聚苯胺/聚吡咯-纳米二氧化硅复合薄膜的合成及防腐性能

doi:10.7503/cjcu20160390

摘要/Abstract

摘要：

采用循环伏安法(CV)在316不锈钢(316SS)表面聚合生成聚苯胺/聚吡咯-纳米二氧化硅(PAni/PPy-SiO₂)共聚复合薄膜. 通过电化学工作站、傅里叶变换红外光谱仪(FTIR)、 X射线光电子能谱仪(XPS)和扫描电子显微镜(SEM)等考察了聚苯胺(PAni)、聚苯胺/聚吡咯(PAni/PPy)与PAni/PPy-SiO₂薄膜的电化学聚合过程、分子结构和特征形貌; 在3.5%(质量分数)NaCl水溶液中利用Tafel极化曲线和电化学阻抗谱(EIS)分别考察了PAni, PAni/PPy与PAni/PPy-SiO₂薄膜对不锈钢的防腐性能. 结果表明, 通过电化学法可以在316不锈钢表面生成PAni/PPy-SiO₂共聚复合薄膜; 相对于PAni薄膜与PAni/PPy薄膜, PAni/PPy-SiO₂薄膜有着更密实的表面结构, 其对不锈钢的保护能力优于PAni/PPy薄膜和PAni薄膜, 纳米SiO₂的掺杂通过加强膜层的机械屏蔽作用并抑制腐蚀反应过程中电荷的传递, 提高了薄膜的防腐能力.

关键词: 聚苯胺, 聚吡咯, 二氧化硅, 复合薄膜, 防腐性能

Abstract:

In this article, polyaniline/polypyrrole-nanosilicon dioxide(PAni/PPy-SiO₂) composite membrane was prepared by cyclic voltammetry(CV) method on the surface of 316 stainless steel(316SS). The electrochemical polymerization process, structural and morphological characteristics of polyaniline(PAni), polyaniline/polypyrrole(PAni/PPy) and PAni/PPy-SiO₂ membranes were investigated by cyclic voltammetry(CV), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM), respectively. The antiseptic properties of PAni, PAni/PPy and PAni/PPy-SiO₂ membranes to stainless steel were studied by the Tafel polarization curve and electrochemical impedance spectroscopy(EIS) in 3.5%(mass fraction) NaCl aqueous solution. The results show that PAni/PPy-SiO₂ composite membrane can form on the surface of 316 stainless steel by electrochemical process. Compared with PAni and PAni/PPy membranes, PAni/PPy-SiO₂ composite membrane has tighter surface structure. The metal protection ability of PAni/PPy-SiO₂ is better than those of PAni/PPy and PAni membranes. The anti-corrosion ability of membrane is improved because of the strengthening mechanical shielding effect of membrane with nano SiO₂ and the inhibition of charge transfer during the corrosion reaction process.

Key words: Polyaniline, Polypyrrole, Silica, Composite membrane, Anti-corrosion performance

中图分类号:

O646
TG178

TrendMD:

李传宪, 石恩华, 杨爽, 姚博, 杨飞, 燕群. 聚苯胺/聚吡咯-纳米二氧化硅复合薄膜的合成及防腐性能. 高等学校化学学报, 2016, 37(11): 2025.

LI Chuanxian, SHI Enhua, YANG Shuang, YAO Bo, YANG Fei, YAN Qun. Synthesis and Anti-corrosion Properties of Polyaniline/Polypyrrole-nano Silicon Dioxide Composite Membrane^†. Chem. J. Chinese Universities, 2016, 37(11): 2025.

