常温湿法制备聚酰亚胺/银复合薄膜的微结构与性能研究
摘要
本文采用由均苯四甲酸酐(PMDA)和4,4'-二胺基二苯醚(ODA)型成品聚酰亚胺(PI)薄膜,在碱液(KOH)的水溶液中使其表面水解生成聚酰胺酸(此时以钾盐的形式存在),随后将其放入银盐(含[Ag(NH3)2]+)溶液中进行离子交换,使薄膜水解的聚酰胺酸层中载入银氨离子,在具有还原性的双氧水溶液中进行短时间的还原处理后,制备出具有高反射、高导电性能的聚酰亚胺/银复合薄膜。
影响PI/Ag复合薄膜表面银层微结构与反射和导电等性能的关系进行了研究,采用扫描电子显微镜(SEM)和X射线光电子能谱(XPS)跟踪了聚酰亚胺薄膜表面银纳米粒子还原聚集及最终形成银层的生长过程。探索了多种因素对复合薄膜性能的影响进行了研究,并确定了较佳的制备工艺。
当薄膜在经过KOH (4M)水解3个小时水解处理,并在银氨溶液(0.02M)中离子交换20分钟,且经双氧水(0.01M)还原大约一分钟时,PI/Ag复合薄膜的反射率最高可以达到84.4%,方块电阻最低接近0.5Ω/sq。
Double-Surface-Silvered polyimide films have been prepared by alkali hydroxylation of pristine polyimide film surface in KOH aqueous solution and incorporation of [Ag(NH3)2]+ ions through subsequent ion exchange. Finally, the polyimide films were immersed into peroxide solution for certain minutes to reduce the doped [Ag(NH3)2]+ ions and fabricate high conductive and reflective PI/Ag hybrid films.
Factors of effect on reflectivity and conductive characteristis were studied and the best preparition route was selected. The formation process of the silvered polymeric films was traced by SEM observation and XPS.
Silvered films were found that the surface reflectivity could be detected upmost to 84.4% and surface resistance at ca. 0.5Ω/sq after treatment of the condition:KOH(4M) treatment for 3h, ion exchange for 20min, H2O2(0.01M) reduction for about 1 minute.
影响PI/Ag复合薄膜表面银层微结构与反射和导电等性能的关系进行了研究,采用扫描电子显微镜(SEM)和X射线光电子能谱(XPS)跟踪了聚酰亚胺薄膜表面银纳米粒子还原聚集及最终形成银层的生长过程。探索了多种因素对复合薄膜性能的影响进行了研究,并确定了较佳的制备工艺。
当薄膜在经过KOH (4M)水解3个小时水解处理,并在银氨溶液(0.02M)中离子交换20分钟,且经双氧水(0.01M)还原大约一分钟时,PI/Ag复合薄膜的反射率最高可以达到84.4%,方块电阻最低接近0.5Ω/sq。
Double-Surface-Silvered polyimide films have been prepared by alkali hydroxylation of pristine polyimide film surface in KOH aqueous solution and incorporation of [Ag(NH3)2]+ ions through subsequent ion exchange. Finally, the polyimide films were immersed into peroxide solution for certain minutes to reduce the doped [Ag(NH3)2]+ ions and fabricate high conductive and reflective PI/Ag hybrid films.
Factors of effect on reflectivity and conductive characteristis were studied and the best preparition route was selected. The formation process of the silvered polymeric films was traced by SEM observation and XPS.
Silvered films were found that the surface reflectivity could be detected upmost to 84.4% and surface resistance at ca. 0.5Ω/sq after treatment of the condition:KOH(4M) treatment for 3h, ion exchange for 20min, H2O2(0.01M) reduction for about 1 minute.
引文
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[4]Southward R E, Thompson D W. Reflective and conductive silvered polyimide films for space applications prepared via a novel single-stage self-metallization technique[J]. Mater. Design,2001,22:565-576
[5]丁孟贤.聚酰亚胺——化学、结构与性能的关系及材料[M].北京：科学出版社,2006.
