电、磁场处理对聚烯烃基纳米复合材料介电性能的影响
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摘要
复合材料由两种或两种以上的材料组合而成,其中各组分在性能上互相取长补短,产生协同效应,使复合材料的综合性能优于原组成材料,甚至可以衍生出一些新功能。聚烯烃/无机填料复合材料是目前应用非常广泛的一类复合材料,其性能由聚烯烃基体和无机填料的性能、无机填料的添加量及其在基体中的分布状态等决定。由于聚烯烃属于软物质,其结构与性能容易受到外场的影响,而且微米、纳米尺度的无机填料又可能对某些外场的刺激做出响应,因此外场对聚烯烃基复合材料结构与性能影响的研究得到了国内外许多科研人员的关注,外场处理可能成为辅助制备新型、高性能聚烯烃基复合材料的有效方法。
本课题在聚烯烃/碳纳米管、聚烯烃/纳米碳化硅复合材料的热成型加工过程中分别单独施加电场、磁场或同时施加电场和磁场,研究了电、磁场处理对复合材料介电性能的影响及规律,并对电、磁场的作用机理进行了分析。研究结果表明:电场和磁场单独处理都能使碳纳米管在聚烯烃中沿外场方向取向及改变纳米SiC在聚烯烃中的分布状态,导致纳米复合材料的电导率、介电常数和损耗角正切值等发生不同程度变化;随着聚烯烃熔融粘度的减小和预处理电场强度的增加,电、磁场处理对纳米复合材料性能的影响表现得更明显;非均匀电场处理对纳米复合材料的影响效果远好于均匀电场处理;电场和磁场处理对同一纳米复合材料的作用效果不同,电场和磁场联合处理的效果可能具有协同性,也可能接近于其中一种场单独作用的效果,结果主要取决于聚烯烃和填料的属性。
Matrix composites consist of two or more than two materials, and the performance of each component produces mutual complementary and synergistic effects, making the comprehensive performance of composites better than Original constituent materials, even deriving some new functions. At present ,Polyolefin /Inorganic filler matrix composite is a very extensive class of composite materials, whose performance depends on the performance of polyolefin and Inorganic filler、the substitutability of Inorganic filler and its distribution state, etc. As a soft-matter, the structure and performance of polyolefin are easily affected by the external field stimulation, and the micron, nanometer scale inorganic filler is respond sensitively to the external field stimulation, therefore, the research about the effect on the structure and performance of Polyolefin matrix composites by the external field stimulation draws many domestic scientific researchers' attention, and the external field processing may become an effective method of making auxiliary preparations of new, high-performance Polyolefin matrix composites.
This subject separately applied electric field and magnetic field or applied both at the same time on Polyolefin/CNTs、Polyolefin、nano-SiC matrix composites in the hot-press-molding process ,studied the effects and regular patterns of magnetic、electric treatment on the properties of matrix composites and analyzed the function mechanism. The results show that : separately applying electric field and magnetic field makes Polyolefin/CNTs in Polyolefin orient along the external field stimulation direction and changes the distribution state of nano-SiC ,leading to the conductivity、dielectric constant dissipation factor of nano-composites varying in degree; with the decrease of melting viscosity and the increase of pretreatment electric intensity, effect of magnetic field and electric field on properties of Polyolefin matrix composites is more obvious; the effect of non-uniform electric field processing on nano-composites is much better than that of uniform electric field processing; the effects of electric field and magnetic field processing on the same nano-composites are different, the effect of electric field and magnetic field joint processing either may have the synergy, or get close to the effect of either separate field, and the results mainly depend on the properties of Polyolefin and Inorganic filler.
