镀膜复合粒子的制备及导电性能研究
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摘要
镀银玻璃微球在军事、国防、电子、光学、医学、工业催化、生物工程等领域具有重要的应用价值。但银镀层易脱落,导致电阻变大,性能下降,如何用简单可行的方法得到结合牢固的镀层成为人们努力追求的目标。本文提出了新的无钯活化方法,成功在空心玻璃微球和聚合物微球表面化学镀银,探讨了活化机理和基体与镀层作用机理及复合粒子在导电填料方面的应用。主要研究内容和结论如下：
(1)采用甲醛还原银氨溶液方法能够很好地镀覆经过除油、粗化、敏化及活化预处理后的空心玻璃微球,活化过程赋予基材大的比表面积和高活性,比表面积变为原来的28.8倍,极大程度上促进了银粒子沉积,形成了大量孔穴,银离子沉积后,体系表面积下降,能量降低,可以自发发生。
(2)超声波振动能有效分散溶液中固体粒子,增加表面活性,使沉积银颗粒细化,特别有利于银的径向沉积,且能简化工艺。镀液配制方法显著影响银的析出,从而影响到镀层的表面形貌,适量降低银液滴加速度和可以减缓镀覆速率,能够避免微球表面部分区域出现较大凸起；降低反应温度亦可降低化学镀速率,使单质银均匀沉积。
(3)采用乳液聚合方法可以制备单分散性较好的聚苯乙烯粉体,利用透析膜可以分离聚合体系中的小分子,单体、乳化剂、引发剂比例影响聚苯乙烯粉体粒径大小及分布。粉体镀银后电阻率达6×10-3Ω·cm,可以用作导电填料。
(4)一种较佳的银导电胶配方为：填充粒子为粒径为5 um～8 um的镀银粉体,其各部分的较佳质量配比为,环氧树脂：镀银粉体=100:260,其中镀银粉体为枝状和球状按1：3质量比,固化剂DDM,发现其耐银迁移性为银导电胶的3倍以上,满足使用要求。
(5)一种成功的银导电胶固化工艺为：选用芳香二胺中的4,4-二氨基二苯甲烷(DDM)作为改性树脂体系的固化剂,其用量为30wt%左右,可以满足完全固化的要求。利用非等温DSC方法确定改性聚醚醚酮／环氧树脂体系的固化制度：80℃/2h+125℃/2h+180℃/3h,即80℃预固化2h,再升温至125℃固化2h,180℃后固化3h。
(6)活化后的玻璃微球和镀层的作用机理包括强的化学键和机械咬合作用机理,大大提高了镀层结合力和耐迁移能力,同时提高了导电胶的可靠性。
本文的创新点在于：
1)首次提出氢氧化铁凝胶活化体系,成功在玻璃微球和聚合物微球表面进行化学镀银；
2)探索了氧化铁在玻璃微珠表面的沉积机理和在化学镀中的作用机制；
3)探讨了镀层形态的影响因素和形貌控制方法；
4)制备了复合镀膜银导电胶并探讨了其性能。
The Ag-coated cenospheres can be of great application interest in war industry, national defence, electronics,optics, medicine, industrial catalysis, bio-engineering and so on. But the silver layer's being brushed off easily causes the rising of the resistance of the Ag-coated cenospheres and weakening of their performance, hunting for a simple and feasible method to make silver coating tight and firm is all the researchers'aim. In this paper, new Pd-free activating agent is introduced, and Ag-coated cenospheres and Ag-coated polymer microspheres are produced, mechanism of activating and the coated layer and its application as conductive filler are studied。The main content of the research and conclusion are as follows:
(1) The results show that the formaldehyde can react with silver nitrate-ammonia to form silver layer on the surfaces of cenosphere which is pretreated within four steps: degreaseing, coarsening, sensitizing,activation, activation enlarging specific surface area and reactivity, whose specific surface area is 28.8 times of bebore,which promote silver deposition. A great deal of little holes formed during pretreatment make room for silver ion, whose surface area and energe will drops if reacted, such is of spontaneity.
(2) Ultrasonic can effectively disperse the cenosphere particles, enhance surface activity, promote radical deposition, simplify process.The way to make the electroless plating solution remarkably affect the deposit of silver, also the appearance of the micro cenospheres. Lowering feeding rate of silver nitrate-ammonia and reaction temperature can slow plating,so as to prevent big Ag particles from depositing on the cenosphere surface,in this way good samples is manufactured.
(3) Emulsion polymerization is fit to prepare polystyrene microspheres of good monodispersion, dialyzer is helpful to separate small molecules from polymer system. The ratio of monomer, emulsifier, nitiator affect the size and distribution of microspheres. electrical resistivity of silver coated microspheres is 6x10~(-3)Ω·cm,which can be used as conductive fillers.
(4) An excellent fomula of conductive adhesive is:epoxy:filler (5μm～8μm)= 100:260, filler(dendritic particles:microspheres=1:3 wt), DDM as curing agent, whose Ag-migratory is 3 times as silver conductive adhesive, fit for use.
(5) A successful curing process is:DDM as curing agent,30wt%,according DSC to fix:80℃/2h+125℃/2h+180℃/3h
(6) Influence mechanism of cenospheres and the coated layer consist of chemical bond and occluding, which promote to form compact layer and Ag-migratory and increase adhesive's reliability
The main innovation are:
1) bring Fe(OH)3 gel as activator for the first time in the world, electroless silver deposition on surface of cenospheres and PS microspheres is carried out.
2) Deposition mechanism of ferric oxide on surface of cenospheres is studied;
3) The effect on configuration of layer and control of morphology of coating is discussed;
4) conductive adhesive is prepared and its performances is studied.
