纳米钛酸钡/环氧树脂复合材料的制备和性能研究
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摘要
现代电子科技的迅猛发展,对电子材料的介电性能提出了越来越高的要求,迫切需要具有高介电常数、低损耗、同时具有较高力学性能和可加工性能的介电材料,这就使得高介电常数材料的重要性日益显著。复合材料能兼容陶瓷粒子的高介电性能以及聚合物优良的机械性能和绝缘性,是当前介电材料领域研究的主要方向之一。将陶瓷粉体与聚合物进行复合是制备具有高介电常数且易加工的复合材料的一种很有前景的方法。这类以高介电常数的陶瓷粉未分散于三维连续的聚合物基体中形成的聚合物基复合材料在电子领域具有广泛的应用,近年来,在高储能电容器中的应用也引起了广泛关注。
     本文以环氧树脂作为基体,以纳米BaTiO_3为高介电填充组分,引入羰基铁粉为第三组分,用浇铸法制备了纳米BaTiO_3/环氧树脂二相复合材料和纳米BaTiO_3/环氧树脂/Fe三相复合材料。分别测试了其介电性能和力学性能,并对复合材料的微观形貌进行了表征。
     选择两种硅烷偶联剂对二相复合材料体系中纳米钛酸钡进行表面处理后与环氧树脂基体复合。比较偶联剂对复合材料介电性能、热性能及力学性能的影响。结果表明,采用KH550硅烷偶联剂处理后的复合材料具有较佳的介电性能及力学性能,且纳米钛酸钡在基体中分散效果也较好;纳米钛酸钡填充含量对复合材料的两相界面和介电性能有很大的影响;随着纳米BaTiO_3的加入以及含量的增加,材料体系的热分解温度有一定的提高。
     通过对三相体系介电性能的研究,结果发现:羰基铁粉的含量对材料的介电常数有显著的影响;SEM显示,羰基铁粉含量的增加有利于其在基体中均匀分散。其中羰基铁粉的加入量较低,仅为1%-7%质量分数。羰基铁粉的加入无论对较低含量还是较高含量的体系其影响基本一致,即均导致了介电常数和介电损耗的增加。在钛酸钡含量较高时,少量羰基铁粉的加入就造成了介电损耗的急剧上升。这主要是因为导电组分的加入增加了体系的电导电流,从而引起电导损耗上升。从提高材料介电性能的角度,羰基铁粉的加入提高了其介电常数,但同时也导致其介电损耗的增加。因此对三相体系需要更精确地选择第三导电组分的种类和控制其含量,以及调控它们在复合材料中的分散形貌,以达到同时改善其介电常数和介电损耗的目的。
Modern electronic technology in the rapid development of electronic materials for the dielectric properties put forward higher requirements,the urgent need for a high-k,low loss,at the same time with high mechanical and processing properties, which on the high dielectric constant materials made of the importance of the growing significantly.Composite particles can be compatible with high dielectric properties of ceramic,as well as good insulation and mechanical properties of polymers,is one of the major directions in the field of study on the dielectric material. Composite materials are prepared by filled ceramic powder into the polymer to carry out a high dielectric constant and easy processing,which is a promising method.Such high dielectric constant of ceramic powder dispersed in a row of three-dimensional polymer matrix in the form of polymer matrix composites has a wide range of applications in the field of electronics.In recent years,high-energy storage capacitors in a wide range of applications also concern.
     In this paper,nano-BaTiO_3/Epoxy composite materials and nano-BaTiO_3/ Epoxy/Fe ternary composites were prepared by casting with epoxy resin as a matrix, nano-BaTiO_3 as higher dielectric filling components,the introduction of carbonyl iron powder for the third component.
     BaTiO_3 was treated by two of the silane coupling agents on the dual system of nano-composite materials and then was mixed into epoxy matrix.Dielectric properties and mechanical properties composite material were tested.Dielectric properties,thermal properties and mechanical properties were compared of the effect by using the coupling agent composite and morphology of the composite were characterized.The results showed that the composite treated by the silane coupling agent KH550 has the best dielectric properties and mechanical properties,and nano-BaTiO_3 dispersed in the matrix in the best;The concentration of nano-BaTiO_3 particles also has an effect on the Interface and the dielectric properties of composites; The material system of thermal decomposition temperature to increase to a certain with the accession nano-BaTiO_3 particles.
