聚氨酯/纳米银复合薄膜的制备及结构与性能研究
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摘要
本文采用热处理还原银盐原位引入银粒子的方法，成功制备了聚氨酯/天然石墨-纳米银(PU/C-Ag)导电复合薄膜，用两种不同的银源制备了PU/Ag复合薄膜，并通过透射电镜(TEM)、扫描电镜(SEM)观察了该复合薄膜的微观结构，用X射线衍射仪(XRD)跟踪了银的还原和银粒子的生长过程，探讨了加热温度和加热时间对银还原过程的影响，并研究了纳米银的生成和聚集对PU/C复合体系导电性能的影响。
对PU/C和PU/C-Ag两种复合体系进行了比较，结果表明：PU/C-Ag的导电性要明显高于PU/C。这是因为银盐引入后，随着热处理的进行，银粒子不断的生成和聚集，并最终以纳米尺寸(约10nm)均匀分散在聚合物基体中。纳米银粒子在天然石墨粒子之间起到了桥梁的作用，改善了复合体系的导电通路，显著提高了复合体系的导电性。
为了研究分子链柔顺性对银的迁移的影响，本文制备了PU/Ag和聚酰亚胺(PI)/Ag复合薄膜，通过比较二者的电阻，以及扫描电镜观察复合薄膜表面的粒子形貌，发现PU/Ag复合薄膜中的银粒子并没有迁移到复合薄膜的表面。这是由于PU的玻璃化转变温度(Tg)低，链段柔软，分子链紧密堆积，限制了银粒子的迁移运动。而PI因为分子链刚性较大，不容易紧密堆积，形成的银粒子可以沿链间自由体积迁移，另一方面，高温条件下，增加了银粒子迁移动力，因此银粒子能迁移到薄膜的表面。
分别采用醋酸银(AgAc)和硝酸银(AgNO_3)来作银源制备PU/Ag复合薄膜，通过SEM和TEM的观察，发现用AgAc作银源时还原出来的银粒子呈球状，而AgNO_3作银源时还原出来的银粒子呈现不规则的形状。
以醋酸银为银源，制得了具有中等反射率的PU/Ag复合薄膜，其上表面的反射率在35％～50％，下表面的反射率在40％～60％。
Conductive polyurethane / graphite-silver nanoparticles (PU/C-Ag) composite films have been successfully prepared. The silver nanoparticles were introduced via in-situ reduction of the incorporated silver salts. PU/Ag composite films have also been fabricated by employing two different silver complexes. TEM and SEM were used to observe the micro structure of the composite films. XRD measurement was preformed to trace the silver reduction and aggregation process. The influences of heat treatment temperature and time on the reduction of silver have been studied. Also, the growth and conglomeration of the silver nanoparticles and their effects on the conductivity of the PU/C composite films have been investigated.
Surface resistance measurements indicated that the conductivity of PU/C-Ag was obviously higher than PU/C. It is suggested that the silver particles, which were introduced by thermal reduction of the incorporated silver complexes and uniformly distributed in the polymer matrix, act as conductive path in the composite system by contacting the graphite particles in the system and therefore give a better conductivity.
In order to study the influence of flexibility of polymer chain on the silver's migration, PU/Ag and polyimide (PI)/Ag composite films were prepared in our work. The morphology and surface topography of the films were observed by TEM and SEM. And it is found that the silver particles had not migrated to the films surface as it happened in PI/Ag system. This is because the PU has a lower Tg and therefore more flexible chains as compared with the PI's, which would result in a more compacted polymer chains and restricted the migration of silver particles. In contrast, the PI chains are rigid and difficult to be packed very closely. Therefore there is a larger free volume which could facile the silver migration at high temperature to the surface of the composite films.
Silver acetate (AgAc) and silver nitrate (AgNO_3) were used as silver precursors in our research to prepare PU/Ag composite films. The shapes of the formed silver particles are rather different. For the silver acetate system, the silver is present as spherical particles. While for the silver nitrate system, irregular particles were observed.
PU/Ag composite films with modest reflectivity( 35-50% on the upside, 40-60% on the underside) were prepared when AgAc were used as silver origins.