(1)采用甲醛还原银氨溶液方法能够很好地镀覆经过除油、粗化、敏化及活化预处理后的空心玻璃微球,活化过程赋予基材大的比表面积和高活性,比表面积变为原来的28.8倍,极大程度上促进了银粒子沉积,形成了大量孔穴,银离子沉积后,体系表面积下降,能量降低,可以自发发生。
(2)超声波振动能有效分散溶液中固体粒子,增加表面活性,使沉积银颗粒细化,特别有利于银的径向沉积,且能简化工艺。镀液配制方法显著影响银的析出,从而影响到镀层的表面形貌,适量降低银液滴加速度和可以减缓镀覆速率,能够避免微球表面部分区域出现较大凸起；降低反应温度亦可降低化学镀速率,使单质银均匀沉积。
(3)采用乳液聚合方法可以制备单分散性较好的聚苯乙烯粉体,利用透析膜可以分离聚合体系中的小分子,单体、乳化剂、引发剂比例影响聚苯乙烯粉体粒径大小及分布。粉体镀银后电阻率达6×10-3Ω·cm,可以用作导电填料。
(4)一种较佳的银导电胶配方为：填充粒子为粒径为5 um～8 um的镀银粉体,其各部分的较佳质量配比为,环氧树脂：镀银粉体=100:260,其中镀银粉体为枝状和球状按1：3质量比,固化剂DDM,发现其耐银迁移性为银导电胶的3倍以上,满足使用要求。
(5)一种成功的银导电胶固化工艺为：选用芳香二胺中的4,4-二氨基二苯甲烷(DDM)作为改性树脂体系的固化剂,其用量为30wt%左右,可以满足完全固化的要求。利用非等温DSC方法确定改性聚醚醚酮／环氧树脂体系的固化制度：80℃/2h+125℃/2h+180℃/3h,即80℃预固化2h,再升温至125℃固化2h,180℃后固化3h。
(6)活化后的玻璃微球和镀层的作用机理包括强的化学键和机械咬合作用机理,大大提高了镀层结合力和耐迁移能力,同时提高了导电胶的可靠性。
本文的创新点在于：
1)首次提出氢氧化铁凝胶活化体系,成功在玻璃微球和聚合物微球表面进行化学镀银；
2)探索了氧化铁在玻璃微珠表面的沉积机理和在化学镀中的作用机制；
3)探讨了镀层形态的影响因素和形貌控制方法；
4)制备了复合镀膜银导电胶并探讨了其性能。
The Ag-coated cenospheres can be of great application interest in war industry, national defence, electronics,optics, medicine, industrial catalysis, bio-engineering and so on. But the silver layer's being brushed off easily causes the rising of the resistance of the Ag-coated cenospheres and weakening of their performance, hunting for a simple and feasible method to make silver coating tight and firm is all the researchers'aim. In this paper, new Pd-free activating agent is introduced, and Ag-coated cenospheres and Ag-coated polymer microspheres are produced, mechanism of activating and the coated layer and its application as conductive filler are studied。The main content of the research and conclusion are as follows:
(1) The results show that the formaldehyde can react with silver nitrate-ammonia to form silver layer on the surfaces of cenosphere which is pretreated within four steps: degreaseing, coarsening, sensitizing,activation, activation enlarging specific surface area and reactivity, whose specific surface area is 28.8 times of bebore,which promote silver deposition. A great deal of little holes formed during pretreatment make room for silver ion, whose surface area and energe will drops if reacted, such is of spontaneity.
(2) Ultrasonic can effectively disperse the cenosphere particles, enhance surface activity, promote radical deposition, simplify process.The way to make the electroless plating solution remarkably affect the deposit of silver, also the appearance of the micro cenospheres. Lowering feeding rate of silver nitrate-ammonia and reaction temperature can slow plating,so as to prevent big Ag particles from depositing on the cenosphere surface,in this way good samples is manufactured.
(3) Emulsion polymerization is fit to prepare polystyrene microspheres of good monodispersion, dialyzer is helpful to separate small molecules from polymer system. The ratio of monomer, emulsifier, nitiator affect the size and distribution of microspheres. electrical resistivity of silver coated microspheres is 6x10~(-3)Ω·cm,which can be used as conductive fillers.
(4) An excellent fomula of conductive adhesive is:epoxy:filler (5μm～8μm)= 100:260, filler(dendritic particles:microspheres=1:3 wt), DDM as curing agent, whose Ag-migratory is 3 times as silver conductive adhesive, fit for use.
(5) A successful curing process is:DDM as curing agent,30wt%,according DSC to fix:80℃/2h+125℃/2h+180℃/3h
(6) Influence mechanism of cenospheres and the coated layer consist of chemical bond and occluding, which promote to form compact layer and Ag-migratory and increase adhesive's reliability
The main innovation are:
1) bring Fe(OH)3 gel as activator for the first time in the world, electroless silver deposition on surface of cenospheres and PS microspheres is carried out.
2) Deposition mechanism of ferric oxide on surface of cenospheres is studied;
3) The effect on configuration of layer and control of morphology of coating is discussed;
4) conductive adhesive is prepared and its performances is studied.
引文
[1]步文博,徐洁,丘泰等.吸波材料的基础研究及微波损耗机理的探讨[J].材料导报,2001,15(5):14～17.
[2]Nortier J R,Van der Neut C A,Baker D E.Table for the design of Jaumann microwave absorber[J].Microwave Journal,1987,12:219-222.
[3]YU Xiaoling. Simulation and design for stratified iron fiber absorbing materials[J]. Materials and Design,2002(23):51-57
[4]毛东森,卢立义.环氧乙烷银催化剂的研究进展[J].精细石油化工,1995(3):1-5.
[5]刘大壮,孙培勤.催化工艺开发[M].北京：气象出版社.2002:3
[6]顾立军,谢颖,郑慧玲,刘宝生,陈小平,王乐夫.C_3H_6选择性催化还原NO催化剂Ag／γ-AI_2O_3的研究[J].煤炭转化,2003,26(3)：84-87.