     The dielectric properties of the nano-BaTiO_3 / Epoxy / Fe composites system were studied.It was found that:the content of carbonyl iron powder had significantly effected on the dielectric constant of the material,in which the addition of carbonyl iron powder was low,only 1%-7%of the mass fraction;SEM showed that carbonyl iron content in favor of the increase in the uniform dispersion matrix..The impact on the system are basically the same with the addition of carbonyl iron content of both the lower or higher,which resulted in the dielectric constant and dielectric loss increased.In a high level with barium titanate,the small amount by addition of carbonyl iron resulted in the sharp rise on dielectric loss.This was mainly due to by the addition of conductive component of the conductivity increase of the current system,which led to increase the loss of conductivity.
     From the point of improving the material properties,by the addition of carbonyl iron powder,it could improve its dielectric constant,but it also led to an increase in dielectric loss.Therefore it was needed for more accurate selection of the third component types to control their content for three-phase system,as well as the regulation and control of composite materials in the dispersed morphology.
     In order to achieve and at the same time to improve its dielectric constant and dielectric loss,further study is also needed.The results for the ceramic/polymer matrix composite materials of high dielectric applications have laid a solid foundation.
引文
[1]Kuo D.H,Chang C.C.,Wang W.K.et al.Dielectric behaviours of multi-doped BaTiO_3/epoxy composites.J.Eur.Ceram.Soc.,2001,21(9):1171-1177.
    [2]Bai Y.,Cheng Z.Y.,Bharti V.,Xu H.S.,Zhang Q.M.High-dielectric-constant ceramic-powder polymer composites.Appl.Phys.Lett.,2000,76(25):3804-3806.
    [3]Bhattacharya S.K.,Tummala R.R.Integral passive for next generation of electronic packaging:Application of epoxy/ceramic nano-composites as integral capacitors.Microelectronics Journal,2001,32(1):11-19.
    [4]汤清华,潘晓光,叶龙,石康源。高储能密度电容器复合介质材料的研究.华中理工大学学报,1996,24(3):64-67.
    [5]L.Ramajo et al.Effect of silane as coupling agent on the dielectric properties of BaTiO_3-epoxy composites,Composites:Part A 38(2007) 1852-1859.
    [6]Zhi-Min Dang,Yan-Fei Yu et al.Study on microstructure and dielectric property of the BaTiO_3/epoxy resin composites.Composites Science and Technology(2007) 1-7.
    [7]Dong-Hau Kuo et al.Dielectric properties of three ceramic/epoxy composites,Materials Chemistry and Physics,85(2004) 201-206.
    [8]Sangyong Lee,Jin-Gul Hyun et al.A Study on Dielectric Constants of Epoxy/SrTiO_3Composite for Embeddec Capacitor Films(ECFs),IEEE Transactions c,n Advanced Packaging(2007) 1-6.
    [9]C.Zhang,R.Mason.Dielectric Properties of Alumina-Polymer Nanocornposites,2005Annual Report Conference on Electrical Insulation and Dielectric Phenomena,721-724.
    [10]Chao Zhang,Gary C Stevens.The Dielectric Behaviour of the Interface in Polymer Nanocomposites.2007 IEEE,423-427.
    [11]M.Gonzalez et al.The Dielectric Behaviour of High Dielectric Permittivity Pclymer-Matrix Composites.29th European Microwave Conference-Munich 1999:223-226.
    [12]Sung-Dong Cho et al.Epoxy/BaTiO_3 Composite Films and Pastes for High Dielectric Constant and Low-Tolerance Embedded Capacitors Fabrication in Organic Substrates,IEEE Transactions on Electronics Packaging Manufacturing,vol.28,No.4,October 2005,297-303.
    [13]Lai Qi et al.High-Dielectric-Constant Silver-Epoxy Composites as Embedded Dielectrics.Advanced Materials.2005,17,1777-1781.
    [14]Kyoung Sik Moon et al.Dielectric Properties of Epoxy-Dielectrics-Carbon Black Composite for Phantom Materials at Radio Frequencies Journal of Applied Polymer Science,Vol 77,1294-1302.