对PU/C和PU/C-Ag两种复合体系进行了比较，结果表明：PU/C-Ag的导电性要明显高于PU/C。这是因为银盐引入后，随着热处理的进行，银粒子不断的生成和聚集，并最终以纳米尺寸(约10nm)均匀分散在聚合物基体中。纳米银粒子在天然石墨粒子之间起到了桥梁的作用，改善了复合体系的导电通路，显著提高了复合体系的导电性。
为了研究分子链柔顺性对银的迁移的影响，本文制备了PU/Ag和聚酰亚胺(PI)/Ag复合薄膜，通过比较二者的电阻，以及扫描电镜观察复合薄膜表面的粒子形貌，发现PU/Ag复合薄膜中的银粒子并没有迁移到复合薄膜的表面。这是由于PU的玻璃化转变温度(Tg)低，链段柔软，分子链紧密堆积，限制了银粒子的迁移运动。而PI因为分子链刚性较大，不容易紧密堆积，形成的银粒子可以沿链间自由体积迁移，另一方面，高温条件下，增加了银粒子迁移动力，因此银粒子能迁移到薄膜的表面。
分别采用醋酸银(AgAc)和硝酸银(AgNO_3)来作银源制备PU/Ag复合薄膜，通过SEM和TEM的观察，发现用AgAc作银源时还原出来的银粒子呈球状，而AgNO_3作银源时还原出来的银粒子呈现不规则的形状。
以醋酸银为银源，制得了具有中等反射率的PU/Ag复合薄膜，其上表面的反射率在35％～50％，下表面的反射率在40％～60％。
Conductive polyurethane / graphite-silver nanoparticles (PU/C-Ag) composite films have been successfully prepared. The silver nanoparticles were introduced via in-situ reduction of the incorporated silver salts. PU/Ag composite films have also been fabricated by employing two different silver complexes. TEM and SEM were used to observe the micro structure of the composite films. XRD measurement was preformed to trace the silver reduction and aggregation process. The influences of heat treatment temperature and time on the reduction of silver have been studied. Also, the growth and conglomeration of the silver nanoparticles and their effects on the conductivity of the PU/C composite films have been investigated.
Surface resistance measurements indicated that the conductivity of PU/C-Ag was obviously higher than PU/C. It is suggested that the silver particles, which were introduced by thermal reduction of the incorporated silver complexes and uniformly distributed in the polymer matrix, act as conductive path in the composite system by contacting the graphite particles in the system and therefore give a better conductivity.
In order to study the influence of flexibility of polymer chain on the silver's migration, PU/Ag and polyimide (PI)/Ag composite films were prepared in our work. The morphology and surface topography of the films were observed by TEM and SEM. And it is found that the silver particles had not migrated to the films surface as it happened in PI/Ag system. This is because the PU has a lower Tg and therefore more flexible chains as compared with the PI's, which would result in a more compacted polymer chains and restricted the migration of silver particles. In contrast, the PI chains are rigid and difficult to be packed very closely. Therefore there is a larger free volume which could facile the silver migration at high temperature to the surface of the composite films.
Silver acetate (AgAc) and silver nitrate (AgNO_3) were used as silver precursors in our research to prepare PU/Ag composite films. The shapes of the formed silver particles are rather different. For the silver acetate system, the silver is present as spherical particles. While for the silver nitrate system, irregular particles were observed.
PU/Ag composite films with modest reflectivity( 35-50% on the upside, 40-60% on the underside) were prepared when AgAc were used as silver origins.