[7]高宁,付斌,郑卫明,王广柏,王全义.一步法合成吲哚的Ag/SiO_2催化剂[J].化学工业与工程,2003,20(5):310～312,封3.
[8]金积铨.银催化剂的发展和EO/EG生产技术进步[J].石化技术,1999,6(2)：65-68.
[9]王海京,许根慧,陈洪钫.正丁烷选择氧化流化床催化剂研究[J].精细石油化工,1997,(4)：9～12.
[10]川上浩,小山田雅明.化学镀Ag粉体制造工艺[P].JP,11061424,1999-03-05.
[11]A.P. Alivisatos, Semiconductor Clusters Nanocrystals and Quantum Dots[J]. Science,1996,271:933-937.
[12]新子貴史,無電解ヌツキ法にょるる银被覆粉體の制法ゎよひ光学特性[J].粉體ゎよひ粉末冶金,1995,42(1):90-94
[13]N.S.Hoyer, in"Power Metallurgy Handbook" Vol.7,9~(th)Edn[M], ASM International, New York,1996.
[14]P.B.Joshi, N.S.S.Murti, V.L.Gadgeel, Preparation and characterization of Ag-ZnO powders for application in electrical contact materials[J]. Journal of Materials Science letters,1995,14:1099-1101
[15]H.F.Chang, C.H.Pitt, G.B.Alexander, Electroless silver plating of oxide particles in aqueous solution[J]. J. Mater. Sci.,1993:5207-5210
[16]Linnert, T.,Mulvaney,P., Henglein, A. J. Phys.Chem 1993,97:679-682.
[17]Mirkin, C. A.,Letsinger, R.L.,Mucic, R. C.,Storhoff,J.J. Nature 1996, 382:607～609.
[18]Elghanian,R., Storhoff,J.J., Mucic, R. C.,Letsinger, R.L., Mirkin, C. A. science 1997,277:1078～1081.
[19]Alivisatos, A.P., Johnsson, K.P., Peng, X., Wilson,T.E., Loweth, C.J., Bruchez, M.P., Schultz, P.G. Nature 1996,382:609～611.
[20]刘正春,贺全国,肖鹏峰.自组装化学镀银[J].化学学报,2002,60(3):627-632.
[21]张钦京,杨德钧.我国化学镀技术交流与发展.表面工程资讯.2005,5(2):5～6.
[22]Ryo Enomoto,Motoo Asai. Adhesive for electroless plating,printed circuit boards and method of producing the same [P].US,5055321,1991-10-08.
[23]渡边秀美,木村修,金属粒子分散强化ァ ル ミ ナ の機械的特性—Ⅱ—無電解ヌ ムツキ分散法一[J].粉体ゎよひ粉末冶金,1991,38(3):331-334.
[24]Gerald A. Krulik, Nenad V. Mandich,Rajwant Singh.Plating rate improvement for electroless silver and gold plating[P]. US.5318621,1994-06-07.
[25]Nenad V.Mandich, Gerald A. Krulik, Rajwant Singh.Electroless silver plating composition[J]. US,5322553,1994-06-21.
[26]Alexander S.Kozlov,Thirumalai Palanisamy,Dave Narasimhan.Electroless silver plating[P]. US.6387542B1,2002-04-14.
[27]Che-Hsiung Hsu,Wilfred Sweeny. Silver-plated fibers of poly(p-phenylene terephthalamide) and a process for making them[P].US,5549972,1996-08-27.
[28]Carl Hutchinson,Hartmut Mahlkow,Christian Sparing.Bath and method of electroless plating of silver on metal surfaces [P].US,6869637B2,2005-03-22.
[29]Martin H.Blees,Antonius A.M.Van Weert.Method of applying a silver layer to a glass substrate[P]. US,6027862,2002-02022
[30]李春露.化学镀镍的工业应用[J].表面工程资讯,2005,(5)2:1-2.
[31]Ryo Enomoto,Oogaki.Adhesive for electroless plating and method of preparation of circuit board using this adhesive [P]. US,5021472,1991-06-04.
[32]张胡海,黄新民.化学镀的应用研究[J].机械工人.热加工,2005,(01):54-56.
[33]李酽,刘刚,刘红霞,刘传生,李铀,王芬.化学镀层的性能及基体的镀前处理[J].航空制造技术,2004,(07):86～88.
[34]陈曙光,刘君武,丁厚福.化学镀的研究现状、应用及展望[J].热加工工艺,2000,(02)：23～25.
[35]李昕,杨昌英,周俊婷,张桂燕,孙玉宝,王其龙.化学镀镍配方的优化及镀镍过程机理的研究[J].化学与生物工程,2005,(03)：31-33.
[36]王福生,许芸芸,宋兵魁,韩晓丽,张宝贵.化学镀Ni-P合金工艺的研究[J].天津化工,2004,(05)：1～3.
[37]张天顺,张放,刘艺华,郭丽.化学镀镍及其展望[J].机械工程师,1995,(05):41～42.
[38]熊晓东,翟玉春,田彦文.联氨化学镀液的研究概况[J].电镀与精饰,1996,(05)：21～25.
[39]贺英,桑文斌,王均安.化学镀工艺在微电子材料中的研究和应用[J].微纳电子技术,2003,(05)：23～27.
[40]姜晓霞,沈伟,化学镀理论及实践[M].北京：国防工业出版社,2002.
[41]沉伟,化学镀铜的沉积过程与镀层性能[J].材料保护,2000,33(1),33～35.
[42]Paunovic, Kinetics and Mechanism of Electroless Metal Deposition In Proceedings of The Symposium on Electroless Deposition of Metals and Alloys.ECS Inc., New Jersey,1988
[43]Zhou Y, Liu H J, Yu S H, Preparation of nanocrystalline silver by the method of liquid-solid arc discharge combined with hydrothermal treatment[J]. Mater. Resear. Bull,1999,34(10-11):1683-1688.
