聚苯胺/改性石墨复合材料的电化学制备及其防腐蚀性能研究
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摘要
采用恒电流法、恒电流阶跃电流法、循环伏安法及自聚合法等4种方法将聚苯胺(PANI)原位沉积在自制的改性石墨(MGE)上,制备出聚苯胺/改性石墨复合材料(PANI/MGE)。利用扫描电镜和红外光谱对PANI/MGE的微观形貌和分子结构进行了表征,利用电化学阻抗谱研究了不同聚合方法所得复合材料的防腐蚀性能。结果表明,4种聚合方法所得复合材料微观形貌与聚合前的改性石墨相似,都呈现平面的片层结构,没有聚合物团簇聚集现象产生。4种聚合方法均能成功实现聚苯胺的原位沉积,聚苯胺与改性石墨之间存在较强的相互作用,且以恒电流阶跃所得复合材料中两者的相互作用最强。5种不同涂层中,恒电流阶跃聚合所得涂层的防腐蚀性能最好,稳定的自腐蚀电位及涂层阻抗最高;循环伏安聚合及恒电流聚合所得两种复合涂层的阻抗及自腐蚀电位均随时间的延长而逐渐下降,涂层很快失效。
Polyaniline(PANi) was in situ deposited on the surface of modified graphite(MGE) via different electrochemical methods to prepare composites of PANi/MGE.Their morphology and microstructure were examined by scanning electron microscopy(SEM) and the Fourier transform infrared spectroscopy(FT-IR).While their anticorrosion properties were assessed by corrosion potential measurement and electrochemical impedance spectrometry.Experimental results showed that MGE as a support material can provide sufficient reaction sites for the deposition of aniline to form the film-like composites of PANI/MGE.There exists strong interaction at the interface of PANI and MGE.Test results of anticorrosion performance illustrated that among others,the composite of PANI/MGE prepared by polymerization with constant current step technique showed the best corrosion resistance and the highest open circuit potential.
Polyaniline(PANi) was in situ deposited on the surface of modified graphite(MGE) via different electrochemical methods to prepare composites of PANi/MGE.Their morphology and microstructure were examined by scanning electron microscopy(SEM) and the Fourier transform infrared spectroscopy(FT-IR).While their anticorrosion properties were assessed by corrosion potential measurement and electrochemical impedance spectrometry.Experimental results showed that MGE as a support material can provide sufficient reaction sites for the deposition of aniline to form the film-like composites of PANI/MGE.There exists strong interaction at the interface of PANI and MGE.Test results of anticorrosion performance illustrated that among others,the composite of PANI/MGE prepared by polymerization with constant current step technique showed the best corrosion resistance and the highest open circuit potential.
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].J.Electrochem.Soc.,1985,132:1022
[3]Syed A A,Dinesan M K.Review:Polyaniline—a novel polymeric material[J].Talanta,1991,38:815
[4]Kang E T,Neoh K G,Tan K L.Polyaniline:A polymer with many interesting intrinsic redox states[J].Prog.Polym.Sci.,1998,23:277
[5]Novák P,Müller K,Santhanam K S V,et al.Electrochemically active polymers for rechargeable batteries[J].Chem.Rev.,1997,97:207
[6]Diaz A F,Logan J A.Electroactive polyaniline films[J].J.Electroanal.Chem.Interf.Electrochem.,1980,111:111
[7]Lu C,Wang H R,Qu J E,et al.Application progress of carbon materials in metal corrosion protection[J].Corros.Sci.Prot.Techol.,2014,26:254(路晨,王海人,屈钧娥等.碳材料在金属防腐蚀中的应用研究进展[J].腐蚀科学与防护技术,2014,26:254)
[8]Zhang F,Liu J J,Li X Y,et al.Application of graphite in anticorrosion paint[J].Mater.Prot.,2007,40(5):27(张锋,刘景军,李效玉等.石墨在防腐蚀涂料中使用的研究[J].材料保护,2007,40(5):27)
[9]Gong Y N,Yu L J,Pan C X.Graphene and its applications in metal corrosion resistance:A review[J].Chin.J.Ship Res.,2016,11(1):80(龚佑宁,于连江,潘春旭.石墨烯及其在金属防腐中应用的研究进展[J].中国舰船研究,2016,11(1):80)