引文
[1] 傅明源，孙酣经．聚氨酯弹性体及其应用[M]，北京：化学工业出版社，1999
[2] Patricia M. Frontini, Marta Rink, Andea Pavan. Development of Polyurethane Engineering Thermoplastics. Ⅰ. Preparation and Structure[J]. Appl Polym. Sci, 1993,48:2003
[3] 李绍雄，刘益军．聚氨酯树脂及其应用[M]，北京：化学工业出版社，2002
[4] 朱吕民．聚氨酯合成材料[M]，南京：江苏科学技术出版社，2002
[5] 赵孝彬，杜磊，张小平．聚氨酯弹性体及其微相分离[J]．高分子材料科学与工程，2002，18(2)：16-20
[6] 李俊贤．塑料工业手册：聚氨酯[M]．北京：化学工业出版社，1999
[7] 曹学均．美国国家纳米技术计划[J]．国外科技动态，2000，6：18-19
[8] 华中一．纳米科学与技术[J]．新材料产业，2000，12：73-77
[9] 黄锐．纳米塑料——聚合物/纳米无机复合材料研制、应用与进展[M]．北京：中国轻工业出版社，2002
[10] 杨红艳．聚氨酯/纳米碳酸钙复合材料及性能的研究[D]．成都：西华大学，2006
[11] 林原，江畹兰，白乃斌，刘军．超细金属微粒及其复合聚合物的研究进展[J]．化工新型材料，1998，(3)：16-19
[12] Southward Robin E., Thompson D. Scott, Thompson D. W., Caplan Maggie L. and A.K.St.Clair. Reflective Polyimide Films via in situ formation of a silvered surface. [J]. Poly. Mater. Sci. Eng., 1995,7:382-383
[13] Southward Robin E., Thompson D. Scott, Thompson David W., et al. Preparation of silvered potyimide mirrors via self-metalizating poly(amic acid) resins Metal-containing polymeric Materials [C]. Proc.Int.Symp., 1996:349-356
[14] Warner Julia D., Pevzner Miriam, Dean C. J., Kranbuehl D. E., et al. Synthesis of hexafuoroisopropylidene-containing polyimide-silver nanocomposite fillms evolving specularly reflective metal surfaces [J]. Mater. Chem., 2003, 13:1847-1852
[15] Southward Robin E., Thompson David W.. Inverse CVD:A Novel Synthetic Approach to Metallized Polymeric Films[J]. Adv. Mater., 1999,11(12):1043-1047
[16] B.L. French, Luke M. Davis, E. S. Munzinger, J. W. J. Slavin, P. C. Christy, D. W. Thompson, and R. E. Southward. Palladium-Polyimide Nanocomposite Membranes: Synthesis and Characterization of Reflective and Electrically Conductive Surface-Metallized Films[J]. Chem. Mster, 2005,17(8):2091-2010
[17] Kensuke Akamatsu, Shingo Ikeda, Hidemi Nawafune. Site-Selective Direst Silver Metallization on Surface-Modified Polyimide Layers [J]. Langmuir, 2003,19: 10366-10371
[18] 崔岩，张成义，张万喜，孙广平，孙国恩，聚合物基金属纳米复合材料研究进展[J]．高分子材料科学与工程，20(2)：19-23
[19] Yin Y D, Xu X L, Ge X W, RADIAT Phys Chem. 1998,53:67
[20] Zhou H S, Wada T, Sasabe H, Synth, Met, 1996,81:129
[21] Lopes WA, Jaeger HM. Nature, 2001, 414:735
[22] 丁孟贤，何白天．聚酰亚胺新型材料[M]．北京：科学出版社，1998
[23] Robin E. Southward, David W. Thompson, Anne K. St. Clair.. Control of Reflectivity and Surface Conductivity in Metallized Polyimide Films Prepared via in Situ Silver(Ⅰ) Reduction [J].Chem. Mater., 1997,9:501-510
