AZ31镁合金表面防腐涂层的制备及耐蚀性研究
|
摘要
选择聚吡咯(PPy)作为涂层材料,在经硅烷预处理后的AZ31镁合金表面化学氧化合成PPy。运用傅立叶变换红外光谱(FTIR)研究了膜层结构,用扫描电镜(SEM)及能谱分析(EDS)研究了膜层表面形貌及成分分布特征,用电化学极化曲线、交流阻抗(EIS)测试和盐水浸泡实验评定了金属/膜层体系的耐蚀性能。
研究了BTESPT和APS两种硅烷偶联剂对AZ31镁合金预处理后的耐蚀性能,硅烷在镁合金表面形成SiOSi网状薄膜结构,并通过SiOMg键与镁合金表面相连,由于硅烷的阻挡作用提高了镁合金的耐腐蚀性能。不同pH的3.5wt%NaCl溶液以碱性环境对金属/硅烷体系的腐蚀程度最轻,中性其次,酸性最严重。由于亲水的氨基基团,氨基硅烷对镁合金基体的保护性能比含硫硅烷略差。
研究了预处理、氧化剂、反应温度和聚合时间等多种聚合参数对PPy形貌、耐蚀性的影响规律。PPy膜对镁合金腐蚀有一定的抑制作用,腐蚀电流密度降低了1个数量级；硅烷预处理提高Mg/PPy体系的耐蚀性能,使腐蚀电位正移了110mV,腐蚀电流密度减小了约2个数量级。其余聚合条件相同时,过硫酸铵((NH4)2S2O8)合成的PPy膜耐蚀性要比氯化铁(FeCl3)相对好。掺杂阴离子的存在对Mg/APS/PPy体系具有一定的缓蚀作用。以(NH4)2S2O8作氧化剂、十二烷基苯磺酸钠(SDBS)作掺杂剂时化学原位聚合的最佳时间是10min。5～10℃的聚合温度比室温好。
探讨了PPy的成膜机理。PPy与基体之间是通过物理吸附连接,PPy的附着性和连续性较差,对镁合金的防护性能有限。经硅烷预处理后,硅烷膜一方面与金属基体通过SiOMg键结合,另一方面与PPy通过化学键连接,增强了PPy和镁基体的结合力,生成的薄膜附着力好,缺陷也相对较少,使Mg/silane/PPy的耐腐蚀性相应提高。
Polypyrrole (PPy) was chemically synthesized on the surface of the silane pretreated AZ31 magnesium alloy. Fourier transform infrared spectroscopy (FTIR) was used for structural characterization of the formed silane and PPy films. Scanning electron microscope (SEM) and energy dispersive X-ray (EDS) analysis were used for observation of surface morphology and elements analysis of the films. The corrosion behavior of silane film and PPy film was studied in 3.5wt% NaCl solution using electrochemical polarization test, electrochemical impedance spectroscopy and immersion test at room temperature.
The corrosion behavior of AZ31 Mg pretreated with BTESPT and APS silane respectively was studied. The silane moleculars were cross-linked through SiOSi, and the silane film was linked to the Mg alloy by SiOMg. Silane pretreatment can improve the corrosion protection performance of AZ31 Mg alloy and a lower corrosion rate correlated with higher pH. Mg/APS played worse anti-corrosion performance than Mg/BTESPT because of hydrophilic NH2 group.
The anti-corrosion performances of PPy films through different polymerization processes were investigated, including pretreatment, oxidant, reaction temperature and time. The PPy film showed a certain corrosion inhibition on the AZ31 magnesium alloy, with a decrease in the corrosion current density by one order of magnitude. Silane pretreatment can improve the corrosion protection performance of the Mg/PPy system, causing a positive shift of the corrosion potential by 110 mV and a decrease in the corrosion current density by two orders of magnitude. PPy using (NH4)2S2O8 as an oxidant showed better protection performance than FeCl3. Doped anion played a certain corrosion inhibition in Mg/APS/PPy system.10min was the best polymerization time of PPy using sodium dodecyl benzene sulfonate (SDBS) as a doping agent and (NH4)2S2O8 as an oxidant. And polymerization at temperature of 5～10℃was better than at room temperature.