    [15]Lai Qi et al.Three-Phase Percolative Silver-BaTiO_3-Epoxy Nano-composites with High Dielectric Constants.Journal of Applied Polymer Science,Vol 102,2006,967-971.
    [16]Yang Rao et al.Novel High Dielectric Constant Nano-Structure Polymer-Ceramic Composite for Embedded Capacitor Application.2000 Electronic Components and Technology Conference,183-187.
    [17]Xu Man et al.Study on Preparation and Dielectric Properties of Nano-Ag/Epoxy Resin Composite.2006 IEEE,852-856.
    [18]Jianwen Xu et al.Optimization of Epoxy-Barium Titanate Nano-composites for High Performance Embedded Capacitor Components.IEEE Transactions on Electronics Packaging Manufacturing,vol.30,No.2,June 2007,248-253.
    [19]Yang Rao et al.Novel Polymer-Ceramic Nano-composites Based on High Dielectric Constant Epoxy Formula for Embedded Capacitor Application Journal of Applied PolymerScience,Vol83,1084-1090(2002).
    [20]H.L.W.Chan,Q.Q.Zhang et al.Dielectric Permittivity of PCLT/PVDF-TRFE Nanocomposites,Vol,7No.2,April 2000,204-207.
    [21]YangRaoetal.HighKPolymer-ceramicNano-compositeDevelopment,Characteri2;ation,and Modeling for Embedded Capacitor RF Application.2001 Electronic Components and Technology Conference.
    [22]Yang Rao et al.Material Characterization of High Dielectric Constant Polymer-Ceramic Composite for Embedded Capacitor to RF Application.2001 International Symposium on Advanced Packaging Materials.280-285.
    [23]Sangyong Lee et al.Multi-Functional Epoxy/SrTiO_3 Ceramic Powder Embedded Capacitor Films(ECFs)forOrganicSubstrates.2006ElectronicsPackagingTechnologyConference,549-552.
    [24]Jiangyi Chen,E.Pan,Hualing Chen.Wave propagation in magneto-electro-elastic multilayer ecolates Jnternational Journal of Solids and Structures 44(2007)1073-1085.
    [25]You-ming Cao,Jun Sun and De-mei Yu.Development of New Toughening Modified Dielectric Epoxies,Proceeding of The 6~(th) International Conference on Properties and Applications of Dielectric Materials,(2000)903-907.
    [26]B.Shri Prakash,K.B.R.Varma.Dielectric behavior of CCTO/epoxy and Al-CCTO/epoxy composites,Composites Science and Technology 67 (2007)2363-2368.
    [27]Jieying Yang et al.Study on Properties of Low Dielectric Loss Resin Matrix.Journal of Applied Polymer Science,Vol 102,2006,315-319.
    [28]Jiongxin Lu et al.Dielectric Loss Control of High-K Polymer Composites by Coulomb Blockade Effects of Metal Nano-particles for Embedded Capacitor Applications.IEEE Press,Wiley-Interscience,2005.
    [29]Chao Zhang et al.Dielectric Properties of Epoxy and Polyethylene Nano-composites.Proceedings of 2005 International Symposium on Electrical Insulating Materials,June 5-9,2005,Kitakyushu,Japan,721-724.
    [30]Chao Zhang and Gary C Stevens.Dielectric Properties of Boron Nitride Filled Epoxy Composites,2006 Annual Report Conference on Electrical Insulation arid Dielectric Phenomena 19-22.
    [31]熊传溪,董丽杰等.PVDF/改性BaTiO_3复合材料介电性能研究[J].高分子材料科学与工程,2003,19(1)152-155.
    [32]杨晓军,杨志民等.高介电常数EP/BT复合材料介电性能的研究[J].化工新型材料,2006,3(12)27-30.
    [33]李杰,韦平等.高介电复合材料及其介电性能的研究[J].绝缘材料,2003,5,3-6.
    [34]邢光建,杨志民等.高介电性能的陶瓷-聚合物复合材料的研究现状[J].高分子材料科学与工程,2005,21(3)54-58.
    [35]马寒冰,唐超等.环氧树脂/DDS固化剂体系介电常数和介质损耗因数的研究[J].变压器,2007,144(1)26-30.