[44]Vorobyova S A, Lesnikovich A I, Sobal N S, Preparation of silver nanoparticles by interphase reduction, Colloids and Surfaces A[J]. Physicochemical and Engineering Aspects,1999,152(3):375-379.
[45]谭富彬,赵玲,刘林.纳米银粉的液相化学制备及其特性[J].贵金属,1999,20(3)：9～12.
[46]黄少强,邱文革.玻璃微球表面化学镀银[J].电镀与涂饰,2004,23(1):7～9.
[47]黄少强,邱文革,陈江涛.非金属粉体化学镀银影响因素的研究[J].材料保护,2004,37(10):23～25.
[48]王宇,张骁勇,毛丽,曹志壮.空心玻璃微珠化学镀银的研究[j].材料科学与工程学报,2004,22(5):753～756.
[49]毛倩瑾,于彩霞,王群,张丰,葛凯勇,周美玲.空心微珠表面金属化及其电磁防护性能研究[J].北京工业大学学报,2003,(1):108～111.
[50]LING Guo-ping,LI Jian,WANG Shang-jun.PREPARATION AND CHARACTERISTICS OF NEW TYPE NANOCOMPOSITE POWDER [J]. Journal of Zhejiang University Science,2001,(4):376-378
[51]Lin Su-Jien, YehJien-Wei,Chang Shou-Yi. Preparation and characterization of AlCrTaTiZr multi-element nitride coatings[J].Surface and Coatings Technology, 2006,201(6)3275-3280
[52]史桂梅,张志东,杨洪才,李丙泽.化学镀法合成纳米Ag包覆Al2O3复合粉[J].东北大学学报(自然科学版),2004,25(8)：768-770
[53]黄磊.陶瓷粉体化学镀银研究[硕士学位论文].杭州：浙江大学,2003.
[54]H.M.Cheng, B.L.Zhou, A.Kitahara, S.Akiyama,K.Kobayahsi.Effect of silicon additions on characteristics of carbon fiber reinforced aluminum composites during thermal exposure[J].J.Mater.Res.1996, (11):1284-1292.
[55]S.G.Warrier, S.H.Chen, S.K.Wu, and R.Y.Lin. Interface Characterization of Ceramic Fiber-Reinforced Ti Alloy Composites Manufactured by Infrared Processing[J] Metallurgical and Materials Transaction,1996,27(A):1379-1394.
[56]邱文革,黄少强,陈江涛.玻璃纤维及二氧化硅微粒表面的化学镀银工艺[J].材料保护,2005,38(8):29-30,34.
[57]凤仪,袁海龙.碳纳米管的化学镀银[J].功能材料,2004,35(3)：317-319
[58]李辰砂,王清滨,张宝友,曹茂盛,卢伟哲,李志,梁吉.碳纳米管对聚合物纤维抗静电能力的影响[J].哈尔滨工业大学学报,2004,36(4):433-436.
[59]陈小华,张高明,李宏健,彭景翠.碳纳米管的化学镀银及SEM研究[J].湖南大学学报(自然科学版),1999,(6):14-17,56.
[60]王红强,李新海,郭华军,张宝,郭永兴.石墨化中间相炭微球表面镀银的电化学性能[J].中南大学学报(自然科学版),2003,34(6)：615-618
[61]G.A. Shafeev, E.D. Obraztsova, S.M. Pimenov.Laser-assisted etching of diamonds in air and in liquid media[J].Applied Physics A:Materials Science & Processing,1997,65(1):29-32
[62]R. Q. Guo, P. K. Rohatgi, D. Nath.Compacting characteristics of aluminium-fly ash powder mixtures[J]. Journal of Materials Science,1996,31(20):5513-5519
[63]S. P.McBride, A. Shukla and A. Bose.Processing and characterization of a lightweight concrete using cenospheres[J] Journal of Materials Science,2002,37(19):4217-4225
[64]Gaohui Wu, Hiaoli Huang,et al.Electromagnetic interfering shielding of aluminum alloy-cenospheres composite[J] Journal of Materials Science,1573-4803 [Online]
[65]R. J.Cardoso, A. Shukla, A. Bose.Effect of particle size and surface treatment on constitutive properties of polyester-cenosphere composites[J] Journal of Materials Science,2002,37(3):603-613
[66]Y. Hanada, K. Sugiokal, H. Takase,et al.Selective metallization of polyimide by laser-induced plasma-assisted ablation (LIPAA)[J].Applied Physics A:Materials Science & Processing,2005,80(1):111-115
[67]A. Huczko.Template-based synthesis of nanomaterials[J].Applied Physics A: Materials Science & Processing,2000,70(4):365-376
[68]K. Sugiokal,2, Y. Gomi3, H. Yamaoka,et al.Development of practical system for laser-induced plasma-assisted ablation (LIPAA) for micromachining of glass materials[J]. Applied Physics A:Materials Science & Processing,2004,79(4-6):1001-1003
[69]G. A. Shafeev. Laser-assisted activation and metallization of polyimides[J]. Applied Physics A:Materials Science & Processing,1992,55(4):387-390
[70]Nortier J R,Van der Neut C A,Baker D E.Table for the design of Jaumann microwave absorber[J].Microwave Journal,1987,12:219-222.
[71]YU Xiaoling. Simulation and design for stratified iron fiber absorbing materials[J]. Materials and Design,2002(23):51-57
[72]A.P. Alivisatos, Semiconductor Clusters Nanocrystals and Quantum Dots[J]. Science,1996,271:933-937.
[73]N.S.Hoyer, in"Power Metallurgy Handbook" Vol.7,9~(th)Edn[M], ASM International, New York,1996.