[24] 郑玉斌，张善举，柯扬船，吴忠文．聚合物表面金属化的研究[J]．功能高分子学报，1996，19(4)
[25] 杜仕国，闫军，张同来，崔海萍．环氧树脂基铜粉导电涂料各组分对其导电性能的影响[J]．涂料工业，2004，34(8)：10-12
[26] 蒋红梅，袁宏，高保娇．王久芬．环氧—聚氨酯互穿聚合物网络导电涂料[J]．涂料工业，1999，(3)：12-15
[27] 周向东，刘朋生．超细导电粉末改性聚氨酯弹性体及其性能表征[J]．中国塑料，2005，19(4)：45-48
[28] 陈精华，刘伟区，宣宣宁，张斌．有机硅改性聚氨酯弹性体材料的研究[J]．聚氨酯工业，2004，19(1)：12-14
[29] 张田林，李再峰．纳米氢氧化镁补强阻燃聚氨酯弹性体[J]．弹性体，2004，14(5)：16-19
[30] 李丽霞，吕志平，王东凯．聚氨酯/纳米碳酸钙弹性体的制备与力学性能研究[J]．太原理工大学报，2003，34(6)：638-641
[31] 宋晓艳，张玉清，张杰，李俊贤．聚氨酯弹性体／蒙脱土纳米复合材料的合成与性能[J]．高分子学报，2004，5：640-644
[32] 马晓燕，梁国正，鹿海军，朱光明．累托石粘土/热塑性聚氨酯弹性体纳米复合材料的热性能研究[J]．高分子学报，2003，5：655-660
[33] 马晓燕，鹿海军，梁国正，颜红侠，吕美丽．累托石粘土／热塑性聚氨酯弹性体纳米复合材料的研究[J]．高分子学报，2003，1：62-67
[34] 倪平，李静，索继栓，李树本．TiO_2增强聚氨酯弹性体的制备和表征[J]．聚氨酯工业，2004，19(2)：6-9
[35] 张志华，沈军，吴广明，夏长生，杨帆，付甜，孙骐，王珏．SiO_2不同的掺杂方式对聚氨酯树脂材料性能的影响[J]．材料导报，2003，17：128-130
[36] 唐冬雁，许晴岩，蔡伟民，周德瑞，赵连城．BaTiO_3纳米粉／COPUIPNs复合体系的制备及力学性能研究[J]．材料科学与工艺，2003，11(2)：181-184
[37] 许鹏学，潘肇琦，杲云．聚氨酯/石墨导电复合材料的结构与性能表征[J]．中国塑料，2004，18(4)：43-46
[38] 王武生，潘才元，曾俊，阮德礼，钟峰．在线性或交联的聚氨酯粒子内原位还原制备纳米银粒子[J]．高等学校化学学报，2001，22(4)：700-702
[39] Jae Whan Cho, Jung Hyun So, Polyurethane-silver fibers prepared by infiltration and reduction of silver nitrate[J]. Materials Letters, 2006, 60:2653-2656
[40] Park Soo-Tin,Jang Yu-Sin. Preparation and characterization of activated carbon fibers supported with siver metal for antibacterial behavior[J]. Joumal of Colloid and Iterface Science,2003,261:239
[41] 王东青，李伟，刘学栋，黄岐善．医用聚氨酯弹性体的应用研究进展[J]．现代化工，2006，26：100-102
[42] Chi-Wei Chou,Shan-hui Hsu,Han Chang, Sheng-Mao Tseng,Hong-Ru Lin. Enhanced thermal and mechanical properties and biostability of polyurethane containing silver nanoparticles[J]. Polymer Degradation and Stability, 2006, 91:1017 -1024
[43] 龚文化，曾黎明．聚合物基导电复合材料研究进展[J]．化工新型材料，2002，30(4)：38-40
[44] M.Narkis, G.Lidor, A Vaxman, L.Zuri. New Injection Moldable Electrotastatic Dissipative (ESD) Composites Based on Very Low Carbon Black Loadings[J]. J.Electrost., 1999, 47:201-214
[45] 韩永芹．石墨/粘结剂导电复合材料性能的研究[J]．玻璃钢/复合材料，2006(2)：32-33
[46] 吴战鹏．具有高反射和高导电特性聚酰亚胺银复合薄膜的制备及其形成机理研究[D]，北京：北京化工大学，2005
[47] 宋芳，武德珍，张倩，齐胜利，姜立忠，金日光．原位一步法法制备BTDA／4，4'-ODA/4，4'SDA聚酰亚胺表面银化薄膜[J]．高分子学报，2006(4)：325-329
[48] 张艳芳，吴战鹏，齐胜利，蔡晴，庞中华，武德珍，金日光．聚酰亚胺/银复合膜的制备及其亚微相态与性能研究[J]．复合材料学报，2005，22(4)：30-34
[49] 齐胜利，吴战鹏，罗芸，宋芳，武德珍，金日光．原位一步法制备PMDA／ODA基PI/Ag复合薄膜[J]．功能高分子学报，2005，18(2)：222-226
[50] 丁孟贤，何天白．聚酰亚胺新型材料[M]，北京：科学出版社，1998
[51] 宋芳．分子结构对原位一步法制备聚酰亚胺银纳米复合薄膜表面性能的影响[D]，北京，北京化工大学，2005
[52] 贺蓉，钱雪峰，印杰，朱子康，王海林．银纳米棱镜的形成及其光学性能研究[J]．高等学校化学学报，2003，24(8)：1341-1345