图/表 13

Fig.1 Cyclic voltammograms for PAni(A), PPy(B), PAni/PPy(C) and PAni/PPy-SiO2(D)

Fig.2 N1s XPS spectra of PAni(A), PPy(B) and PAni-PPy(C)

Table 1 Components of N1s according to binding energy data from XPS

Membrane	Atomic fraction(%)
Membrane	—NH—	N⁺	—NH⁺	—N
PAni	16		61	23
PPy	63	27
PAni/PPy	34	40	16	10

Fig.3 FTIR spectra of PAni(a), PAni/PPy(b), PAni/PPy(c) and PAni/PPy-SiO2(d) membranes

Fig.4 Cyclic voltammograms of PAni(A), PPy(B), PAni/PPy(C) and PAni/PPy-SiO2(D) membranes in 1 mol/L H2SO4 solution

Fig.5 SEM images of PAni(A), PPy(B), PAni/PPy(C) and PAni/PPy-SiO2(D—F) with different SiO2 contents (D) PAni/PPy-SiO2(20∶1); (E) PAni/PPy-SiO2(10∶1); (F) PAni/PPy-SiO2(20∶3).

Fig.6 Tafel curves for bare 316SS(a), 316SS/PAni(b), 316SS/PAni/PPy(c), 316SS/PAni/PPy-SiO2(20∶1)(d) electrodes in 3.5%(mass fraction) NaCl solution

Fig.7 Tafel curves for 316SS/PAni/PPy-SiO2 electrodes with different SiO2 contents in 3.5% NaCl solution a. PAni/PPy-SiO2(20∶1); b. PAni/PPy-SiO2(40∶3); c. PAni/PPy-SiO2(10∶1); d. PAni/PPy-SiO2(40∶5); e. PAni/PPy-SiO2(20∶3).

Table 2 Ecorr and icorr in accordance with Tafel curves of different membranes on 316SS

Membrane	E_corr/V	i_corr/(A·cm^-2)
Bare 316SS	-0.34	2.827×10^-4
PAni	-0.17	6.723×10^-5
PAni/PPy	-0.03	1.891×10^-5
PAni/PPy-SiO₂(20∶1)	0.09	4.761×10^-6
PAni/PPy-SiO₂(40∶3)	0.108	3.517×10^-6
PAni/PPy-SiO₂(10∶1)	0.122	2.748×10^-6
PAni/PPy-SiO₂(40∶5)	0.115	3.138×10^-6
PAni/PPy-SiO₂(20∶3)	0.104	3.635×10^-6

Fig.8 EIS spectra for bare 316SS(a), 316SS/PAni(b), 316SS/PAni/PPy(c), 316SS/PAni/PPy-SiO2(20∶1)(d) electrodes in 3.5% NaCl solution

Fig.9 EIS spectra for 316SS/PAni/PPy-SiO2 electrodes with different SiO2 contents in 3.5% NaCl Solution a. PAni/PPy-SiO2(20∶1); b. PAni/PPy-SiO2(40∶3); c. PAni/PPy-SiO2(10∶1); d. PAni/PPy-SiO2(40∶5); e. PAni/PPy-SiO2(20∶3).

Fig.10 Equivalent circuit of 316SS membrane

Table 3 EIS fitting parameters of different membranes on 316SS

Membrane	R_s/(Ω·cm²)	C_c/(F·cm^-2)	n₁	R_c/(Ω·cm²)	C_dl/(F·cm^-2)	n₂	R_ct/(Ω·cm²)
PAni	8.25	0.00041086	0.77961	136.5	0.0039012	0.76774	605.6
PAni/PPy	9.27	0.00027486	0.81575	169.2	0.0028021	0.75622	1029.3
PAni/PPy-SiO₂(20∶1)	10.64	0.00020994	0.85938	202.3	0.0020668	0.82984	1512.8
PAni/PPy-SiO₂(40∶3)	10.29	0.00015672	0.86344	245.6	0.0014717	0.81137	1773.4
PAni/PPy-SiO₂(10∶1)	8.50	0.00012482	0.84834	296.3	0.0010392	0.85789	1905.2
PAni/PPy-SiO₂(40∶5)	7.62	0.00013026	0.87125	261.7	0.0012971	0.83695	1835.7
PAni/PPy-SiO₂(20∶3)	9.01	0.00018267	0.89767	214.8	0.0017236	0.84891	1623.1