[74]P.B.Joshi, N.S.S.Murti, V.L.Gadgeel, Preparation and characterization of Ag-ZnO powders for application in electrical contact materials[J]. Journal of Materials Science letters,1995,14:1099-1101
[75]H.F.Chang, C.H.Pitt, G.B.Alexander, Electroless silver plating of oxide particles in aqueous solution[J]. J. Mater. Sci.,1993:5207-5210
[76]陈康生.玻璃微珠的新制法[J].四川化工,2006,9(1):16-17.
[77]刘伯元,黄世鲜,江广城.超细玻璃微珠的研究[C].2002年中国工程塑料加工应用技术研讨会论文集.济南：中国工程塑料工业协会加工应用专委会,188～192.
[78]宋庆功,丛宪忠.玻璃微球及其应用[J].现代物理知识,1997,(3):29～30.
[79]胡少枝.空心玻璃微球在航空和宇航材料中的应用[J].材料工程,1990,(5):25-27.
[80]刘宝珠.“HB粉煤灰活化剂”的研制及在建材中的应用[J].砖瓦.2004,(7):75～77.
[81]刘巧明,夏传义.用于微电子封装的化学镀纯镍工艺[J].材料保护,1995,(01)：14～17.
[82]黄松荣,丁忠浩.粉煤灰深层次的综合利用.中国粉体技术[J].2001,,(7)12:122-125.
[83]韩怀强等.粉煤灰利用技术[M].北京：化学工业出版社,2001.
[84]Paunovic, Kinetics and Mechanism of Electroless Metal Deposition In Proceedings of The Symposium on Electroless Deposition of Metals and Alloys.ECS Inc., New Jersey,1988
[85]刘荣杰,卫志贤,蔡力.铜粉导电胶的制各研究[J].中国胶粘剂,2000,9(2):12-13,18.
[86]路庆华.新型导电胶的研究:(Ⅱ)耐银迁移导电胶的研究[J].功能材料,1998,29(4):439～441
[87]F. C. Walsh,M. E. Herron. Electrocrystallization and Electrochemical Control of Crystal Growth:Fundamental Considerations and Electrodeposition of Metals[J]. J.Phys.D:Appl.Phys,1991,24:217～225.
[88]E.Budevski,G.Staikov,W.J.Lorenz.Electrocrystallization:Nucleation and Growth Phenomena[J].Electrochim Acta,2000,45(15-16):2559～2574.
[89]虞苏玮,安维丹,欧萌,李刚.高性能非银导电胶粘剂研究及应用[J].电子工艺技术,1997,18(1)：34～39.
[90]DAVID W M.Copper-based conductive polymers:A new concept in conductive resins[J].J Adhesion.2000,74:301～315.
[91]TANIGAKI,TSU YOSHI,IZAWA,et al.Resin compositions,resin moldings and their methods of production[P].US 6096245,2000-08-01.
[92]杨小峰.CLD-20结构性导电胶的研制与应用[J].中国胶粘剂,1999,8(2):39-41,44.
[93]DAVID W M. Copper-based conductive polymers:A new concept in conductive resins[J].J Adhesion.2000,74:301～315.
[94]Zhou Y, Liu H J, Yu S H, Preparation of nanocrystalline silver by the method of liquid-solid arc discharge combined with hydrothermal treatment[J]. Mater. Resear.Bull,1999,34(10-11):1683～1688.
[95]Vorobyova S A, Lesnikovich A I, Sobal N S, Preparation of silver nanoparticles by interphase reduction, Colloids and Surfaces A[J]. Physicochemical and Engineering Aspects,1999,152(3):375-379.
[96]谭富彬,赵玲,刘林.纳米银粉的液相化学制备及其特性[J].贵金属,1999,20(3)：9-12.
[97]陈康生.玻璃微珠的新制法[J].四川化32,2006,9(1):16-17.
[98]刘伯元,黄世鲜,江广城.超细玻璃微珠的研究[C].2002年中国工程塑料加工应用技术研讨会论文集.济南：中国工程塑料工业协会加工应用专委会,188-192.
[99]Bogush G H, Zukoski I V. Uniform silica particle precipitation:an aggregative growth mode[J]. Journal of Colloid and Interface Science,1991,142(1): 19-34.
[100]叶为春.硅基贵金属膜材料的制备、形貌控制及性质分析：[博士学位论文].兰州：兰州大学,2008
[101]Chen S L, Dong P, Yang G H, et al. The size dependence of growth rate of monodisperse silica particles from tetraalkoxysilanes[J]. Journal of Colloid and Interface Science,1997,189:268-272.
[102]Vorobyova S A, Lesnikovich A I, Sobal N S, Preparation of silver nanoparticles by interphase reduction, Colloids and Surfaces A[J]. Physicochemical and Engineering Aspects,1999,152(3):375-379.
[103]Scharifker,Hills.Theoretical and Experimental Studies of Multiple Nucleation[J].Electrochim Acta,1983,28(7):879-889.
[104]Ouassim Ghodbanea,Lionel Roue,Daniel Belanger.Copper electrodeposition on pyrolytic graphite electrodes:Effect of the copper salt on the electrodeposition process[J].Electrochimica Acta,2007,52:5843-5855.
[105]胡兵.改性聚醚醚酮增韧环氧树脂的研究：[博士学位论文].武汉：武汉理工大学,2007
[106]吴懿平,吴大海,袁忠发,等.镀银铜粉导电胶的研究[J].电子元件与材料,2005,24(4)：32-35
[107]曾黎明.功能复合材料及其应用[M].北京：化学工业出版社,2006.10-13.
[108]查全性.电极过程动力学导论[M].北京:科学出版社,2002:306-310.
[2]Nortier J R,Van der Neut C A,Baker D E.Table for the design of Jaumann microwave absorber[J].Microwave Journal,1987,12:219-222.
[3]YU Xiaoling. Simulation and design for stratified iron fiber absorbing materials[J]. Materials and Design,2002(23):51-57
[4]毛东森,卢立义.环氧乙烷银催化剂的研究进展[J].精细石油化工,1995(3):1-5.