The mechanism on formation of PPy film was discussed. PPy was connected to the Mg alloy by physical adsorption, which induced the poor adhesion and continuity of PPy film, decreased its corrosion protection performance. After silane pretreatmen, silane film was linked to the Mg alloy by SiOMg, while linked to PPy by chemical bond, which enhanced the adhesion between PPy and Mg matrix, made the arrangment uniform and reduced the defects of PPy film.
研究了BTESPT和APS两种硅烷偶联剂对AZ31镁合金预处理后的耐蚀性能,硅烷在镁合金表面形成SiOSi网状薄膜结构,并通过SiOMg键与镁合金表面相连,由于硅烷的阻挡作用提高了镁合金的耐腐蚀性能。不同pH的3.5wt%NaCl溶液以碱性环境对金属/硅烷体系的腐蚀程度最轻,中性其次,酸性最严重。由于亲水的氨基基团,氨基硅烷对镁合金基体的保护性能比含硫硅烷略差。
研究了预处理、氧化剂、反应温度和聚合时间等多种聚合参数对PPy形貌、耐蚀性的影响规律。PPy膜对镁合金腐蚀有一定的抑制作用,腐蚀电流密度降低了1个数量级；硅烷预处理提高Mg/PPy体系的耐蚀性能,使腐蚀电位正移了110mV,腐蚀电流密度减小了约2个数量级。其余聚合条件相同时,过硫酸铵((NH4)2S2O8)合成的PPy膜耐蚀性要比氯化铁(FeCl3)相对好。掺杂阴离子的存在对Mg/APS/PPy体系具有一定的缓蚀作用。以(NH4)2S2O8作氧化剂、十二烷基苯磺酸钠(SDBS)作掺杂剂时化学原位聚合的最佳时间是10min。5～10℃的聚合温度比室温好。
探讨了PPy的成膜机理。PPy与基体之间是通过物理吸附连接,PPy的附着性和连续性较差,对镁合金的防护性能有限。经硅烷预处理后,硅烷膜一方面与金属基体通过SiOMg键结合,另一方面与PPy通过化学键连接,增强了PPy和镁基体的结合力,生成的薄膜附着力好,缺陷也相对较少,使Mg/silane/PPy的耐腐蚀性相应提高。
Polypyrrole (PPy) was chemically synthesized on the surface of the silane pretreated AZ31 magnesium alloy. Fourier transform infrared spectroscopy (FTIR) was used for structural characterization of the formed silane and PPy films. Scanning electron microscope (SEM) and energy dispersive X-ray (EDS) analysis were used for observation of surface morphology and elements analysis of the films. The corrosion behavior of silane film and PPy film was studied in 3.5wt% NaCl solution using electrochemical polarization test, electrochemical impedance spectroscopy and immersion test at room temperature.
The corrosion behavior of AZ31 Mg pretreated with BTESPT and APS silane respectively was studied. The silane moleculars were cross-linked through SiOSi, and the silane film was linked to the Mg alloy by SiOMg. Silane pretreatment can improve the corrosion protection performance of AZ31 Mg alloy and a lower corrosion rate correlated with higher pH. Mg/APS played worse anti-corrosion performance than Mg/BTESPT because of hydrophilic NH2 group.
The anti-corrosion performances of PPy films through different polymerization processes were investigated, including pretreatment, oxidant, reaction temperature and time. The PPy film showed a certain corrosion inhibition on the AZ31 magnesium alloy, with a decrease in the corrosion current density by one order of magnitude. Silane pretreatment can improve the corrosion protection performance of the Mg/PPy system, causing a positive shift of the corrosion potential by 110 mV and a decrease in the corrosion current density by two orders of magnitude. PPy using (NH4)2S2O8 as an oxidant showed better protection performance than FeCl3. Doped anion played a certain corrosion inhibition in Mg/APS/PPy system.10min was the best polymerization time of PPy using sodium dodecyl benzene sulfonate (SDBS) as a doping agent and (NH4)2S2O8 as an oxidant. And polymerization at temperature of 5～10℃was better than at room temperature.
The mechanism on formation of PPy film was discussed. PPy was connected to the Mg alloy by physical adsorption, which induced the poor adhesion and continuity of PPy film, decreased its corrosion protection performance. After silane pretreatmen, silane film was linked to the Mg alloy by SiOMg, while linked to PPy by chemical bond, which enhanced the adhesion between PPy and Mg matrix, made the arrangment uniform and reduced the defects of PPy film.