[6]杨祖华,王刚,王鸿灵.聚酰亚胺薄膜的制备及其摩擦学性能研究[J].材料科学与工程学报,2004,22(1)：105-109
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[10]刘润山,赵三平,张廷余,等.抗高温蠕变高粘结性共聚酰亚胺应变胶研究[J].功能高分子学报,2000(2)：49-53
[11]Zhu P K,Li Z B. Preparation and Characterization of Negative Photosensitive Polysiloxaneimide[J]. Appl Plym Sci,1995,55:1111-1116
[12]Nye S A,Swim S A. Polymidess ynthesizedfmmsiloxane egnilibated 1,3-Bis(3, 4-diearboxyphenyl)-1,1,3,3'-tetram-ethylsilormedianh ydnide[J]. Appl Polym Sci, 1991,43:1539-1547
[13]Kariuki N N, Luo J, Hassan S A. Assembly of biometallic gold-silver nanopartilces via selective interparticle dicarboxylate-silver linkages[J]. Chem. Mater.,2006,18: 123-132
[14]樊友兵,李鸿岩,周升,等.聚酰亚胺/纳米二氧化钛复合物的合成与性能研究[J].绝缘材料,2004(3)：22-25.
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[16]COMELIUS C, HIBSHMAN C, MARAND E. J Membrane Sci,2002,202(1-2): 97
[17]SMAIHI M, SCHROTIER J C J Memb rane Sci,1999,161(1):157
[18]李传峰,钟顺和.催化学报,2001,22(5)：49
[19]Guo X, Fang J, Watari T. Novel Sulfonated Polyimides as Polyelectrolytes for Fuel Cell Application.2. Synthesis and Proton Conductivity of Polyimides from 9,9-Bis (4-aminophenyl)fluorene-2,7-disulfonic Acid[J]. Macromolecules,35:6707-6713
[20]李福成.聚酰亚胺/无机纳米复合材料的制备、结构与性能[J].工程塑料应用,2006,34(4)：68-71
[21]Johns I B, McElhill E A, Smith J O. Thermal stability of some organic compounds [J]. J. Chem. Eng. Data,1962,7 (2):277-281
[22]Southward R E, Thompson D S, Thompson D W. Prepartion of silvered polyimide mirrors via self-metallizing poly(amic acid) resins[J]. Metal-containing Polym. Mater., 1996:349-356
[23]齐胜利.聚酰亚胺/银复合薄膜的制备及相关机理研究[D].北京：北京化工大学,2008
[24]崔永丽,张仲华,江利,欧雪梅.聚酰亚胺的性能及应用.塑料科技,2005,3：50-53
[25]张秀菊,陈鸣才,黄玉急,丛广民.聚酞亚胺的性能、应用及发概况.广州化学,1998,3：58-66
[26]方志宁.新型聚酰亚胺材料及其合成.2009,10：124-127
[27]Tang J C, Lin G L, Yang H C. Polyimide-silica nanocomposites exhibiting low thermal expansion coefficient and water absorption from surface-modified silica[J]. J. Appl. Polym. Sci.,2007,104:4096-4105
[28]Akamatsu K, Shinkal H, Ikeda S. Controlling interparticle spacing among metal nanoparticles through metal-catalyzed decomposition of surrounding polymer matrix[J]. J.Am. Chem. Soc.,2005,127:7980-7981
[29]Ranucci E, Sandgren A, Andronova N. Improved polyimide/metal adhesion by chemical modification approaches[J]. J. Appl. Polym. Sci.,2001,82:1971-1985
[30]Ikeda S, Yanagimoto H, Akamatsu K. Copper/polyimide heterojunctions:controlling interfacial structures through an additive-based, all-wet chemical process using ion-doped precursors [J]. Adv. Funct. Mater.2007,17:889-897
[31]Li Y, Lu Q, Qian X. Preparation of surface bound silver nanoparticles on polyimide by surface modification method and its application on electroless metal deposition [J]. Appl. Surf. Sci.,2004,233:299-306
[32]Matsuda S, Yasuda Y, Ando S. Fabrication of polyimide-blend thin films containing uniformly oriented silver nanorods and their use as flexible, linear polarizers [J]. Adv. Mater.,2005,17:2221-2224
[33]Rubira A F, Rancourt J D, Taylor L T. Chemical factors that influence the production of conductivie and/or reflective silver-doped polyimide films[J]. J. Macromol. Sci.-Pure Appl. Chem.,1998, A35(4):621-636
[34]Matsuda S, Ando S. Anisotropy in optical transmittance and molecular chain orientation of silver-dispersed uniaxially drawn polyimide films[J]. Polym. Adv. Technol.,2003,14:458-470