本课题在聚烯烃/碳纳米管、聚烯烃/纳米碳化硅复合材料的热成型加工过程中分别单独施加电场、磁场或同时施加电场和磁场,研究了电、磁场处理对复合材料介电性能的影响及规律,并对电、磁场的作用机理进行了分析。研究结果表明:电场和磁场单独处理都能使碳纳米管在聚烯烃中沿外场方向取向及改变纳米SiC在聚烯烃中的分布状态,导致纳米复合材料的电导率、介电常数和损耗角正切值等发生不同程度变化;随着聚烯烃熔融粘度的减小和预处理电场强度的增加,电、磁场处理对纳米复合材料性能的影响表现得更明显;非均匀电场处理对纳米复合材料的影响效果远好于均匀电场处理;电场和磁场处理对同一纳米复合材料的作用效果不同,电场和磁场联合处理的效果可能具有协同性,也可能接近于其中一种场单独作用的效果,结果主要取决于聚烯烃和填料的属性。
Matrix composites consist of two or more than two materials, and the performance of each component produces mutual complementary and synergistic effects, making the comprehensive performance of composites better than Original constituent materials, even deriving some new functions. At present ,Polyolefin /Inorganic filler matrix composite is a very extensive class of composite materials, whose performance depends on the performance of polyolefin and Inorganic filler、the substitutability of Inorganic filler and its distribution state, etc. As a soft-matter, the structure and performance of polyolefin are easily affected by the external field stimulation, and the micron, nanometer scale inorganic filler is respond sensitively to the external field stimulation, therefore, the research about the effect on the structure and performance of Polyolefin matrix composites by the external field stimulation draws many domestic scientific researchers' attention, and the external field processing may become an effective method of making auxiliary preparations of new, high-performance Polyolefin matrix composites.
This subject separately applied electric field and magnetic field or applied both at the same time on Polyolefin/CNTs、Polyolefin、nano-SiC matrix composites in the hot-press-molding process ,studied the effects and regular patterns of magnetic、electric treatment on the properties of matrix composites and analyzed the function mechanism. The results show that : separately applying electric field and magnetic field makes Polyolefin/CNTs in Polyolefin orient along the external field stimulation direction and changes the distribution state of nano-SiC ,leading to the conductivity、dielectric constant dissipation factor of nano-composites varying in degree; with the decrease of melting viscosity and the increase of pretreatment electric intensity, effect of magnetic field and electric field on properties of Polyolefin matrix composites is more obvious; the effect of non-uniform electric field processing on nano-composites is much better than that of uniform electric field processing; the effects of electric field and magnetic field processing on the same nano-composites are different, the effect of electric field and magnetic field joint processing either may have the synergy, or get close to the effect of either separate field, and the results mainly depend on the properties of Polyolefin and Inorganic filler.
引文
[1]覃奇贤,刘淑兰.复合材料与表面处理技术[J].电镀与精饰,2009,31(8):30-33.
[2]于研,张长春,李世辉,等.场致作用在聚合物加工过程中的应用研究[J].塑料科技,2004,(1):26-29.
[3]代威,傅正义,卢北平,等.电磁场在材料科学中的应用[J].国外建材科技,2004,25 (3):7-10.
[4]李兰中.关于带电粒子在复合场中运动问题的解析[J].科技创新导报,2010,(9):250.
[5] Zhenni Zhou,Guohong Zhang,Kaiming Wu.Effect of strong magnetic field on isothermal transformation of degenerate pearlite in an Fe-C-Mo alloy[J].Acta Metall.Sin.2010,23(4):248-254.
[6] Gerzeski R H.Mechanical property enhancement of an EPON 828-TETA epoxy resin system via magnetic fields co-processing[C].Soc.For the Advancement of Material and Process Engineering . 36th International SAMPE Symp,1991,33(2):63-69.
[7]陈贻瑞,范震冈,方洞浦,等.磁场对酚醛环氧树脂交联的影响[J].高等学校化学学报,1987,12(8):1136-1140.
[8]赵克熙.原苏联芳纶复合材料研究进展及其在固体发动机壳体上的应用[J].航天情报研究系列报道,1993,(8):532-546.
[9]王军,陈卫东,贾绍义,等.磁化技术在化工领域中的应用[J].化学工业与工程,2000,17(3):177-183.
[10]胡晖,高红,贾绍义.磁场对物质理化性质的影响[J].磁性材料及器件,2000,31(3):36-41.
[11]王国全.磁化学研究进展及其应用[J].化工进展,1998,(1):30-32.
[12]苏致兴,姚芳莲,张萍.磁场对醋酸乙烯酯乳液聚合反应的影响[J].高等学校化学学报,1989,10(6):667-669.