引文
[1]张鹏,曾大本.异军突起的镁合金压铸.特种铸造及有色合金,2000,6：55-57
[2]陈晓阳,曾大本.镁合金铸件的应用现状及发展前景.铸造,1999,11：53-55
[3]宋光龄.镁合金腐蚀与防护.北京：化学工业出版社,2006
[4]王渠东,吕宜振,曾小勒.镁合金在电子器材壳体中的应用.材料导报,2000,14(6)：22-24
[5]李光玉.镁合金表面涂层和化学镀层的研究：[博士学位论文].吉林：吉林大学,2006
[6]孟岩,潘建亮.汽车轻量化材料的应用.技术与应用,2010,18(5)：24-27
[7]李卫平,朱立群.镁及其合金表面防护性涂层国外研究进展,材料保护2005,38(2)：41-46
[8]蒋百灵,张淑芬,吴国建,等.镁合金微弧氧化陶瓷层显微缺陷与相组成及其耐蚀性.中国有色金属学报,2002,12(3)：454-457
[9]李鑫庆,陈迪勤,余静琴.化学转化膜技术与应用.北京：机械工业出版社,2005
[10]郭洪飞,安茂忠,刘荣娟.镁及其合金表面化学转化处理技术.轻合金加工技术,2003,31(8)：35-41
[11]程英亮,吴海兰,李玲玲,等.ZK6镁合金磷酸盐及锡酸盐化学转化膜.中国有色金属学报,2007,17(5)：676-682
[12]Gray J E, Luan B. Protective coatings on magnesium and its alloys—a critical review. Journal of Alloys and Compounds,2002,336:88-113
[13]徐以兵.铝合金和镁合金的表面硅烷化处理研究[硕士学位论文].长沙：湖南大学,2008
[14]Van Ooij W J, Child T. Protecting metals with silane coupling. Chemical technology,1998,28(2):26-35
[15]Van Ooij W J, Zhu D Q, Palanivel V, et al. The potential of silanes for chromate replacement in metal finishing industries. Silicon Chemistry,2006,3(1-2):11-30
[16]Zhu D Q, van Ooij W J. Surface modification of metals by silanes in Adhesion aspects of polymeric coatings. Utrecht:VSP,2003,2:81-89
[17]Van Ooij W J, Zhu D Q, Stacy M, et al. Corrosion protection properties of organofunctional silanes—An Overview. Tsinghua Science and Technology, 2005,10(6):639-664
[18]Zucchi F, Frignani A, Grassi V, et al. Organo-silane coatings for AZ31 magnesium alloy corrosion protection. Materials Chemistry and Physics,2008, 110(2-3):263-268
[19]Montemor M F, Ferreira M G S. Analytical and microscopic characterisation of modified bis-[triethoxysilylpropyl] tetrasulphide silane films on magnesium AZ31 substrates. Progress Organic Coatings,2007,60(3):228-237
[20]Montemor M F, Ferreira M G S. Electrochemical study of modified bis-[triethoxysilylpropyl] tetrasulfide silane films applied on the AZ31 Mg alloy. Electrochimica Acta,2007,52(27):7486-7495
[21]Chen M A, Xie X, Xu G F, et al. Structural characterization and corrosion properties of BTESPT silane films on Surface of 2024-T6 aluminium alloy. Materials Science Forum,2007,546-549:1111-1116
[22]路学斌,郭照辉,黄荣,等.紫铜表面3-巯丙基三乙氧基硅烷薄膜的制备与耐蚀性能.物理化学学报,2010,27(1)：108-112
[23]陈明安,谢玄,戚海英,等.2A12-T6铝合金表面双-(γ-三乙氧基硅丙基)四硫化物薄膜的特性.物理化学学报,2006,22(8)：1025-1029
[24]陈明安,杨汐,张新明,等Mg-Gd-Y-Zr合金表面含硫硅烷薄膜的结构与耐蚀性能.中国有色金属学报,2008,18(1)：24-29
[25]王雪明,李爱菊,李国丽,等.金属表面制备KH-560硅烷膜涂层的工艺研究.中国表面工程,2004,6：27-31
[26]王雪明,李爱菊,李国丽,等.硅烷偶联剂在防腐涂层金属预处理中的应用研究材.料科学与工程学报,2005,23(1)：146-150
[27]沈腊珍.电磁屏蔽用导电聚吡咯薄膜的研究：[博士学位论文].天津：天津大学,2006
[28]Arkles B. Tailoring surfaces with silanes. Chemical Technology,1977,7: 766-778
[29]龚建民.金属表面硅烷膜的制备及耐蚀性能研究：[硕士学位论文].安徽：合肥工业大学,2009
[30]乔红斌,佘金阳,古绪鹏,等.硅烷偶联剂在涂料与涂装中的应用进展.安徽工业大学学报,2008,25(4)：379-382
[31]王雪明.硅烷偶联剂在金属预处理及有机涂层中的应用研究：[硕士学位论文].山东：山东大学,2005