    [36]朱兴松,刘立柱等.环氧树脂/蒙脱土纳米复合材料的介电性能研究[J].绝缘材料,2005,2,27-33.
    [37]徐曼,曹晓珑等.纳米SiO_2/环氧树脂复合体系性能研究-(Ⅱ)复合材料的介电特性和力学特性[J].高分子材料科学与工程,2005,21(1)156-159.
    [38]党智敏,王海燕等.新型高温高介无机/有机功能复合材料[J].复合材料学报,2005,22(5)68-51.
    [39]沈源,傅仁力等.氮化硅/环氧复合电子基板材料制备及性能[J].热固性树脂,2007,22(1)16-18.
    [40]石智强,王智权等.丙烯酸树脂/钛酸钡纳米复合材料的研究[J].电子元件与材料,2004,23(5)1-2.
    [41]王桂芹,陈晓东等.钛酸钡陶瓷材料的制备及电磁性能研究[J].无机材料学报,2007,22(2)3-6.
    [42]刘源波,王琪.固相剪切碾磨方法制各聚丙烯/钛酸钡高介电常数复合材料[J].功能高分子学报,2007,19(2)117-121.
    [43]刘旭燕,李三喜.Ba_(0.5)Sr_(0.5)TiO_3/PMMA复合材料介电性能研究[J].现代塑料加工应用,2007,19(3)9-12.
    [44]张根明,李旭东.BaTiO_3粉体的制备及其研究进展[J].科技信息,2007,11.
    [45]马寒冰,唐安斌等.苯并噁嗪/钛酸钡复合材料介电性能的研究[J].电子元件与材料,2006,25(9)55-56.
    [46]党智敏,王海燕等.高介电常数的聚合物基纳米复合电介质材料[J].中国电机工程学报.2006,26(15)100-104.
    [47]朱宝库,谢曙辉等.高介电常数聚酰亚胺/钛酸钡复合膜的制备与性能研究[J].功能材料,2005,4(36)546-548.
    [48]郭云亮,张涑戎等.偶联剂的种类和特点及应用[J].橡胶工业,2003,50(11).
    [49]王海燕.钛酸钡/聚偏氟乙烯复合材料的制备及其介电性能研究[D].兰州:兰州理工大学,2005.
    [50]陈倩.渗流型β相聚偏氟乙烯基复合厚膜材料的制备和介电性能研究[D].浙江:浙江大学,2007.
    [51]王岚.多壁碳纳米管/聚偏氟乙烯高介电纳米复合材料的制备及其性能研究[D].北京:北京化工大学,2005.
    [52]杨果,潘勤彦等.柔性胺改性剂对环氧树脂力学性能的影响[J].材料工程,2006,5,123-127.
    [53](法)R.科埃略,B.阿拉德尼兹著.电介质材料及其介电性能[M].北京:科学出版社,2000.
    [54](加拿大)洛兰,(美)科逊原著.电磁学原理及应用[M].成都:成都科技大学出版社,1988.
    [55]李标荣,莫以豪,王筱珍编.无机介电材料[M].上海:上海科学技术出版社,1986.
    [56]钟海庆编.红外光谱法入门[M].北京:化学工业出版社,1984.
    [57]陆婉珍主编.现代近红外光谱分析技术[M].北京:中国石化出版社,2007.
    [58]翁诗甫编著.傅里叶变换红外光谱仪[M].北京:化学工业出版社,2005.
    [59]高家武等编著.高分子材料热分析曲线集[M].北京:科学出版社,1990.
    [60]Li J Y,Rao N.Dramatically enhanced effective electro striction in ferroelectric polymeric composites[J].Applied Physics L etters,2002,(9):1860.
    [61]Bai Y,Cheng ZY,B harti V,Xu H S,Zhang QM.High-dielectric- constant ceramic-powder polymer composites[J].Applied Physics Letters,2000,(1):3804.
    [62]Dolye W T.The Clausius-Mossotti problem for cubic arrays of spheres[J].J Apply Phys,1978,49(3):795.
    [63]Doyle W T,Jacobs.I S.Effective cluster model of dielectric enhancement in metal-insulator composites[J].Phys Rev B,1990,(15):9319.
    [64]江平开,徐传骧,刘辅宜,王寿泰.金属-绝缘体复合材料介电增强的研究[J].西安交通大学学报,1997,(2):6.