[13]周朝华,苏致兴.磁场对聚合物立体构型影响的研究(Ⅰ)—聚甲基丙烯酸甲酯[J].高等学校化学学报,1981,2(3):372-376.
[14]宁超峰,李兴远.磁场存在下制备的聚氨酯弹性体的形态[J].合成橡胶工业,2000,23(5):320-321.
[15]刘强,崔建忠,刘晓涛,等.磁场对熔融结晶聚丙烯薄膜晶体结构的影响[J].东北大学学报(自然科学版).2005,26(2):125-128.
[16]韩宝忠,郭文敏,李忠华.碳化硅/低密度聚乙烯复合材料的直流伏安特性[J].复合材料学报,2008,25(5):19-24.
[17]韩宝忠.聚合物基非线性复合材料制备过程中施加电、磁场对其性能及微观结构的影响[D].哈尔滨:哈尔滨理工大学(博士后研究工作报告),2008:53-76.
[18]金福云,段成志.磁场中的有机反应[J].西南民族学院学报(自然科学版),1996,22(1):89-92.
[19]黄开金,谢长生,张邦文.磁场诱导排列的纳米Fe/环氧树脂基有序纳米复合材料的电性能[J].中国粉体工业,2008,(4):11-15.
[20]杜新胜,马利,陈秀娣.磁场环境下聚苯胺的合成与性能研究[J].青岛科技大学学报(自然科学版),2008,29(5):432-436.
[21]杜新胜,陈秀娣,马利.磁场环境下氧化剂和掺杂剂浓度对聚苯胺性能的影响[J].胶体与聚合物,2008,26(2):25-28.
[22]常方高,王丹丹,胡棚,等.磁场对Ni/硅橡胶复合材料交流电导率及介电性质的影响[J].复合材料学报,2010,27(5):13-17.
[23]马凤莲.磁场处理对聚乙烯基复合材料介电性能和微观结构的影响[D].哈尔滨:哈尔滨理工大学(硕士学位论文),2009:35-49.
[24]冯涛.磁场处理对热固性复合材料介电性能及微观结构的影响[D].哈尔滨:哈尔滨理工大学(硕士学位论文),2009:22-49.
[25] Baozhong HAN,Fenglian MA,Tao Feng,et al.Effect of Magnetic Field Treatment on Properties of Thermosetting Polymers and Their Composites[C] . The 9th International Conference on Properties and Applications of Dielectric Materials,Harbin,China,July 19-23,2009:1158-1162.
[26] Fenglian MA,Baozhong HAN,Yanjie WANG,et al.Effect of Magnetic Conductivity Properties of Carbon Filler/LDPE Composites[C] . The 9th International Conference on Properties and Applications of Dielectric Materials ,Harbin,China,July 19-23,2009:1192-1195.
[27]肖学山,董远达,莫志深.电场对聚合物形成的影响研究进展[J].材料学报,2000,14(11):53-54.
[28] Tsuchida,Eishun,Irle,et al.Journal of Polymer Science,1973.11(4):789.
[29] Weatherley L R , Etuk B , Murray K R . Powder Technology Second Symposium on Advances in Particulate Technology.1991,65(1-3):227.
[30] SerPico J M,et al.Effect Of Block Copolymer On The Electric Field Induced Morphology Of Polymer Blends[J].Macromolecules,1991,24:6879-6881.
[31] SerPico J M , et al . Electric Field-Induced Morphologies In Diblock Copolymer Containing Polymer Blends[J].Macromolecule,1992,(25):6373.
[32]肖学山,莫志深,董远达,等.高真空强静电场对熔融结晶尼龙-11晶体结构的影响[J].高分子材料科学与工程,2002,18(1):165-167.
[33]肖学山,董远达,乔秀颖,等.高真空强静电场下聚合物薄膜微晶生长形态转变研究[J].高分子学报,2001,(2):261-264.
[34]肖学山,董远达,莫志深,等.电场诱导下的间规聚苯乙烯晶体结构和形态研究[J].高分子材料科学与工程,2002,18(2):90-92.
[35]李从武,潘昂.外电场下光聚合反应动力学的表征方法[J].高分子学报,1994,(1):108-112.
[36]朱成康,姚春燕,彭伟.电场效应与光敏树脂中纤维取向的研究[J].浙江工业大学学报,2004,32(1):69-72.