[32]Vignesh P, Zhu D Q, van Ooij W J. Nanoparticle-filled silane films as chromate replacements for aluminum alloys. Progess in Organic Coatings,2003,47(4): 384-392
[33]Van Ooij,傅德生,傅原.硅烷偶联剂在金属上的应用.表面技术,1998,28(4)：37-40
[34]Trabelsi W, Triki E, Dhouibi L, et al. The use of pre-treatments based on doped silane solutions for improved corrosion resistance of galvanised steel substrates. Surface and Coatings Technology,2006,200(14-15):4240-4250
[35]Montemor M F, Ferreira M G S. Cerium salt activated nanoparticles as fillers for silane films:Evaluation of the corrosion inhibition performance on galvanised steel substrates. Electrochimica Acta,2007,52(24):6976-6987
[36]Trabelsi W, Cecilio P, Ferreira M G S, et al. Surface evaluation and electrochemical behaviour of doped silane pre-treatments on galvanised steel substrates. Progress in Organic Coatings,2007,59(3):214-223
[37]Sundararajan G P, van Ooij W J. Silane based pretreatments for automotive steels. Surface Engineering,2000,16(4):315-320
[38]Zucchi F, Grassi V, Frignani A, et al. Octadecyl-trimethoxy-silane film formed on copper in different conditions. Materials Chemistry and Physics,2007, 103(2-3),340-344
[39]Cabral A M, Duarte R G, Montemor M F, et al. A comparative study on the corrosion resistance of AA2024-T3 substrates pre-treated with different silane solutions--Composition of the films formed. Progress in Organic Coatings,2005, 54(4):322-331
[40]Cabral A M, Duarte R G, Montemor M F, et al. Analytical characterisation and corrosion behaviour of bis-[triethoxysilylpropyl]tetrasulphide pre-treated AA2024-T3. Corrosion Science,2005,47(3):869-881
[41]郭增昌,王云芳,王汝敏.铝合金表面自组装膜层的表征及耐蚀性研究.材料保护,2007,40(7)：1-5
[42]郭增昌,王云芳,王汝敏.铝合金表面不同硅烷化预处理的耐蚀性研究.中国腐蚀与防护学报,2007,27(3)：172-175
[43]Song G, Atrens A, Stjohn D, et al. The electrochemical corrosion of pure magnesium in 1 N NaCl. Corrosion Science,1997,39(5):855-875
[44]张微,龙军峰,张津,等.硅烷增强镁合金防腐有机涂层的研究.表面技术,2009,38(6)：51-53
[45]Sutar D S, Padma N, Aswal D K, et al. Preparation of nanofibrous polyaniline films and their application as ammonia gas sensor. Sensors and Actuators B: Chemical, 2007,128(1):286-292
[46]Cecchetto L, Denoyelle A, Delabouglise D, et al. A silane pre-treatment for improving corrosion resistance performances of emeraldine base-coated aluminium samples in neutral environment. Applied Surface Science,2008, 254(6):1736-1743
[47]Van Ooij W J. Metal substrate with enhanced corrosion resistance and improved paint adhesion[P]. United States Patent,5,539,031,1996
[48]Franquet A, Le Pen C, Terryn H, et al. Effect of bath concentration and curing time on the structure of non-functional thin organosilane layers on aluminium. Electrochimica Acta,2003,48(9):1245-1255
[49]何天白,胡汉杰.功能高分子与新技术.北京：化学工业出版社,2001
[50]邢存章,于跃芹.有机化学.济南：山东大学出版社,2001
[51]阎实.制备工艺影响多孔基底上沉积PPy导电薄膜性能的研究[硕士学文论文].天津：天津大学,2004
[52]陈世刚.导电聚合物对金属腐蚀防护的机理研究[硕士学位论文].青岛：中国海洋大学,2008
