISTIAN B, PATRICK Q, PHILIPPE T. Microwave characterization of filled polymers [J]. Journal of Applied Physics,2001,89(8):4532-40.
[82]ZOIS H, APEKIS L, MAMUNYA Y P. Dielectric properties and morphology of polymer composites filled with dispersed iron [J]. Journal of Applied Polymer Science,2003, 88(13):3013-20.
[83]DANG Z M, FAN L Z, SHEN Y, et al. Study on dielectric behavior of a three-phase CF/(PVDF+BaTiO3) composite [J]. Chemical Physics Letters,2003,369(1-2):95-100.
[84]姚胜红.碳纳米管/聚偏氟乙烯高介电纳米复合材料的显微结构控制与介电性能的关联[D].北京:北京化工大学材料科学与工程,2009.
[85]HUANG J X, KANER R B. Nanofiber formation in the chemical polymerization of aniline:A mechanistic study [J]. Angewandte Chemie-International Edition,2004,43(43): 5817-21.
[86]TAMURA R, LIM E, MANAKA T, et al. Analysis of pentacene field effect transistor as a Maxwell-Wagner effect element [J]. Journal of Applied Physics,2006,100(11): 114515-7.
[87]SADIGHI J P, SINGER R A, BUCHWALD S L. Palladium-Catalyzed Synthesis of Monodisperse, Controlled-Length, and Functionalized Oligoanilines [J]. Journal of the American Chemical Society,1998,120(20):4960-76.
[88]ALVARO M, APRILE C, FERRER B, et al. Functional molecules from single wall carbon nanotubes. Photoinduced solubility of short single wall carbon nanotube residues by covalent anchoring of 2,4,6-triarylpyrylium units [J]. Journal of the American Chemical Society,2007,129(17):5647-55.
[89]OSSWALD S, HAVEL M, GOGOTSI Y. Monitoring oxidation of multiwalled carbon nanotubes by Raman spectroscopy [J]. Journal of Raman Spectroscopy,2007,38(6): 728-36.
[90]WU B Y, HOU S H, YIN F, et al. Amperometric glucose biosensor based on multilayer films via layer-by-layer self-assembly of multi-wall carbon nanotubes, gold nanoparticles and glucose oxidase on the Pt electrode [J]. Biosensors & Bioelectronics, 2007,22(12):2854-60.
[91]KIM S W, KIM J K, LEE S H, et al. Thermophysical properties of multi-walled carbon nanotube-reinforced polypropylene composites [J]. International Journal of Thermophysics,2006,27(1):152-60.
[92]AGRAWAL M, PICH A, ZAFEIROPOULOS N E, et al. Fabrication of hollow titania microspheres with tailored shell thickness [J]. Colloid and Polymer Science,2008, 286(5):593-601.
[93]AGRAWAL M, PICH A, GUPTA S, et al. Temperature sensitive hybrid microgels loaded with ZnO nanoparticles [J]. Journal of Materials Chemistry,2008,18(22):2581-6.
[94]AGRAWAL M, PICH A, GUPTA S, et al. Synthesis of novel tantalum oxide sub-micrometer hollow spheres with tailored shell thickness [J]. Langmuir,2008,24(3): 1013-8.
[95]CHEN L C, HO Y C, GUO W S, et al. Enhanced visible light-induced photoelectrocatalytic degradation of phenol by carbon nanotube-doped TiO2 electrodes [J]. Electrochimica Acta,2009,54(15):3884-91.
[96]ZHANG F J, CHEN M L, OH W C. Fabrication of Carbon Nanotube/TiO2 Composite Photocatalysts and Their Electro-photolysis for Organic Dye [J]. Asian Journal of Chemistry,2009,21(9):7077-92.
[97]WU Y C, LIU X L, YE M, et al. Preparation and properties of carbon nanotube-TiO2 nanocomposites [J]. Acta Physico-Chimica Sinica,2008,24(1):97-102.
[98]OH W C, CHEN M L. Synthesis and characterization of CNT/TiO2 composites thermally derived from MWCNT and titanium(IV) n-butoxide [J]. Bulletin of the Korean Chemical Society,2008,29(1):159-64.
[99]CHEN M, ZHANG F J, OH W. Photocatalytic Decomposition of MB Solution by CNT/TiO2 Composites Prepared from MWCNT and Titanium Source [J]. Proceedings of the 2nd International Conference on Asian-European Environmental Technology and Knowledge Transfer,2008,190-2.
[100]SHEN Y, LIN Y H, LI M, et al. High dielectric performance of polymer composite films induced by a percolating interparticle barrier layer [J]. Advanced Materials,2007, 19(10):1418-22.
[101]YANG C, LIN Y H, NAN C W. Modified carbon nanotube composites with high dielectric constant, low dielectric loss and large energy density [J]. Carbon,2009,47(4): 1096-101.
[102]SHEN Y, LIN Y H, LI M, et al. High dielectric performance of polymer composite films induced by a percolating interparticle barrier layer [J]. Advanced Materials,2007, 19(10):1418-22.
[103]SHEN Y, LIN Y H, NAN C W. Interfacial effect on dielectric properties of polymer nanocomposites filled with core/shell-structured particles [J]. Advanced Functional Materials,2007,17(14):2405-10.
[104]COTE L J, KIM F, HUANG J. Langmuir-Blodgett Assembly of Graphite Oxide Single Layers [J]. Journal of the American Chemical Society,2008,131(3):1043-9.
[105]HUMMERS W S, OFFEMAN R E. Preparation of Graphitic Oxide [J]. Journal of the American Chemical Society,1958,80(6):1339-9.
[106]DU X S, XIAO M, MENG Y Z, et al. Direct synthesis of poly(arylenedisulfide)/carbon nanosheet composites via the oxidation with graphite oxide [J]. Carbon,2005,43(1): 195-7.
[107]HE H, FORSTER M, KLINOWSKI J. Structure of Graphite Oxide Revisited [J]. The Journal of Physical Chemistry B,1998,102(23):4477-82.
[108]SONG Y, QU K, ZHAO C, et al. Graphene Oxide:Intrinsic Peroxidase Catalytic Activity and Its Application to Glucose Detection [J]. Advanced Materials,22(19): 2206-10.
[109]MURUGARAJ P, MAINWARING D, MORA-HUERTAS N. Dielectric enhancement in polymer-nanoparticle composites through interphase polarizability [J]. Journal of Applied Physics,2005,98(5):054304-6.