参考文献 35

[1]	陈世刚, 赵文元. 腐蚀科学与防护技术, 2009, 21( 3), 269)
	Chen S., G. , Zhao W., Y. , Corros. Sci. Prot. Technol., 2009, 21( 3), 269 (
[2]	Slimane A., B. , Connan, C. , Vaulay M., J. , Chehimi M., M. , J. Colloids Surf. A, 2009, 332( 2), 157- 163
[3]	DeBerry D., W. , J. Electrochem. Soc., 1985, 132( 5), 1022- 1026
[4]	Zhang, T. , Zeng C., L. , J. Electrochim. Acta, 2005, 50( 24), 4721- 4727
[5]	Mollahosseini, A. , Noroozian, E. , J. Synth. Met., 2009, 159( 13), 1247- 1254
[6]	龙晋明, 王少龙, 王静. 材料保护, 2003, 36( 12), 23- 26
	Long J., M. , Wang S., L. , Wang, J. , J. Mater. Prot., 2003, 36( 12), 23- 26 (
[7]	徐慧, 王新颖, 刘小育. 腐蚀科学与防护技术, 2012, 3( 2), 127- 131
	Xu, H. , Wang X., Y. , Liu X., Y. , Corros. Sci. Prot. Technol., 2012, 3( 2), 127- 131 (
[8]	李倩倩, 黄健涵, 刘素琴, 关鲁雄, 黄可龙. 化学学报, 2008, 66( 5), 571- 575
	Li Q., Q. , Huang J., H. , Liu S., Q. , Guan L., X. , Huang K., L. , J. Acta Chim. Sin. (Engl. Ed. ), 2008, 66( 5), 571- 575 (
[9]	Olad, A. , Barati, M. , Shirmohammadi, H. , J. Prog. Org. Coat., 2011, 72( 4), 599- 604
[10]	贾艺凡, 刘朝辉, 廖梓珺, 王飞, 叶圣天, 班国东, 丁逸栋, 林锐. 表面技术, 2016, 45( 3), 164- 168
	Jia Y., F. , Liu C., H. , Liao Z., J. , Wang, F. , Ye S., T. , Ban G., D. , Ding Y., D. , Lin, R. , J. Surf. Technol., 2016, 45( 3), 164- 168 (
[11]	Redondo M., I. , Breslin C., B. , J. Corros. Sci., 2007, 49( 4), 1765- 1776
[12]	吕龙飞. 苯胺-吡咯共聚物复合材料的制备、表征及其防腐蚀性能, 镇江: 江苏科技大学, 2014)
	Lv L., F. , Preparation, Characterization and Anti-corrosion Performance of Aniline-pyrrole Copolymer Composite Materials, Jiangsu University of Science and Technology, Zhenjiang, 2014 (
[13]	刘万民, 何拥军, 李芝坛. 表面技术, 2010, 39( 3), 58- 60
	Liu W., M. , He Y., J. , Li Z., T. , J. Surf. Technol., 2010, 39( 3), 58- 60 (
[14]	Grari, O. , Dhouibi, L. , Lallemand, F. , Buron C., C. , Taouil A., E. , Hihn J., Y. , J. Ultrason. Sonochem., 2015, 22, 220- 226
[15]	Chen Z. Q., Wang G. X., Xu G. Y., Colloid and Interface Chemistry, Higher Education Press, Beijing, 2001, 101— 105
	( 陈宗淇, 王光信, 徐桂英. 胶体与界面化学. 北京: 高等教育出版社, 2001, 101— 115)
[16]	Stilwell D., E. , Park S., M. , J. Electrochem. Soc., 1988, 135( 10), 2491- 2496
[17]	Tü, ken T. , Arslan, G. , Yazı, cı B. , Erbil, M. , J. Prog. Org. Coat., 2004, 49( 2), 153- 159
[18]	李美超, 朱婉霞, 朱静娜, 莫卫民. 高等学校化学学报, 2012, 33( 1), 128- 132