[35]Wu Z, Wu D, Yang W. Preparation of highly reflective and conductive metallized polyimide films through surface modification:processing, morphology and properties[J]. J. Mater. Chem.,2006,16:310-316
[36]Southward R E, Thompson D W. Inverse CVD:A novel synthetic approach to metallized polymeric films[J]. Adv. Mater.,1999,11(12):1043-1047
[37]曹红葵.聚酰亚胺性能及合成方法[J].化学推进剂与高分子材料,2008,6(3)：24-26
[38]童跃进,李悦生,丁孟贤.聚酰亚胺的预聚体——聚酰胺酯的研究进展[J].高分子通讯,1998,(3)：44-50
[39]吕生华,吕庆莉,梁国正.聚酰亚胺树脂合成及应用研究的新进展[J].西北轻工业学院学报,2002,20(2)：73-78
[40]李生柱.聚酰亚胺的现状和将来[J].化工新型材料,1999,27(11)：12-17
[41]许发功.无机纳米粒子的制备、表征及作为生物探针的应用[D].安徽：安徽师范大学,2004
[42]杨帅奇.常温下湿法制备双面聚酰亚胺/银复合薄膜[B].北京：北京化工大学,2008
[43]Tripathi A K, Roy A, Goel T C. Optically transparent and non-linear LiNbO3: polyimide composite:preparation and characterization[J]. J. Mater. Sci. Lett.,1997, 16:1045-1047
[44]Green P F, Berger L L. Effects of polyimide chemical structure and environment on the diffusivity of copper[J]. Thin Solid Films,1993,224(2):209-216
[45]Rozovskis G, Vinkevicius J, Jaciauskiene J. Plasma modification of polyimide for improving adhesion[J]. J. Adhes. Sci. Tech.,1996,10:399-406
[46]Matsuda S, Yasuda Y, Ando S. Fabrication of polyimide-blend thin films containing uniformly oriented silver nanorods and their use as flexible, linear polarizers[J]. Adv. Mater.,2005,17:2221-2224
[47]Xu F J, Kang E T, Neoh K G. Uv-induced coupling of 4-vinylbenzyl chloride on hydrogen-terminated Si(100) surfaces for the preparation of well-defined polymer-Si hybrids via surface-initiated ATRP[J]. Macromolecules,2005,38:1573-1580
[48]Foitzik A, Faupel F. Structural investigation of the silver-polyimide interface by cross-sectional tem and ion-beam sputtering[J]. Mater. Res. Soc. Symp. Proc.,1991, 203:59-64
[49]Yang C Y, Chen J S, Hsu S L C. Investigation of the interfacial reaction between metal and fluoride-contained polyimides[J]. J. Vac. Sci. Technol.,2005, A 23(4): 862-868
[50]Southward R E, W.Thompson D, S.H.Sproul. Control of surface specular reflectivity and electrical conductivity in silvered polyimide films via in situ thermal reduction of (perfluoroalkanoato) silver(i) complexes[J]. Polym. Mater. Sci. Eng.,1998,78:11-12
[51]Wu Z, Wu D, Qi S. Preparation of surface conductive and highly reflective silvered polyimide films by surface modification and in situ self-metallization technique[J]. Thin Solid Films,2005,493:179-184
[52]武德珍,吴战鹏,齐胜利.一种双面高反射高导电聚酰亚胺/银薄膜的制备方法[P].中国专利,1803312.2006-07-19
[53]李福成,訾静.聚酰亚胺(PI)/无机纳米复合材料的制备、结构与性能[J].纤维复合材料,2005,3：6-10
[54]Wu Dezhen, Zhang Tao, Wang Wencai, Zhang Liqun and Jin Riguang. Reflectivity and conductive surface-silvered polyimide films prepared by surface graft copolymerization and electroless plating [J]. Polym. Adv. Technol.2008.19(3). 335-341
[55]Denis Weaire. Kelvin's ideal foam structure[J]. Physics:Conference Series 158 (2009) 012005
[56]Yujie Xiong, Isao Washio, Jingyi Chen, Martin Sadilek, and Younan Xia, Trimeric Clusters of Silver in Aqueous AgNO3 Solutions and Their Role as Nuclei in Forming Triangular Nanoplates of Silver. Angew. Chem. Int. Ed.2007,46,4917-4921
[2]丁孟贤,何天白.聚酰亚胺新型材料.北京：科学出版社,1998
[3]邹胜欧.聚酰亚胺发展动向.化工新型材料,1999,27(3)：3
[4]Southward R E, Thompson D W. Reflective and conductive silvered polyimide films for space applications prepared via a novel single-stage self-metallization technique[J]. Mater. Design,2001,22:565-576
[5]丁孟贤.聚酰亚胺——化学、结构与性能的关系及材料[M].北京：科学出版社,2006.