[5]刘大壮,孙培勤.催化工艺开发[M].北京：气象出版社.2002:3
[6]顾立军,谢颖,郑慧玲,刘宝生,陈小平,王乐夫.C_3H_6选择性催化还原NO催化剂Ag／γ-AI_2O_3的研究[J].煤炭转化,2003,26(3)：84-87.
[7]高宁,付斌,郑卫明,王广柏,王全义.一步法合成吲哚的Ag/SiO_2催化剂[J].化学工业与工程,2003,20(5):310～312,封3.
[8]金积铨.银催化剂的发展和EO/EG生产技术进步[J].石化技术,1999,6(2)：65-68.
[9]王海京,许根慧,陈洪钫.正丁烷选择氧化流化床催化剂研究[J].精细石油化工,1997,(4)：9～12.
[10]川上浩,小山田雅明.化学镀Ag粉体制造工艺[P].JP,11061424,1999-03-05.
[11]A.P. Alivisatos, Semiconductor Clusters Nanocrystals and Quantum Dots[J]. Science,1996,271:933-937.
[12]新子貴史,無電解ヌツキ法にょるる银被覆粉體の制法ゎよひ光学特性[J].粉體ゎよひ粉末冶金,1995,42(1):90-94
[13]N.S.Hoyer, in"Power Metallurgy Handbook" Vol.7,9~(th)Edn[M], ASM International, New York,1996.
[14]P.B.Joshi, N.S.S.Murti, V.L.Gadgeel, Preparation and characterization of Ag-ZnO powders for application in electrical contact materials[J]. Journal of Materials Science letters,1995,14:1099-1101
[15]H.F.Chang, C.H.Pitt, G.B.Alexander, Electroless silver plating of oxide particles in aqueous solution[J]. J. Mater. Sci.,1993:5207-5210
[16]Linnert, T.,Mulvaney,P., Henglein, A. J. Phys.Chem 1993,97:679-682.
[17]Mirkin, C. A.,Letsinger, R.L.,Mucic, R. C.,Storhoff,J.J. Nature 1996, 382:607～609.
[18]Elghanian,R., Storhoff,J.J., Mucic, R. C.,Letsinger, R.L., Mirkin, C. A. science 1997,277:1078～1081.
[19]Alivisatos, A.P., Johnsson, K.P., Peng, X., Wilson,T.E., Loweth, C.J., Bruchez, M.P., Schultz, P.G. Nature 1996,382:609～611.
[20]刘正春,贺全国,肖鹏峰.自组装化学镀银[J].化学学报,2002,60(3):627-632.
[21]张钦京,杨德钧.我国化学镀技术交流与发展.表面工程资讯.2005,5(2):5～6.
[22]Ryo Enomoto,Motoo Asai. Adhesive for electroless plating,printed circuit boards and method of producing the same [P].US,5055321,1991-10-08.
[23]渡边秀美,木村修,金属粒子分散强化ァ ル ミ ナ の機械的特性—Ⅱ—無電解ヌ ムツキ分散法一[J].粉体ゎよひ粉末冶金,1991,38(3):331-334.
[24]Gerald A. Krulik, Nenad V. Mandich,Rajwant Singh.Plating rate improvement for electroless silver and gold plating[P]. US.5318621,1994-06-07.
[25]Nenad V.Mandich, Gerald A. Krulik, Rajwant Singh.Electroless silver plating composition[J]. US,5322553,1994-06-21.
[26]Alexander S.Kozlov,Thirumalai Palanisamy,Dave Narasimhan.Electroless silver plating[P]. US.6387542B1,2002-04-14.
[27]Che-Hsiung Hsu,Wilfred Sweeny. Silver-plated fibers of poly(p-phenylene terephthalamide) and a process for making them[P].US,5549972,1996-08-27.
[28]Carl Hutchinson,Hartmut Mahlkow,Christian Sparing.Bath and method of electroless plating of silver on metal surfaces [P].US,6869637B2,2005-03-22.
[29]Martin H.Blees,Antonius A.M.Van Weert.Method of applying a silver layer to a glass substrate[P]. US,6027862,2002-02022
[30]李春露.化学镀镍的工业应用[J].表面工程资讯,2005,(5)2:1-2.
[31]Ryo Enomoto,Oogaki.Adhesive for electroless plating and method of preparation of circuit board using this adhesive [P]. US,5021472,1991-06-04.
[32]张胡海,黄新民.化学镀的应用研究[J].机械工人.热加工,2005,(01):54-56.
[33]李酽,刘刚,刘红霞,刘传生,李铀,王芬.化学镀层的性能及基体的镀前处理[J].航空制造技术,2004,(07):86～88.
[34]陈曙光,刘君武,丁厚福.化学镀的研究现状、应用及展望[J].热加工工艺,2000,(02)：23～25.
[35]李昕,杨昌英,周俊婷,张桂燕,孙玉宝,王其龙.化学镀镍配方的优化及镀镍过程机理的研究[J].化学与生物工程,2005,(03)：31-33.
[36]王福生,许芸芸,宋兵魁,韩晓丽,张宝贵.化学镀Ni-P合金工艺的研究[J].天津化工,2004,(05)：1～3.
[37]张天顺,张放,刘艺华,郭丽.化学镀镍及其展望[J].机械工程师,1995,(05):41～42.
[38]熊晓东,翟玉春,田彦文.联氨化学镀液的研究概况[J].电镀与精饰,1996,(05)：21～25.
[39]贺英,桑文斌,王均安.化学镀工艺在微电子材料中的研究和应用[J].微纳电子技术,2003,(05)：23～27.
[40]姜晓霞,沈伟,化学镀理论及实践[M].北京：国防工业出版社,2002.
[41]沉伟,化学镀铜的沉积过程与镀层性能[J].材料保护,2000,33(1),33～35.