[37]丁强.环氧树脂浇注绝缘的预电应力效应[D].哈尔滨:哈尔滨理工大学(硕士学位论文),2002:11-31.
[38] Chang Ming Li,Wen Min Guo,Bao Zhong Han,Zhong Hua Li.The electrical pre-stress effect on field dependent conductivity of the polyethylene and carborundum composite[C].ICPADM 2006,Bali,Indonesia:751-754.
[39] Jong-Yeol Shin,In-Bum Jeong,Hyun-Min Choi,et al.Electrical Insulating Properties of Nano-composites According to Additive[C] . The 9th International Conference on Properties and Applications of Dielectric Materials,Harbin,China,July 19-23,2009:841-844.
[40]张洪艳,电场诱导下制备不饱和树脂/纳米石墨微片复合导电材料[D].厦门:华侨大学(博士论文),2000:25-60.
[41]周歧发,张清琦,张进修,等.电场对PT/Epoxy纳米复合材料性能的影响[J].中国科学(A辑),1998,28(8):721-726.
[42] Zhou Qi fa,Zhang Jin xiu,Cheng Zhong yang,et al.Effect of Electric Field on Properties of 0-3 Nano-Composites with PbTiO3 Ultrafine Particles[J].中山大学学报(自然科学版),1997,36(2):54-57.
[43] Kenji Hata,Sumio lijima,et al.Water-assisted highly efficient synthesis of impurity-free single-walled carbon nano-tubes[J].Science ,2004,306:1362
[44]杨继敏,孙培梅,童军武,等.碳纳米管/聚合物纳米复合材料研究进展[J].金属材料与冶金工程,2010,38(3):60-63.
[45] (美)M.麦亚潘(M. Meyyappan)主编.碳纳米管—科学与应用[M].刘忠范等译.北京:科学出版社,2007:2-3.
[46]戴剑锋,高建龙,乔宪武,等.CNTs定向排列的CNTs/PMMA电导率低突增效应研究.材料工程,2008,(10):1-4.
[47]朱建军,庞海,刘素英,等.SiC的光谱特性研究[J].稀有金属,1999,23(1):35-41.
[48] Kimura T,Ago H,Tobita M,et al.Polymer Composites of Carbon Nanotubes Aligned by a Magnetic Field[J].Adv Mater, 2002, 14(19):1380- 1383.
[49] Fujiwara M,Oki E,Hamada M,et al.Magnetic Orientation and Magnetic Properties of a Single Carbon Nanotube[J].J Phys Chem A,2001,105(18):4383-4386.
[50] Steinert B W,Dean D R.Magnetic field alignment and electrical properties of solution cast PET–carbon nanotube composite films[J].Polymer,2009,50(3):898-904.
[51] Camponeschi E,Vance R,Al Haikc M,et al.Properties of carbon nanotube–polymer composites aligned in a magnetic field[J] . Carbon ,2007,45(10):2037-2046.
[52] Martin C A,Sandlera J K W,Windle A H,et al.Electric field-induced aligned multi-wall carbon nanotube networks in epoxy composites [J].Polymer,2005,46(3):877-886.
[53] Henning T H,Salama F.Carbon in the universe[J].Seienee,1998,282:2204-2210.
[2]于研,张长春,李世辉,等.场致作用在聚合物加工过程中的应用研究[J].塑料科技,2004,(1):26-29.
[3]代威,傅正义,卢北平,等.电磁场在材料科学中的应用[J].国外建材科技,2004,25 (3):7-10.
[4]李兰中.关于带电粒子在复合场中运动问题的解析[J].科技创新导报,2010,(9):250.
[5] Zhenni Zhou,Guohong Zhang,Kaiming Wu.Effect of strong magnetic field on isothermal transformation of degenerate pearlite in an Fe-C-Mo alloy[J].Acta Metall.Sin.2010,23(4):248-254.
[6] Gerzeski R H.Mechanical property enhancement of an EPON 828-TETA epoxy resin system via magnetic fields co-processing[C].Soc.For the Advancement of Material and Process Engineering . 36th International SAMPE Symp,1991,33(2):63-69.