[6]杨祖华,王刚,王鸿灵.聚酰亚胺薄膜的制备及其摩擦学性能研究[J].材料科学与工程学报,2004,22(1)：105-109
[7]仇武林.新型聚酰亚胺的合成与表征[D].南京：南京理工大学,1995
[8]丁孟贤编著,聚酰亚胺-化学、结构与性能的关系及材料[M].北京：科学出版社,2006.9
[9]李友清,刘丽,刘润山.聚酰亚胺研究[J].精细石油化工进展,2003(3)：38-46
[10]刘润山,赵三平,张廷余,等.抗高温蠕变高粘结性共聚酰亚胺应变胶研究[J].功能高分子学报,2000(2)：49-53
[11]Zhu P K,Li Z B. Preparation and Characterization of Negative Photosensitive Polysiloxaneimide[J]. Appl Plym Sci,1995,55:1111-1116
[12]Nye S A,Swim S A. Polymidess ynthesizedfmmsiloxane egnilibated 1,3-Bis(3, 4-diearboxyphenyl)-1,1,3,3'-tetram-ethylsilormedianh ydnide[J]. Appl Polym Sci, 1991,43:1539-1547
[13]Kariuki N N, Luo J, Hassan S A. Assembly of biometallic gold-silver nanopartilces via selective interparticle dicarboxylate-silver linkages[J]. Chem. Mater.,2006,18: 123-132
[14]樊友兵,李鸿岩,周升,等.聚酰亚胺/纳米二氧化钛复合物的合成与性能研究[J].绝缘材料,2004(3)：22-25.
[15]CORNELIUS C, HIBSHMAN C. Sep Purif Teehnol,2001,25(1):181.
[16]COMELIUS C, HIBSHMAN C, MARAND E. J Membrane Sci,2002,202(1-2): 97
[17]SMAIHI M, SCHROTIER J C J Memb rane Sci,1999,161(1):157
[18]李传峰,钟顺和.催化学报,2001,22(5)：49
[19]Guo X, Fang J, Watari T. Novel Sulfonated Polyimides as Polyelectrolytes for Fuel Cell Application.2. Synthesis and Proton Conductivity of Polyimides from 9,9-Bis (4-aminophenyl)fluorene-2,7-disulfonic Acid[J]. Macromolecules,35:6707-6713
[20]李福成.聚酰亚胺/无机纳米复合材料的制备、结构与性能[J].工程塑料应用,2006,34(4)：68-71
[21]Johns I B, McElhill E A, Smith J O. Thermal stability of some organic compounds [J]. J. Chem. Eng. Data,1962,7 (2):277-281
[22]Southward R E, Thompson D S, Thompson D W. Prepartion of silvered polyimide mirrors via self-metallizing poly(amic acid) resins[J]. Metal-containing Polym. Mater., 1996:349-356
[23]齐胜利.聚酰亚胺/银复合薄膜的制备及相关机理研究[D].北京：北京化工大学,2008
[24]崔永丽,张仲华,江利,欧雪梅.聚酰亚胺的性能及应用.塑料科技,2005,3：50-53
[25]张秀菊,陈鸣才,黄玉急,丛广民.聚酞亚胺的性能、应用及发概况.广州化学,1998,3：58-66
[26]方志宁.新型聚酰亚胺材料及其合成.2009,10：124-127
[27]Tang J C, Lin G L, Yang H C. Polyimide-silica nanocomposites exhibiting low thermal expansion coefficient and water absorption from surface-modified silica[J]. J. Appl. Polym. Sci.,2007,104:4096-4105
[28]Akamatsu K, Shinkal H, Ikeda S. Controlling interparticle spacing among metal nanoparticles through metal-catalyzed decomposition of surrounding polymer matrix[J]. J.Am. Chem. Soc.,2005,127:7980-7981
[29]Ranucci E, Sandgren A, Andronova N. Improved polyimide/metal adhesion by chemical modification approaches[J]. J. Appl. Polym. Sci.,2001,82:1971-1985
[30]Ikeda S, Yanagimoto H, Akamatsu K. Copper/polyimide heterojunctions:controlling interfacial structures through an additive-based, all-wet chemical process using ion-doped precursors [J]. Adv. Funct. Mater.2007,17:889-897
[31]Li Y, Lu Q, Qian X. Preparation of surface bound silver nanoparticles on polyimide by surface modification method and its application on electroless metal deposition [J]. Appl. Surf. Sci.,2004,233:299-306
[32]Matsuda S, Yasuda Y, Ando S. Fabrication of polyimide-blend thin films containing uniformly oriented silver nanorods and their use as flexible, linear polarizers [J]. Adv. Mater.,2005,17:2221-2224
[33]Rubira A F, Rancourt J D, Taylor L T. Chemical factors that influence the production of conductivie and/or reflective silver-doped polyimide films[J]. J. Macromol. Sci.-Pure Appl. Chem.,1998, A35(4):621-636