[42]Paunovic, Kinetics and Mechanism of Electroless Metal Deposition In Proceedings of The Symposium on Electroless Deposition of Metals and Alloys.ECS Inc., New Jersey,1988
[43]Zhou Y, Liu H J, Yu S H, Preparation of nanocrystalline silver by the method of liquid-solid arc discharge combined with hydrothermal treatment[J]. Mater. Resear. Bull,1999,34(10-11):1683-1688.
[44]Vorobyova S A, Lesnikovich A I, Sobal N S, Preparation of silver nanoparticles by interphase reduction, Colloids and Surfaces A[J]. Physicochemical and Engineering Aspects,1999,152(3):375-379.
[45]谭富彬,赵玲,刘林.纳米银粉的液相化学制备及其特性[J].贵金属,1999,20(3)：9～12.
[46]黄少强,邱文革.玻璃微球表面化学镀银[J].电镀与涂饰,2004,23(1):7～9.
[47]黄少强,邱文革,陈江涛.非金属粉体化学镀银影响因素的研究[J].材料保护,2004,37(10):23～25.
[48]王宇,张骁勇,毛丽,曹志壮.空心玻璃微珠化学镀银的研究[j].材料科学与工程学报,2004,22(5):753～756.
[49]毛倩瑾,于彩霞,王群,张丰,葛凯勇,周美玲.空心微珠表面金属化及其电磁防护性能研究[J].北京工业大学学报,2003,(1):108～111.
[50]LING Guo-ping,LI Jian,WANG Shang-jun.PREPARATION AND CHARACTERISTICS OF NEW TYPE NANOCOMPOSITE POWDER [J]. Journal of Zhejiang University Science,2001,(4):376-378
[51]Lin Su-Jien, YehJien-Wei,Chang Shou-Yi. Preparation and characterization of AlCrTaTiZr multi-element nitride coatings[J].Surface and Coatings Technology, 2006,201(6)3275-3280
[52]史桂梅,张志东,杨洪才,李丙泽.化学镀法合成纳米Ag包覆Al2O3复合粉[J].东北大学学报(自然科学版),2004,25(8)：768-770
[53]黄磊.陶瓷粉体化学镀银研究[硕士学位论文].杭州：浙江大学,2003.
[54]H.M.Cheng, B.L.Zhou, A.Kitahara, S.Akiyama,K.Kobayahsi.Effect of silicon additions on characteristics of carbon fiber reinforced aluminum composites during thermal exposure[J].J.Mater.Res.1996, (11):1284-1292.
[55]S.G.Warrier, S.H.Chen, S.K.Wu, and R.Y.Lin. Interface Characterization of Ceramic Fiber-Reinforced Ti Alloy Composites Manufactured by Infrared Processing[J] Metallurgical and Materials Transaction,1996,27(A):1379-1394.
[56]邱文革,黄少强,陈江涛.玻璃纤维及二氧化硅微粒表面的化学镀银工艺[J].材料保护,2005,38(8):29-30,34.
[57]凤仪,袁海龙.碳纳米管的化学镀银[J].功能材料,2004,35(3)：317-319
[58]李辰砂,王清滨,张宝友,曹茂盛,卢伟哲,李志,梁吉.碳纳米管对聚合物纤维抗静电能力的影响[J].哈尔滨工业大学学报,2004,36(4):433-436.
[59]陈小华,张高明,李宏健,彭景翠.碳纳米管的化学镀银及SEM研究[J].湖南大学学报(自然科学版),1999,(6):14-17,56.
[60]王红强,李新海,郭华军,张宝,郭永兴.石墨化中间相炭微球表面镀银的电化学性能[J].中南大学学报(自然科学版),2003,34(6)：615-618
[61]G.A. Shafeev, E.D. Obraztsova, S.M. Pimenov.Laser-assisted etching of diamonds in air and in liquid media[J].Applied Physics A:Materials Science & Processing,1997,65(1):29-32
[62]R. Q. Guo, P. K. Rohatgi, D. Nath.Compacting characteristics of aluminium-fly ash powder mixtures[J]. Journal of Materials Science,1996,31(20):5513-5519
[63]S. P.McBride, A. Shukla and A. Bose.Processing and characterization of a lightweight concrete using cenospheres[J] Journal of Materials Science,2002,37(19):4217-4225
[64]Gaohui Wu, Hiaoli Huang,et al.Electromagnetic interfering shielding of aluminum alloy-cenospheres composite[J] Journal of Materials Science,1573-4803 [Online]
[65]R. J.Cardoso, A. Shukla, A. Bose.Effect of particle size and surface treatment on constitutive properties of polyester-cenosphere composites[J] Journal of Materials Science,2002,37(3):603-613
[66]Y. Hanada, K. Sugiokal, H. Takase,et al.Selective metallization of polyimide by laser-induced plasma-assisted ablation (LIPAA)[J].Applied Physics A:Materials Science & Processing,2005,80(1):111-115
[67]A. Huczko.Template-based synthesis of nanomaterials[J].Applied Physics A: Materials Science & Processing,2000,70(4):365-376
[68]K. Sugiokal,2, Y. Gomi3, H. Yamaoka,et al.Development of practical system for laser-induced plasma-assisted ablation (LIPAA) for micromachining of glass materials[J]. Applied Physics A:Materials Science & Processing,2004,79(4-6):1001-1003
[69]G. A. Shafeev. Laser-assisted activation and metallization of polyimides[J]. Applied Physics A:Materials Science & Processing,1992,55(4):387-390
[70]Nortier J R,Van der Neut C A,Baker D E.Table for the design of Jaumann microwave absorber[J].Microwave Journal,1987,12:219-222.
[71]YU Xiaoling. Simulation and design for stratified iron fiber absorbing materials[J]. Materials and Design,2002(23):51-57
[72]A.P. Alivisatos, Semiconductor Clusters Nanocrystals and Quantum Dots[J]. Science,1996,271:933-937.
