原位聚合沉积制备高质量纳米导电聚苯胺薄膜
摘要
近年来，导电聚苯胺薄膜在光电及微电子器件领域展现出越来越广阔的应用前景，但由于共轭高分子的刚性链结构，不溶不熔，因此解决和改善该类材料的成型加工性成为热点问题。本工作采用苯胺分散聚合体系，分别选用水溶性高分子-聚乙烯吡咯烷酮(PVP)与聚乙烯醇(PVA)为空间稳定剂，在玻璃表面原位沉积制备高质量纳米导电聚苯胺(PANI)薄膜。薄膜表面形貌光滑，膜厚可控，电导率可调。稳定剂PVP及PVA的加入明显降低了薄膜表面粗糙度，改善了薄膜表观质量。研究了苯胺单体浓度，稳定剂浓度，基体表面性质及反应时间对薄膜质量的影响。结果表明：对于苯胺浓度为0.2mol／L的体系，稳定剂PVP浓度在0.125wt％～4wt％范围内，及稳定剂PVA浓度在2.5wt％—3wt％范围内，是制备高质量PANI薄膜的最佳稳定剂浓度。PANI薄膜电导率随膜厚的增大而增大，达到饱和厚度时，电导率也达到最高。以PVP为稳定剂制备的薄膜电导率最高可达4.4 S·cm~(-1)，以PVA为稳定剂制备的薄膜电导率最高可达9.5 S·cm~(-1)。红外光谱结果表明PANI薄膜中不含有稳定剂PVP。紫外光谱结果表明与普通溶液法制备的PANI粉末相比，纳米尺寸PANI薄膜的紫外吸收峰分别发生了红移与蓝移。通过对比可知，以PVP为稳定剂制备PANI薄膜的表观形貌较好，以PVA为稳定剂制备PANI薄膜的饱和厚度较高，且相同膜厚的PANI薄膜电导率较高。采用十八烷基三氯硅烷(OTS)改性玻璃表面，使玻璃表面从亲水性变为疏水性，加速了PANI的沉积且提高了薄膜厚度。
研究发现，聚苯胺在玻璃表面成膜经历成核，生长和饱和三个阶段；且玻璃表面聚苯胺的沉积与聚合早于分散液中的苯胺聚合反应，这可用异相催化机理解释。吸附在玻璃表面的苯胺阳离子自由基改变了自身电子分布，降低反应的活化能，因此其反应活性高于分散液中的苯胺聚合反应，使得聚苯胺优先在玻璃表面沉积成膜。
Recently conducting polyaniline (PANI) films have wide application prospect in optoelectronic and microelectronic devices, because of its insoluble performance, it's difficult to manufacture PANI using common methods. In this paper, Nano-sized and conducting polyaniline (PANI) films of high quality were prepared directly during dispersion polymerization of aniline on glass surfaces using poly (N-vinylpyrrolidone) (PVP) and poly (vinyl alcohol) (PVA) as stabilizers. This method solved the problem of poor processablity of PANI. Film surface was smooth, the thickness and conductivity of PANI films could be controlled. Film thickness ranged from several nanometers to hundreds of nanometers. Surface roughness was remarkably reduced in the presence of PVP or PVA. The influence of aniline and stabilizer concentration, deposition time and substrate properties on film structure and properties was studied.
It was demonstrated that when aniline concentration was 0.2mol/L, 0.125wt% ~4wt% of PVP and 2.5wt%—3wt% of PVA concentrations were apt to prepare high quality PANI films. Film conductivities increased with increasing film thickness and didn't alter any longer when film thickness got to saturated thickness. The conductivities of films could reache up to 4.4 S·cm~(-1) and 9.5 S·cm~(-1) respectively at room temperature.
研究发现，聚苯胺在玻璃表面成膜经历成核，生长和饱和三个阶段；且玻璃表面聚苯胺的沉积与聚合早于分散液中的苯胺聚合反应，这可用异相催化机理解释。吸附在玻璃表面的苯胺阳离子自由基改变了自身电子分布，降低反应的活化能，因此其反应活性高于分散液中的苯胺聚合反应，使得聚苯胺优先在玻璃表面沉积成膜。
Recently conducting polyaniline (PANI) films have wide application prospect in optoelectronic and microelectronic devices, because of its insoluble performance, it's difficult to manufacture PANI using common methods. In this paper, Nano-sized and conducting polyaniline (PANI) films of high quality were prepared directly during dispersion polymerization of aniline on glass surfaces using poly (N-vinylpyrrolidone) (PVP) and poly (vinyl alcohol) (PVA) as stabilizers. This method solved the problem of poor processablity of PANI. Film surface was smooth, the thickness and conductivity of PANI films could be controlled. Film thickness ranged from several nanometers to hundreds of nanometers. Surface roughness was remarkably reduced in the presence of PVP or PVA. The influence of aniline and stabilizer concentration, deposition time and substrate properties on film structure and properties was studied.
It was demonstrated that when aniline concentration was 0.2mol/L, 0.125wt% ~4wt% of PVP and 2.5wt%—3wt% of PVA concentrations were apt to prepare high quality PANI films. Film conductivities increased with increasing film thickness and didn't alter any longer when film thickness got to saturated thickness. The conductivities of films could reache up to 4.4 S·cm~(-1) and 9.5 S·cm~(-1) respectively at room temperature.
