植酸水溶液中聚吡咯涂层在Cu基体上的制备及其在腐蚀防护中的应用
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摘要
利用植酸作为电解质及掺杂剂,成功地在Cu基体表面制备了具有强效防腐特性的聚吡咯(PPy)涂层。采用原位电化学石英微晶分析天平(EQCM)分析技术对聚吡咯在Cu电极表面上的沉积过程进行了探讨,利用扫描电子显微镜(SEM)以及Fourier转换全反射-红外吸收光谱对制备的导电聚合物PPy涂层形貌与成分进行了表征,研究了涂层的抗腐蚀性能。结果表明,电聚合过程中,Cu基体表面首先沉积一层具有保护作用的Phytate-Cu盐层,可抑制基体进一步溶解并有助于聚吡咯的形核及长大。酸盐掺杂的聚吡咯涂层在3.5%(质量分数)NaCl溶液中对Cu基体表现出良好的防护性,pH值为4的弱酸性条件下制备的聚吡咯膜具有最好的耐蚀保护性能。EQCM-循环伏安结果证实,植酸根掺杂的聚吡咯呈现出阳离子选择透过特性,抑制了Cl-的扩散,并显著地提高了Cu基体的抗腐蚀特性。
Phytic acid(C_6H_(18)O_(24)P_6, Phy) is the principal storage form of phosphorus in many plant tissues, especially bran, corn and seeds. Herein, high protective and stabile polypyrrole(PPy) films were directly electro-synthesized on Cu from aqueous phytic acid solution. The electrodeposition process was monitored with an electrochemical quartz crystal microbalance(EQCM), while the prepared PPy films were characterized by means of SEM, FT-IR and Raman spectroscopy. It was indicated that the growth of these films was facilitated by the initial oxidation of the Cu-electrode in the phytate solution to generate a Cu-phytate pseudo-passive layer. After that, highly adherent and homogenous polypyrrole was facilitated were electrodeposited on Cu in the phytic acid solution. Corrosion protection property of the PPy films were examined through immersion test in 3.5%(mass fraction)Na Cl solution in terms of the amount of Cu ions dissolved from the PPy covered Cu during immersion, which presented the excellent stability and corrosion protective ability of the PPy films. Among others, the PPy film synthesized from the pH=4 phytic acid solution exhibited the best protective performance. EQCM-CV tests indicated that the PPy film doped with phytate anions, acting as cationic perm-selective membrane, can effectively inhibit the diffusion of Cl-to the substrate and therewith improve the anti-corrosion property.
Phytic acid(C_6H_(18)O_(24)P_6, Phy) is the principal storage form of phosphorus in many plant tissues, especially bran, corn and seeds. Herein, high protective and stabile polypyrrole(PPy) films were directly electro-synthesized on Cu from aqueous phytic acid solution. The electrodeposition process was monitored with an electrochemical quartz crystal microbalance(EQCM), while the prepared PPy films were characterized by means of SEM, FT-IR and Raman spectroscopy. It was indicated that the growth of these films was facilitated by the initial oxidation of the Cu-electrode in the phytate solution to generate a Cu-phytate pseudo-passive layer. After that, highly adherent and homogenous polypyrrole was facilitated were electrodeposited on Cu in the phytic acid solution. Corrosion protection property of the PPy films were examined through immersion test in 3.5%(mass fraction)Na Cl solution in terms of the amount of Cu ions dissolved from the PPy covered Cu during immersion, which presented the excellent stability and corrosion protective ability of the PPy films. Among others, the PPy film synthesized from the pH=4 phytic acid solution exhibited the best protective performance. EQCM-CV tests indicated that the PPy film doped with phytate anions, acting as cationic perm-selective membrane, can effectively inhibit the diffusion of Cl-to the substrate and therewith improve the anti-corrosion property.
引文
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[19]Zhu R L,Li G X,Liu X Y.Electrosynthesis of polypyrrole and corrosion protection for stainless steel[J].J.Chin.Soc.Corros.Prot.,2008,28:7(朱日龙,李国希,刘晓阳.聚吡咯的电化学合成及其对不锈钢的保护作用[J].中国腐蚀与防护学报,2008,28:7)
[2]Waltman R J,Bargon J.Electrically conducting polymers:A review of the electropolymerization reaction,of the effects of chemical structure on polymer film properties,and of applications towards technology[J].Can.J.Chem.,1986,64:76
[3]Ates M,Karazehir T,Sezai Sarac A.Conducting polymers and their applications[J].Curr.Phys.Chem.,2012,2:224
[4]Nguyen D N,Yoon H.Recent advances in nanostructured conducting polymers:From synthesis to practical applications[J].Polymers,2016,8:118
[5]de Berry D W.Modification of the electrochemical and corrosion behavior of stainless steels with an electroactive coating[J].J.Electrochem.Soc.,1985,132:1022
[6]Herrasti P,del Rio A I,Recio J.Electrodeposition of homogeneous and adherent polypyrrole on copper for corrosion protection[J].Electrochim.Acta,2007,52:6496
[7]Santos L M M S,Lacroix J C,Chane-Ching K I,et al.Electrochemical synthesis of polypyrrole films on copper electrodes in acidic and neutral aqueous media[J].J.Electroanal.Chem.,2006,587:67
[8]Tüken T,Yaz?c?B,Erbil M.The electrochemical synthesis and corrosion performance of polypyrrole on brass and copper[J].Prog.Org.Coat.,2004,51:152
[9]Shinde V,Sainkar S R,Patil P P.Corrosion protective poly(o-toluidine)coatings on copper[J].Corros.Sci.,2005,47:1352
[10]Prissanaroon W,Brack N,Pigram P J,et al.Electropolymerisation of pyrrole on copper in aqueous media[J].Synth.Met.,2004,142:25
[11]Fenelon A M,Breslin C B.The electropolymerization of pyrrole at a Cu Ni electrode:Corrosion protection properties[J].Corros.Sci.,2003,45:2837
[12]Redondo M I,Breslin C B.Polypyrrole electrodeposited on copper from an aqueous phosphate solution:Corrosion protection properties[J].Corros.Sci.,2007,49:1765
[13]Cascalheira A C,Aeiyach S,Lacaze P C,et al.Electrochemical synthesis and redox behaviour of polypyrrole coatings on copper in salicylate aqueous solution[J].Electrochim.Acta,2003,48:2523
[14]Annibaldi V,Rooney A D,Breslin C B.Corrosion protection of copper using polypyrrole electrosynthesised from a salicylate solution[J].Corros.Sci.,2012,59:179
[15]Graf E.Applications of phytic acid[J].J.Am.Oil Chem.Soc.,1983,60:1861
[16]Crea F,de Stefano C,Milea D,et al.Formation and stability of phytate complexes in solution[J].Coord.Chem.Rev.,2008,252:1108
[17]Lei Y H,Sheng N,Hyono A,et al.Effect of benzotriazole(BTA)addition on polypyrrole film formation on copper and its corrosion protection[J].Prog.Org.Coat.,2014,77:339
[18]Cui X F,Li Q F,Li Y,et al.Microstructure and corrosion resistance of phytic acid conversion coatings for magnesium alloy[J].Appl.Surf.Sci.,2008,225:2098
[19]Zhu R L,Li G X,Liu X Y.Electrosynthesis of polypyrrole and corrosion protection for stainless steel[J].J.Chin.Soc.Corros.Prot.,2008,28:7(朱日龙,李国希,刘晓阳.聚吡咯的电化学合成及其对不锈钢的保护作用[J].中国腐蚀与防护学报,2008,28:7)