[7]陈贻瑞,范震冈,方洞浦,等.磁场对酚醛环氧树脂交联的影响[J].高等学校化学学报,1987,12(8):1136-1140.
[8]赵克熙.原苏联芳纶复合材料研究进展及其在固体发动机壳体上的应用[J].航天情报研究系列报道,1993,(8):532-546.
[9]王军,陈卫东,贾绍义,等.磁化技术在化工领域中的应用[J].化学工业与工程,2000,17(3):177-183.
[10]胡晖,高红,贾绍义.磁场对物质理化性质的影响[J].磁性材料及器件,2000,31(3):36-41.
[11]王国全.磁化学研究进展及其应用[J].化工进展,1998,(1):30-32.
[12]苏致兴,姚芳莲,张萍.磁场对醋酸乙烯酯乳液聚合反应的影响[J].高等学校化学学报,1989,10(6):667-669.
[13]周朝华,苏致兴.磁场对聚合物立体构型影响的研究(Ⅰ)—聚甲基丙烯酸甲酯[J].高等学校化学学报,1981,2(3):372-376.
[14]宁超峰,李兴远.磁场存在下制备的聚氨酯弹性体的形态[J].合成橡胶工业,2000,23(5):320-321.
[15]刘强,崔建忠,刘晓涛,等.磁场对熔融结晶聚丙烯薄膜晶体结构的影响[J].东北大学学报(自然科学版).2005,26(2):125-128.
[16]韩宝忠,郭文敏,李忠华.碳化硅/低密度聚乙烯复合材料的直流伏安特性[J].复合材料学报,2008,25(5):19-24.
[17]韩宝忠.聚合物基非线性复合材料制备过程中施加电、磁场对其性能及微观结构的影响[D].哈尔滨:哈尔滨理工大学(博士后研究工作报告),2008:53-76.
[18]金福云,段成志.磁场中的有机反应[J].西南民族学院学报(自然科学版),1996,22(1):89-92.
[19]黄开金,谢长生,张邦文.磁场诱导排列的纳米Fe/环氧树脂基有序纳米复合材料的电性能[J].中国粉体工业,2008,(4):11-15.
[20]杜新胜,马利,陈秀娣.磁场环境下聚苯胺的合成与性能研究[J].青岛科技大学学报(自然科学版),2008,29(5):432-436.
[21]杜新胜,陈秀娣,马利.磁场环境下氧化剂和掺杂剂浓度对聚苯胺性能的影响[J].胶体与聚合物,2008,26(2):25-28.
[22]常方高,王丹丹,胡棚,等.磁场对Ni/硅橡胶复合材料交流电导率及介电性质的影响[J].复合材料学报,2010,27(5):13-17.
[23]马凤莲.磁场处理对聚乙烯基复合材料介电性能和微观结构的影响[D].哈尔滨:哈尔滨理工大学(硕士学位论文),2009:35-49.
[24]冯涛.磁场处理对热固性复合材料介电性能及微观结构的影响[D].哈尔滨:哈尔滨理工大学(硕士学位论文),2009:22-49.
[25] Baozhong HAN,Fenglian MA,Tao Feng,et al.Effect of Magnetic Field Treatment on Properties of Thermosetting Polymers and Their Composites[C] . The 9th International Conference on Properties and Applications of Dielectric Materials,Harbin,China,July 19-23,2009:1158-1162.
[26] Fenglian MA,Baozhong HAN,Yanjie WANG,et al.Effect of Magnetic Conductivity Properties of Carbon Filler/LDPE Composites[C] . The 9th International Conference on Properties and Applications of Dielectric Materials ,Harbin,China,July 19-23,2009:1192-1195.
[27]肖学山,董远达,莫志深.电场对聚合物形成的影响研究进展[J].材料学报,2000,14(11):53-54.
[28] Tsuchida,Eishun,Irle,et al.Journal of Polymer Science,1973.11(4):789.
[29] Weatherley L R , Etuk B , Murray K R . Powder Technology Second Symposium on Advances in Particulate Technology.1991,65(1-3):227.
[30] SerPico J M,et al.Effect Of Block Copolymer On The Electric Field Induced Morphology Of Polymer Blends[J].Macromolecules,1991,24:6879-6881.