[34]Matsuda S, Ando S. Anisotropy in optical transmittance and molecular chain orientation of silver-dispersed uniaxially drawn polyimide films[J]. Polym. Adv. Technol.,2003,14:458-470
[35]Wu Z, Wu D, Yang W. Preparation of highly reflective and conductive metallized polyimide films through surface modification:processing, morphology and properties[J]. J. Mater. Chem.,2006,16:310-316
[36]Southward R E, Thompson D W. Inverse CVD:A novel synthetic approach to metallized polymeric films[J]. Adv. Mater.,1999,11(12):1043-1047
[37]曹红葵.聚酰亚胺性能及合成方法[J].化学推进剂与高分子材料,2008,6(3)：24-26
[38]童跃进,李悦生,丁孟贤.聚酰亚胺的预聚体——聚酰胺酯的研究进展[J].高分子通讯,1998,(3)：44-50
[39]吕生华,吕庆莉,梁国正.聚酰亚胺树脂合成及应用研究的新进展[J].西北轻工业学院学报,2002,20(2)：73-78
[40]李生柱.聚酰亚胺的现状和将来[J].化工新型材料,1999,27(11)：12-17
[41]许发功.无机纳米粒子的制备、表征及作为生物探针的应用[D].安徽：安徽师范大学,2004
[42]杨帅奇.常温下湿法制备双面聚酰亚胺/银复合薄膜[B].北京：北京化工大学,2008
[43]Tripathi A K, Roy A, Goel T C. Optically transparent and non-linear LiNbO3: polyimide composite:preparation and characterization[J]. J. Mater. Sci. Lett.,1997, 16:1045-1047
[44]Green P F, Berger L L. Effects of polyimide chemical structure and environment on the diffusivity of copper[J]. Thin Solid Films,1993,224(2):209-216
[45]Rozovskis G, Vinkevicius J, Jaciauskiene J. Plasma modification of polyimide for improving adhesion[J]. J. Adhes. Sci. Tech.,1996,10:399-406
[46]Matsuda S, Yasuda Y, Ando S. Fabrication of polyimide-blend thin films containing uniformly oriented silver nanorods and their use as flexible, linear polarizers[J]. Adv. Mater.,2005,17:2221-2224
[47]Xu F J, Kang E T, Neoh K G. Uv-induced coupling of 4-vinylbenzyl chloride on hydrogen-terminated Si(100) surfaces for the preparation of well-defined polymer-Si hybrids via surface-initiated ATRP[J]. Macromolecules,2005,38:1573-1580
[48]Foitzik A, Faupel F. Structural investigation of the silver-polyimide interface by cross-sectional tem and ion-beam sputtering[J]. Mater. Res. Soc. Symp. Proc.,1991, 203:59-64
[49]Yang C Y, Chen J S, Hsu S L C. Investigation of the interfacial reaction between metal and fluoride-contained polyimides[J]. J. Vac. Sci. Technol.,2005, A 23(4): 862-868
[50]Southward R E, W.Thompson D, S.H.Sproul. Control of surface specular reflectivity and electrical conductivity in silvered polyimide films via in situ thermal reduction of (perfluoroalkanoato) silver(i) complexes[J]. Polym. Mater. Sci. Eng.,1998,78:11-12
[51]Wu Z, Wu D, Qi S. Preparation of surface conductive and highly reflective silvered polyimide films by surface modification and in situ self-metallization technique[J]. Thin Solid Films,2005,493:179-184
[52]武德珍,吴战鹏,齐胜利.一种双面高反射高导电聚酰亚胺/银薄膜的制备方法[P].中国专利,1803312.2006-07-19
[53]李福成,訾静.聚酰亚胺(PI)/无机纳米复合材料的制备、结构与性能[J].纤维复合材料,2005,3：6-10
[54]Wu Dezhen, Zhang Tao, Wang Wencai, Zhang Liqun and Jin Riguang. Reflectivity and conductive surface-silvered polyimide films prepared by surface graft copolymerization and electroless plating [J]. Polym. Adv. Technol.2008.19(3). 335-341
[55]Denis Weaire. Kelvin's ideal foam structure[J]. Physics:Conference Series 158 (2009) 012005
[56]Yujie Xiong, Isao Washio, Jingyi Chen, Martin Sadilek, and Younan Xia, Trimeric Clusters of Silver in Aqueous AgNO3 Solutions and Their Role as Nuclei in Forming Triangular Nanoplates of Silver. Angew. Chem. Int. Ed.2007,46,4917-4921