引文
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2. De Berry D W. Modification of the electrochemical and corrosion behavior of stainless steels with an electroactive coating. J Electrochem Soc, 1985, 132(5): 1022-1026
3. Wroblesld D A, Benicewicz B C, Thompson K G, et. al. Corrosion resistant coatings from conducting polymers. ACS Polym Prepr, 1994, 35(1): 265-266
4. Krinichniy V I, Eremenko O N, Rukhman G G, et. al. Sensors based on organic conducting polymers polyaniline. Vysokomol Soedin, Sec A, 1989, 31(8): 1656-1661
5. Anderson M R, Matters B R, Reiss H, et al. Conjugated polymer films for gas separations. Science, 1991, 252(5011): 1412-1415
6. Cao Y, Colaneri N. "Plastic" infared polarizers from uniaxially oriented polyaniline blends. Appl Phys Lett, 1994, 65(16): 2001-2003
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8. Neoh KG, Tan K K, Gob P L, et al. Electroactive polyner-SiO_2 nanocomposites for metal uptake. Polymer, 1999, 40(4): 887-893
9．陶雪钰，陈骁，熊忠等．原位聚合沉积透明导电聚苯胺薄膜的研究进展．化学推进剂与高分子材料，2005，3(6)：23-26
10．王利祥，王佛松．导电聚合物聚苯胺的研究进展Ⅰ．应用化学，1990，7(5)：1-10
11．王利祥，王佛松．导电聚合物聚苯胺的研究进展Ⅱ．应用化学，1990，7(6)：1-8
12．陆珉，吴益华，姜海夏．导电聚苯胺的特性及应用．化工新型材料，1997，(11)：16-20
13．邓建国等．聚苯胺复合材料研究进展．高分子通报，2002，3：33-37
14. Ghosh P, Siddhanta S K, Haque S R, Chakrabarti A. Stable polyaniline dispersions prepared in nonaquous medium: synthesis and characterization. Synth Met, 2001, 123: 83-89
15. Banerjee P, Mandal B M. Conducting polyaniline nanoparticle blends with extremely low percolation thresholds. Macromolecules, 1995, 28(11): 3940-3943
16．彭霞辉，刘静宇．聚苯胺合成研究进展．精细化工中间体，2002，32(6)：23-28
17．曹同玉，戴兵，戴俊燕等．单分散大粒径聚合物微球的合成及应用[J]．高分子通报，1995，3：174-180
18. Shen S, Sudol E D, El-Aasser M S. Dispersion of methyl methacrylate: mechanism of particle??formation. J Polym Sci Polym Chem Ed, 1994, 32: 1087-1100
19. Stejskal J, Kratochvil P, Koubik P T, et.al. Light-scattering characterization of spherical particles prepared by the dispersion polymerization of methyl methacrylate in a non-aqueous medium. Polymer, 1991, 31(10): 1816-1822
20．曹同玉，戴兵，戴俊燕等．分散聚合稳定机理及动力学研究．高分子材料科学与工程，1998，1(14)：31-34
21. Banerjee P, Digar M L, Bhattacharyya S N, et.al. Novel polyaniline dispersions using poly (vinyl methyl ether) stabilizer. Eur Polym J, 1994, 30(4): 499-501
22. Banerjee P, Mandal B M. Conducting polyaniline nanoparticle blends with extremely low percolation thresholds. Macromolecules, 1995, 28(11): 3940-3943
23. Riede A, Helmstedt M, Riede V. Polyaniline dispersions 9. Dynamic light scattering study of particle formation using different stabilizers. Langmuir, 1998, 14: 6767-6771
24. Gospodinova N, Terlemezyan L, Mokreva P, et. al. Preparation and characterization of aqueous polyaniline dispersions. Eur Polym J, 1993, 29(10): 1305-1309
25. Stejskal J, Kratochril P, Armes S P, et.al. Polyaniline dispersion. 6. Stabilization by colloidal silica particles. Macromolecules, 1996, 29(21): 6814-6819
26. Riede A, Helmstedt M, Riede Stejskal J. Polyaniline dispersions 7. Dynamic light scattering study of particle formation. Colloid Polym Sci, 1997, 275: 841-820
27. Stejskal J, Kratochvil P, Helmstedt M. Polyaniline dispersions 5. Poly (vinyl alcohol) and Poly (N-vinylpyrrolidone) as steric stabilizers. Langmuir, 1996,12(14): 3389-3392
28. Stejskal J, Sapurina I, Prokes J, et. al. In-situ polymerized polyaniline films. Synth Met, 1999, 105: 195-202
29. Ayad M M, Sheneshin M A. Effect of acids on in situ Polyaniline film formation. Polym Int, 2004, 53: 1180-1184
30. Ayad M M, Gemaey A H, Salahuddin N, et. al. The kinetics and spectral studies of the in situ polyaniline film formation. J Colloid Interface Sci, 2003, 263: 196-201
31. Sapurina I, Fedorova S. Surface Polymerization and Precipitation Polymerization of Aniline in the Presence of Sodium Tungstate. Langmuir. 2003, 19: 7413-7416
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