[73]N.S.Hoyer, in"Power Metallurgy Handbook" Vol.7,9~(th)Edn[M], ASM International, New York,1996.
[74]P.B.Joshi, N.S.S.Murti, V.L.Gadgeel, Preparation and characterization of Ag-ZnO powders for application in electrical contact materials[J]. Journal of Materials Science letters,1995,14:1099-1101
[75]H.F.Chang, C.H.Pitt, G.B.Alexander, Electroless silver plating of oxide particles in aqueous solution[J]. J. Mater. Sci.,1993:5207-5210
[76]陈康生.玻璃微珠的新制法[J].四川化工,2006,9(1):16-17.
[77]刘伯元,黄世鲜,江广城.超细玻璃微珠的研究[C].2002年中国工程塑料加工应用技术研讨会论文集.济南：中国工程塑料工业协会加工应用专委会,188～192.
[78]宋庆功,丛宪忠.玻璃微球及其应用[J].现代物理知识,1997,(3):29～30.
[79]胡少枝.空心玻璃微球在航空和宇航材料中的应用[J].材料工程,1990,(5):25-27.
[80]刘宝珠.“HB粉煤灰活化剂”的研制及在建材中的应用[J].砖瓦.2004,(7):75～77.
[81]刘巧明,夏传义.用于微电子封装的化学镀纯镍工艺[J].材料保护,1995,(01)：14～17.
[82]黄松荣,丁忠浩.粉煤灰深层次的综合利用.中国粉体技术[J].2001,,(7)12:122-125.
[83]韩怀强等.粉煤灰利用技术[M].北京：化学工业出版社,2001.
[84]Paunovic, Kinetics and Mechanism of Electroless Metal Deposition In Proceedings of The Symposium on Electroless Deposition of Metals and Alloys.ECS Inc., New Jersey,1988
[85]刘荣杰,卫志贤,蔡力.铜粉导电胶的制各研究[J].中国胶粘剂,2000,9(2):12-13,18.
[86]路庆华.新型导电胶的研究:(Ⅱ)耐银迁移导电胶的研究[J].功能材料,1998,29(4):439～441
[87]F. C. Walsh,M. E. Herron. Electrocrystallization and Electrochemical Control of Crystal Growth:Fundamental Considerations and Electrodeposition of Metals[J]. J.Phys.D:Appl.Phys,1991,24:217～225.
[88]E.Budevski,G.Staikov,W.J.Lorenz.Electrocrystallization:Nucleation and Growth Phenomena[J].Electrochim Acta,2000,45(15-16):2559～2574.
[89]虞苏玮,安维丹,欧萌,李刚.高性能非银导电胶粘剂研究及应用[J].电子工艺技术,1997,18(1)：34～39.
[90]DAVID W M.Copper-based conductive polymers:A new concept in conductive resins[J].J Adhesion.2000,74:301～315.
[91]TANIGAKI,TSU YOSHI,IZAWA,et al.Resin compositions,resin moldings and their methods of production[P].US 6096245,2000-08-01.
[92]杨小峰.CLD-20结构性导电胶的研制与应用[J].中国胶粘剂,1999,8(2):39-41,44.
[93]DAVID W M. Copper-based conductive polymers:A new concept in conductive resins[J].J Adhesion.2000,74:301～315.
[94]Zhou Y, Liu H J, Yu S H, Preparation of nanocrystalline silver by the method of liquid-solid arc discharge combined with hydrothermal treatment[J]. Mater. Resear.Bull,1999,34(10-11):1683～1688.
[95]Vorobyova S A, Lesnikovich A I, Sobal N S, Preparation of silver nanoparticles by interphase reduction, Colloids and Surfaces A[J]. Physicochemical and Engineering Aspects,1999,152(3):375-379.
[96]谭富彬,赵玲,刘林.纳米银粉的液相化学制备及其特性[J].贵金属,1999,20(3)：9-12.
[97]陈康生.玻璃微珠的新制法[J].四川化32,2006,9(1):16-17.
[98]刘伯元,黄世鲜,江广城.超细玻璃微珠的研究[C].2002年中国工程塑料加工应用技术研讨会论文集.济南：中国工程塑料工业协会加工应用专委会,188-192.
[99]Bogush G H, Zukoski I V. Uniform silica particle precipitation:an aggregative growth mode[J]. Journal of Colloid and Interface Science,1991,142(1): 19-34.
[100]叶为春.硅基贵金属膜材料的制备、形貌控制及性质分析：[博士学位论文].兰州：兰州大学,2008
[101]Chen S L, Dong P, Yang G H, et al. The size dependence of growth rate of monodisperse silica particles from tetraalkoxysilanes[J]. Journal of Colloid and Interface Science,1997,189:268-272.
[102]Vorobyova S A, Lesnikovich A I, Sobal N S, Preparation of silver nanoparticles by interphase reduction, Colloids and Surfaces A[J]. Physicochemical and Engineering Aspects,1999,152(3):375-379.
[103]Scharifker,Hills.Theoretical and Experimental Studies of Multiple Nucleation[J].Electrochim Acta,1983,28(7):879-889.
[104]Ouassim Ghodbanea,Lionel Roue,Daniel Belanger.Copper electrodeposition on pyrolytic graphite electrodes:Effect of the copper salt on the electrodeposition process[J].Electrochimica Acta,2007,52:5843-5855.
[105]胡兵.改性聚醚醚酮增韧环氧树脂的研究：[博士学位论文].武汉：武汉理工大学,2007
[106]吴懿平,吴大海,袁忠发,等.镀银铜粉导电胶的研究[J].电子元件与材料,2005,24(4)：32-35
[107]曾黎明.功能复合材料及其应用[M].北京：化学工业出版社,2006.10-13.
[108]查全性.电极过程动力学导论[M].北京:科学出版社,2002:306-310.