[2] Patricia M. Frontini, Marta Rink, Andea Pavan. Development of Polyurethane Engineering Thermoplastics. Ⅰ. Preparation and Structure[J]. Appl Polym. Sci, 1993,48:2003
[3] 李绍雄，刘益军．聚氨酯树脂及其应用[M]，北京：化学工业出版社，2002
[4] 朱吕民．聚氨酯合成材料[M]，南京：江苏科学技术出版社，2002
[5] 赵孝彬，杜磊，张小平．聚氨酯弹性体及其微相分离[J]．高分子材料科学与工程，2002，18(2)：16-20
[6] 李俊贤．塑料工业手册：聚氨酯[M]．北京：化学工业出版社，1999
[7] 曹学均．美国国家纳米技术计划[J]．国外科技动态，2000，6：18-19
[8] 华中一．纳米科学与技术[J]．新材料产业，2000，12：73-77
[9] 黄锐．纳米塑料——聚合物/纳米无机复合材料研制、应用与进展[M]．北京：中国轻工业出版社，2002
[10] 杨红艳．聚氨酯/纳米碳酸钙复合材料及性能的研究[D]．成都：西华大学，2006
[11] 林原，江畹兰，白乃斌，刘军．超细金属微粒及其复合聚合物的研究进展[J]．化工新型材料，1998，(3)：16-19
[12] Southward Robin E., Thompson D. Scott, Thompson D. W., Caplan Maggie L. and A.K.St.Clair. Reflective Polyimide Films via in situ formation of a silvered surface. [J]. Poly. Mater. Sci. Eng., 1995,7:382-383
[13] Southward Robin E., Thompson D. Scott, Thompson David W., et al. Preparation of silvered potyimide mirrors via self-metalizating poly(amic acid) resins Metal-containing polymeric Materials [C]. Proc.Int.Symp., 1996:349-356
[14] Warner Julia D., Pevzner Miriam, Dean C. J., Kranbuehl D. E., et al. Synthesis of hexafuoroisopropylidene-containing polyimide-silver nanocomposite fillms evolving specularly reflective metal surfaces [J]. Mater. Chem., 2003, 13:1847-1852
[15] Southward Robin E., Thompson David W.. Inverse CVD:A Novel Synthetic Approach to Metallized Polymeric Films[J]. Adv. Mater., 1999,11(12):1043-1047
[16] B.L. French, Luke M. Davis, E. S. Munzinger, J. W. J. Slavin, P. C. Christy, D. W. Thompson, and R. E. Southward. Palladium-Polyimide Nanocomposite Membranes: Synthesis and Characterization of Reflective and Electrically Conductive Surface-Metallized Films[J]. Chem. Mster, 2005,17(8):2091-2010
[17] Kensuke Akamatsu, Shingo Ikeda, Hidemi Nawafune. Site-Selective Direst Silver Metallization on Surface-Modified Polyimide Layers [J]. Langmuir, 2003,19: 10366-10371
[18] 崔岩，张成义，张万喜，孙广平，孙国恩，聚合物基金属纳米复合材料研究进展[J]．高分子材料科学与工程，20(2)：19-23
[19] Yin Y D, Xu X L, Ge X W, RADIAT Phys Chem. 1998,53:67
[20] Zhou H S, Wada T, Sasabe H, Synth, Met, 1996,81:129
[21] Lopes WA, Jaeger HM. Nature, 2001, 414:735
[22] 丁孟贤，何白天．聚酰亚胺新型材料[M]．北京：科学出版社，1998
[23] Robin E. Southward, David W. Thompson, Anne K. St. Clair.. Control of Reflectivity and Surface Conductivity in Metallized Polyimide Films Prepared via in Situ Silver(Ⅰ) Reduction [J].Chem. Mater., 1997,9:501-510