	Li M., C. , Zhu W., X. , Zhu J., N. , Mo W., M. , Chem. J. Chinese Universities, 2012, 33( 1), 128- 132 (
[19]	吕龙飞, 林生岭, 陈传祥, 文丹, 李潇霜. 表面技术, 2013, 42( 4), 110- 114
	Lv L., F. , Lin S., L. , Chen C., X. , Wen, D. , Li X., S. , J. Surf. Technol., 2013, 42( 4), 110- 114 (
[20]	熊冬柏, 杨春明. 应用化学, 2009, 26( 9), 1054- 1059
	Xiong D., B. , Yang C., M. , Chin. J. Appl. Chem., 2009, 26( 9), 1054- 1059 (
[21]	Han M., G. , Cho S., K. , Oh S., G. , Im S., S. , J. Synth. Met., 2002, 126( 1), 53- 60
[22]	Kang E., T. , Neoh K., G. , Zhang, X. , Zhang, X. , Tan K., L. , Liaw D., J. , J. Surf. Interface Anal., 1996, 24( 1), 51- 58
[23]	Kalendová, A. , Vesel, D. , Kohl, M. , Stejskal, J. , J. Prog. Org. Coat., 2015, 78, 1- 20
[24]	Sheng, N. , Lei Y., H. , Hyonoo, A. , Ueda, M. , Ohtsuka, T. , J. Prog. Org. Coat., 2014, 77( 11), 1724- 1734
[25]	Huang, H. , Wu, J. , Lin, X. , Li, L. , Shang S., M. , Yuen M., C. , Yan G., P. , J. Carbohydr. Polym., 2013, 95( 1), 72- 76
[26]	陈忠平, 褚道葆, 陈君华, 过家好, 伊晓娟, 吴何珍, 高分子学报, 1900, 1( 6), 536- 540
	Chen Z., P. , Chu D., B. , Chen J., H. , Guo J., H. , Yin X., J. , Wu H., Z. , Acta Polym. Sin., 1900, 1( 6), 536- 540 (
[27]	王宏智, 刘炜洪, 李剑, 姚素薇, 张卫国. 高等学校化学学报, 2012, 33( 2), 421- 425
	Wang H., Z. , Liu W., H. , Li, J. , Yao S., W. , Zhang W., G. , Chem. J. Chinese Universities, 2012, 33( 2), 421- 425 (
[28]	罗正鸿, 何腾云, 蔺存国, 戴李宗. 高分子通报, 2007, 9, 9- 13
	Luo Z., H. , He T., Y. , Lin C., G. , Dai L., Z. , J. Polym. Bull., 2007, 9, 9- 13 (
[29]	Jeong A., Y. , Koo S., M. , Kim D., P. , J. Sol-Gel Sci. Technol., 2000, 19( 1-3), 483- 487
[30]	Cook, A. , Gabriel, A. , Siew, D. , Laycock, N. , J. Curr. Appl. Phys., 2004, 4( 2-4), 133- 136
[31]	张鉴清, 曹楚南. 腐蚀与防护, 1998, 8, 32- 36
	Zhang J., Q. , Cao C., N. , Corros. Prot., 1998, 8, 32- 36 (
[32]	张伟, 王佳, 赵增元, 刘学庆. 中国腐蚀与防护学报, 2011, 5, 36- 45
	Zhang, W. , Wang, J. , Zhao Z., Y. , Liu X., Q. , J. Chin. Soc. Corros. Prot., 2011, 5, 36-45 (
[33]	Cao C. N., Electrochemistry of Corrosion(3rd Edition), Chemical Industry Press, Beijing, 2008, 175— 179
	( 曹楚南. 腐蚀电化学原理(第三版). 北京: 化学工业出版社, 2008, 175— 179)
[34]	Sathiyanarayanan, S. , Azim S., S. , Venkatachari, G. , J. Synth. Met., 2007, 157( 18), 751- 757
[35]	Lasia, A. , Modern Aspects of, Electrochemistry , Springer, New York, 2002, 143-248