[31] SerPico J M , et al . Electric Field-Induced Morphologies In Diblock Copolymer Containing Polymer Blends[J].Macromolecule,1992,(25):6373.
[32]肖学山,莫志深,董远达,等.高真空强静电场对熔融结晶尼龙-11晶体结构的影响[J].高分子材料科学与工程,2002,18(1):165-167.
[33]肖学山,董远达,乔秀颖,等.高真空强静电场下聚合物薄膜微晶生长形态转变研究[J].高分子学报,2001,(2):261-264.
[34]肖学山,董远达,莫志深,等.电场诱导下的间规聚苯乙烯晶体结构和形态研究[J].高分子材料科学与工程,2002,18(2):90-92.
[35]李从武,潘昂.外电场下光聚合反应动力学的表征方法[J].高分子学报,1994,(1):108-112.
[36]朱成康,姚春燕,彭伟.电场效应与光敏树脂中纤维取向的研究[J].浙江工业大学学报,2004,32(1):69-72.
[37]丁强.环氧树脂浇注绝缘的预电应力效应[D].哈尔滨:哈尔滨理工大学(硕士学位论文),2002:11-31.
[38] Chang Ming Li,Wen Min Guo,Bao Zhong Han,Zhong Hua Li.The electrical pre-stress effect on field dependent conductivity of the polyethylene and carborundum composite[C].ICPADM 2006,Bali,Indonesia:751-754.
[39] Jong-Yeol Shin,In-Bum Jeong,Hyun-Min Choi,et al.Electrical Insulating Properties of Nano-composites According to Additive[C] . The 9th International Conference on Properties and Applications of Dielectric Materials,Harbin,China,July 19-23,2009:841-844.
[40]张洪艳,电场诱导下制备不饱和树脂/纳米石墨微片复合导电材料[D].厦门:华侨大学(博士论文),2000:25-60.
[41]周歧发,张清琦,张进修,等.电场对PT/Epoxy纳米复合材料性能的影响[J].中国科学(A辑),1998,28(8):721-726.
[42] Zhou Qi fa,Zhang Jin xiu,Cheng Zhong yang,et al.Effect of Electric Field on Properties of 0-3 Nano-Composites with PbTiO3 Ultrafine Particles[J].中山大学学报(自然科学版),1997,36(2):54-57.
[43] Kenji Hata,Sumio lijima,et al.Water-assisted highly efficient synthesis of impurity-free single-walled carbon nano-tubes[J].Science ,2004,306:1362
[44]杨继敏,孙培梅,童军武,等.碳纳米管/聚合物纳米复合材料研究进展[J].金属材料与冶金工程,2010,38(3):60-63.
[45] (美)M.麦亚潘(M. Meyyappan)主编.碳纳米管—科学与应用[M].刘忠范等译.北京:科学出版社,2007:2-3.
[46]戴剑锋,高建龙,乔宪武,等.CNTs定向排列的CNTs/PMMA电导率低突增效应研究.材料工程,2008,(10):1-4.
[47]朱建军,庞海,刘素英,等.SiC的光谱特性研究[J].稀有金属,1999,23(1):35-41.
[48] Kimura T,Ago H,Tobita M,et al.Polymer Composites of Carbon Nanotubes Aligned by a Magnetic Field[J].Adv Mater, 2002, 14(19):1380- 1383.
[49] Fujiwara M,Oki E,Hamada M,et al.Magnetic Orientation and Magnetic Properties of a Single Carbon Nanotube[J].J Phys Chem A,2001,105(18):4383-4386.
[50] Steinert B W,Dean D R.Magnetic field alignment and electrical properties of solution cast PET–carbon nanotube composite films[J].Polymer,2009,50(3):898-904.
[51] Camponeschi E,Vance R,Al Haikc M,et al.Properties of carbon nanotube–polymer composites aligned in a magnetic field[J] . Carbon ,2007,45(10):2037-2046.
[52] Martin C A,Sandlera J K W,Windle A H,et al.Electric field-induced aligned multi-wall carbon nanotube networks in epoxy composites [J].Polymer,2005,46(3):877-886.
[53] Henning T H,Salama F.Carbon in the universe[J].Seienee,1998,282:2204-2210.
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