[24] 郑玉斌，张善举，柯扬船，吴忠文．聚合物表面金属化的研究[J]．功能高分子学报，1996，19(4)
[25] 杜仕国，闫军，张同来，崔海萍．环氧树脂基铜粉导电涂料各组分对其导电性能的影响[J]．涂料工业，2004，34(8)：10-12
[26] 蒋红梅，袁宏，高保娇．王久芬．环氧—聚氨酯互穿聚合物网络导电涂料[J]．涂料工业，1999，(3)：12-15
[27] 周向东，刘朋生．超细导电粉末改性聚氨酯弹性体及其性能表征[J]．中国塑料，2005，19(4)：45-48
[28] 陈精华，刘伟区，宣宣宁，张斌．有机硅改性聚氨酯弹性体材料的研究[J]．聚氨酯工业，2004，19(1)：12-14
[29] 张田林，李再峰．纳米氢氧化镁补强阻燃聚氨酯弹性体[J]．弹性体，2004，14(5)：16-19
[30] 李丽霞，吕志平，王东凯．聚氨酯/纳米碳酸钙弹性体的制备与力学性能研究[J]．太原理工大学报，2003，34(6)：638-641
[31] 宋晓艳，张玉清，张杰，李俊贤．聚氨酯弹性体／蒙脱土纳米复合材料的合成与性能[J]．高分子学报，2004，5：640-644
[32] 马晓燕，梁国正，鹿海军，朱光明．累托石粘土/热塑性聚氨酯弹性体纳米复合材料的热性能研究[J]．高分子学报，2003，5：655-660
[33] 马晓燕，鹿海军，梁国正，颜红侠，吕美丽．累托石粘土／热塑性聚氨酯弹性体纳米复合材料的研究[J]．高分子学报，2003，1：62-67
[34] 倪平，李静，索继栓，李树本．TiO_2增强聚氨酯弹性体的制备和表征[J]．聚氨酯工业，2004，19(2)：6-9
[35] 张志华，沈军，吴广明，夏长生，杨帆，付甜，孙骐，王珏．SiO_2不同的掺杂方式对聚氨酯树脂材料性能的影响[J]．材料导报，2003，17：128-130
[36] 唐冬雁，许晴岩，蔡伟民，周德瑞，赵连城．BaTiO_3纳米粉／COPUIPNs复合体系的制备及力学性能研究[J]．材料科学与工艺，2003，11(2)：181-184
[37] 许鹏学，潘肇琦，杲云．聚氨酯/石墨导电复合材料的结构与性能表征[J]．中国塑料，2004，18(4)：43-46
[38] 王武生，潘才元，曾俊，阮德礼，钟峰．在线性或交联的聚氨酯粒子内原位还原制备纳米银粒子[J]．高等学校化学学报，2001，22(4)：700-702
[39] Jae Whan Cho, Jung Hyun So, Polyurethane-silver fibers prepared by infiltration and reduction of silver nitrate[J]. Materials Letters, 2006, 60:2653-2656
[40] Park Soo-Tin,Jang Yu-Sin. Preparation and characterization of activated carbon fibers supported with siver metal for antibacterial behavior[J]. Joumal of Colloid and Iterface Science,2003,261:239
[41] 王东青，李伟，刘学栋，黄岐善．医用聚氨酯弹性体的应用研究进展[J]．现代化工，2006，26：100-102
[42] Chi-Wei Chou,Shan-hui Hsu,Han Chang, Sheng-Mao Tseng,Hong-Ru Lin. Enhanced thermal and mechanical properties and biostability of polyurethane containing silver nanoparticles[J]. Polymer Degradation and Stability, 2006, 91:1017 -1024
[43] 龚文化，曾黎明．聚合物基导电复合材料研究进展[J]．化工新型材料，2002，30(4)：38-40
[44] M.Narkis, G.Lidor, A Vaxman, L.Zuri. New Injection Moldable Electrotastatic Dissipative (ESD) Composites Based on Very Low Carbon Black Loadings[J]. J.Electrost., 1999, 47:201-214
[45] 韩永芹．石墨/粘结剂导电复合材料性能的研究[J]．玻璃钢/复合材料，2006(2)：32-33
[46] 吴战鹏．具有高反射和高导电特性聚酰亚胺银复合薄膜的制备及其形成机理研究[D]，北京：北京化工大学，2005
[47] 宋芳，武德珍，张倩，齐胜利，姜立忠，金日光．原位一步法法制备BTDA／4，4'-ODA/4，4'SDA聚酰亚胺表面银化薄膜[J]．高分子学报，2006(4)：325-329
[48] 张艳芳，吴战鹏，齐胜利，蔡晴，庞中华，武德珍，金日光．聚酰亚胺/银复合膜的制备及其亚微相态与性能研究[J]．复合材料学报，2005，22(4)：30-34
[49] 齐胜利，吴战鹏，罗芸，宋芳，武德珍，金日光．原位一步法制备PMDA／ODA基PI/Ag复合薄膜[J]．功能高分子学报，2005，18(2)：222-226
[50] 丁孟贤，何天白．聚酰亚胺新型材料[M]，北京：科学出版社，1998
[51] 宋芳．分子结构对原位一步法制备聚酰亚胺银纳米复合薄膜表面性能的影响[D]，北京，北京化工大学，2005
[52] 贺蓉，钱雪峰，印杰，朱子康，王海林．银纳米棱镜的形成及其光学性能研究[J]．高等学校化学学报，2003，24(8)：1341-1345