[10]Gu L,Ding J H,Yu H B.Research in graphene-based anticorrosion coatings[J].Prog.Chem.,2016,28:737(顾林,丁纪恒,余海斌.石墨烯用于金属腐蚀防护的研究[J].化学进展,2016,28:737)
[11]Deyab M A.Corrosion protection of aluminum bipolar plates with polyaniline coating containing carbon nanotubes in acidic medium inside the polymer electrolyte membrane fuel cell[J].J.Power Sources,2014,268:50
[12]Kumar A M,Gasem Z M.Effect of functionalization of carbon nanotubes on mechanical and electrochemical behavior of polyaniline nanocomposite coatings[J].Surface Coat.Technol.,2015,276:416
[13]Mahato N,Cho M H.Graphene integrated polyaniline nanostructured composite coating for protecting steels from corrosion:Synthesis,characterization,and protection mechanism of the coating material in acidic environment[J].Construct.Build.Mater.,2016,115:618
[14]Jafari Y,Ghoreishi S M,Shabani-Nooshabadi M.Polyaniline/Graphene nanocomposite coatings on copper:electropolymerization,characterization,and evaluation of corrosion protection performance[J].Synth.Met.,2016,217:220
[15]Wang Huihui.Preparation and properties of Polyaniline/carbon nanotube composite electroconductive and anticorrosive coating[D].Tianjin University,2013(王慧慧.聚苯胺/碳纳米管复合导电防腐涂层的制备与性能研究[D].天津大学,2013)
[16]Kumar A M,Gasem Z M.In situ electrochemical synthesis of polyaniline/f-MWCNT nanocomposite coatings on mild steel for corrosion protection in 3.5%Na Cl solution[J].Prog.Org.Coat.,2015,78:387
[17]Zhang L H,Li Y S,Wang D.Study on preparation and anti-corrosion properties of Polyaniline/Graphene waterborne coatings[J].Proc.CSEE,2015,35(Suppl.):170(张兰河,李尧松,王冬等.聚苯胺/石墨烯水性涂料的制备及其防腐性能研究[J].中国电机工程学报,2015,35(增刊):170)
[18]Chang C H,Huang T C,Peng C W,et al.Novel anticorrosion coatings prepared from polyaniline/graphene composites[J].Carbon,2012,50:5044
[19]Sun W,Wang L D,Wu T T,et al.Synthesis of low-electrical-conductivity graphene/pernigraniline composites and their application in corrosion protection[J].Carbon,2014,79:605
[20]Fan X Z,Xu H B,Lu Y H,et al.Electrochemical modification and its effect on the pseudocapacitive properties of a graphite electrode[J].New Carbon Mater.,2014,29:508(范新庄,徐海波,芦永红等.石墨电极电化学活化工艺与准电容特性[J].新型炭材料,2014,29:508)
[21]Fan X Z,Gao H,Zhong L,et al.Investigation of the capacitive performance of polyaniline/modified graphite composite electrodes[J].RSC Adv.,2015,5:3743
[22]Wang H L,Hao Q L,Yang X J,et al.Effect of graphene oxide on the properties of its composite with polyaniline[J].ACS Appl.Mater.Interfaces,2010,2:821
[23]Chen F,Liu P,Zhao Q Q.Well-defined graphene/polyaniline flake composites for high performance supercapacitors[J].Electrochim.Acta,2012,76:62
[24]Li X L,Zhong Q N,Zhang X L,et al.In situ polymerization of polyaniline on the surface of graphene oxide for high electrochemical capacitance[J].Thin Solid Films,2015,584:348
[25]Zhang Q H,Wang X H,Jing X B.Synthesis of polyaniline and its spectra properties[J].Chem.World,2001,42:242(张清华,王献红,景遐斌.聚苯胺的合成及其光谱特性[J].化学世界,2001,42:242)
[26]Zhang Y,Wang G J,Pan M.Fast electropolymerization of polyaniline nanofibers on carbon paper[J].Chem.J.Chin.Univ.,2014,35:2234(张悦,汪广进,潘牧.基于碳纸电极电化学快速合成聚苯胺纳米纤维[J].高等学校化学学报,2014,35:2234)
[27]Jin X X,Zhong L,Wan Q Z,et al.Preparation and capacitive property of polyaniline/modified graphite electrode[J].New Chem.Mater.,2017,45(6):103(金晓晓,钟莲,万起展等.聚苯胺/改性石墨电极的制备及电容性能研究[J].化工新型材料,2017,45(6):103)
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