    [65]江平开,王宗光,等.非球形导电粒子与绝缘体复合材料的介电增强研究[J].复合材料学报,1997,(8):91.
    [66]S.Stupp,P.V.Braun,Science 277,1242(1997).
    [67]W.M.Chen,Y.Yuan,L.F.Yan,Preparation of organic/inorganic nano-composites with polyacrylamide hydrogel by ~(60)Corirradiation,Materials Research Bulletin 35,807(2000).
    [68]S.K.Bhattacharya,R.R.Tummala,P.Chahal,G.White,Intern.Symp.Adv.Pack.Mater.68(1997).
    [69]Y.Bai,Z.Y.Cheng,V.Bharti,H.S.Xu,Q.M.Zhang,Appl.Phys.Lett.763804(2000).
    [70]G.M.Tsangarris,G.C.Psarras,N.Kouloumbi,Evalution of the dielectric behavior of particulate composites consisting of a polymeric matrix and a conductive filler,Material Science and Technology 12,533(1996).
    [71]D.Stauffer,Introduction to Percolation Theory,Taylor and Francis:London,198:;.
    [72]S.Kirkpatrick,Rev.Mod.Phys.45,574(1973).
    [73]C.Brosseau,P.Qu(?)ff(?)lec,P.Talbot,J.Appl.Phys.89,4532(2001).
    [74]S.K.Bhattacharya,Metal-Filled Polymers:Properties and Applications;Marcel Dekker:New York,1986.
    [75]J.Delmonte,Metal/Polymer Composites,Van Nostrant Reinhold:New York,1990.
    [76]R.Strumpler,J.Appl.Phys.80,6091(1996).
    [77]H.Zois,L.Apekis,Y.P.Mamunya,J.Appl.Poly.Sci.88,3013(2003).
    [78]Z.M.Dang,L.Z.Fan,S.Yang,C.W.Nan,Chem.Phys.Lett.369,95(2003).
    [79]赵淑金,党智敏,沈洋,范丽珍,南策文,纳米氧化锌的制备及其对复合材料介电性能的影响,稀有金属材料学与工程31,434(2002).
    [80]R.Tchoudakov,O.Breuer,M.Narkis,A.Siegmann,Conductive polymer blends with low carbon black loading:polypropylene/polyamide,Polymer Technology and Science 36,1336(1996).
    [81]Y.P.Mamunya,Y.V.Muzychenko,P.Pissis,E.V.Lebedev,M.I,Shut Percolation phenomena in polymers containing dispersed iron,Polymer Engineering and Science 42,90(2002).
    [82]M.Q.Zhang,G.Yu,H.M.Zeng,H.B.Zhang,Y.H,Hou.Two-step percolation in polymer blends filled with carbon black,Macromolecules 31,6724(1998).
    [83]Dang ZM,Fan LZ,Shen Y,Nan CW.Chemical Physics Letters 2003;269(1-2):95-100.
    [84]Jana A,Kundu TK,Pradhan SK,Chakravorty D.Journal of Applied Physics 2005;97(4):044311-044316.
    [85]Lim ES k,Lee JC,Kim JJ,Paek ET,Chung YK,Lee HY,Integrated Ferroelectrics 2005;74:53-60.
    [86]Zhang C,Mason R,Stevens GC.Dielectric properties of alumina-polymer nano-composites.Nashville,TN,USA:IEEE,2005.pp.721-724.
    [87]Dang ZM,Wang L,Yin Y,Zhang Q,Lei QQ.Advanced Materials 2007;19:852-857.
    [88]方俊鑫,殷之文.电介质物理学[M].科学出版社,1989.17-18.
    [89]Dang ZM,Fan L.Z,Nan C.W.,Dielectric behavior of novel three-phase carbon nanotubes/BaTiO3/PVDF composites,[J].Materials Science and Engineering B,2003,103(2):140-144.
    [90]罗金玲,周志刚,亚纳米铁电陶瓷介电性能的粒度效应[J].无机材料学报,1995,10(2):209-213.
    [91]阮圣平,董玮,吴凤清,王永为,于涛,彭增辉,宣丽,纳米晶钦酸钡的介电性能[J].物理化学学报,2003,19(1):17-20.

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