[53]靳承铀.聚吡咯膜的制备、表征和离子交换性能的研究[博士学位论文].大连：大连理工大学,2006
[54]尹五生.聚吡咯导电材料合成方法的进展.功能材料,1996,27(2)：97-102
[55]王杰,徐友龙,陈曦,等.电化学法制备高密度导电聚吡咯的性能研究.物理学报,2007,56(7)：4256-4261
[56]Saidman S B. The effect of pH on the electrochemical polymerisation of pyrrole on aluminium. Journal of Electroanalytical Chemistry,2002,534(1):39-45
[57]Saidman S B, Vela M E. Electropolymerisation of pyrrole onto aluminium from alkaline solutions containing a surfactant. Thin Solid Films,2005,493(1-2): 96-103
[58]Lehr I L, Saidman S B. Corrosion protection of iron by polypyrrole coatings electrosynthesised from a surfactant solution. Corrosion Science,2007,49(5): 2210-2225
[59]Lehr I L, Saidman S B. Morphology and properties of polypyrrole electrosynthesized onto iron from a surfactant solution. Synthetic Metals,2009, 159(15-16):1522-1528
[60]Flamini D O, Saidman S B. Electrodeposition of polypyrrole onto NiTi and the corrosion behaviour of the coated alloy. Corrosion Science,2010,52(1):229-234
[61]蒋永锋,郭兴伍,翟春泉,等.导电高分子在金属防腐领域的研究进展.功能高分子学报,2002,15(4)：473-479
[62]李倩倩,黄健涵,刘素琴,等.对甲苯磺酸掺杂聚吡咯的合成、表征及其对金属镁的防腐蚀性能研究.化学学报,2008,66(5)：571-575
[63]’李倩倩,黄健涵,刘素琴,等.聚吡咯的化学氧化合成及其对金属镁的防腐蚀性能研究.功能材料,2008,39(3)：526-528
[64]DeBerry D W. Modification of the electrochemical and corrosion behavior of stainless steels with an electroactive. Journal of the Electrochemical society, 1985,132(5):1022-1026
[65]Beck F, Haase V, Schroetz M. Polyheteroaromatic layers on commodity metals (CIPL)-passivation, corrosion protection. AIP Conference Proceedings,1996, 354(1):115-136
[66]刘勇平,刘长久,吕慧丹.导电高分子聚吡咯在防腐领域的研究进展.化工新型材料,2007,35(10)：22-24
[67]Evrim Hur, Gozen Bereket, Yucel Sahin. Corrosion performance of self-doped sulfonated polypyrrole coatings on stainless steel. Materials Chemistry and Physics,2006,100(1):19-25
[68]陈世刚,赵文元,孙常志,等.电化学合成聚吡咯及其腐蚀防护性能研究.腐蚀科学与防护技术,2009,21(3)：269-272
[69]Hermas A A, Nakayama M, Ogura K. Formation of stable passive film on stainless steel by elect rochemical deposition of polypyrrole. Electrochimica Acta, 2005,50(18):3640-3647
[70]Malik M A, Wlodarczyk R, Kulesza P J, et al. Protective properties of hexacyanofer rate containing polypyrrole films on stainless steel. Corrosion Science,2005,47(3):771-783
[71]Paliwoda-Porebska G, Stratmann M, Rohwerder M, et al. On the development of polypyrrole coatings with self-healing properties for iron corrosion protection. Corrosion Science,2005,47(12):3216-3233
[72]张爱勤,郭兴蓬Al/Al2O3/PPY的制备及其在含氯离子溶液中的阻抗特征.腐蚀与防护,2003,24(10)：428-431
[73]杨庆浩,宁方平,胡海军.聚吡咯及其共聚物功能化环氧树脂基防腐涂料制备研究.功能材料,2009,40：568-571
[74]Bereket G, Hur E. The corrosion protection of mild steel by single layered polypyrrole and multilayered polypyrrole/poly(5-amino-l-naphthol) coatings. Progress in Organic Coatings,2009,65(1):116-124
[75]Lehr I L, Saidman S B. Characterisation and corrosion protection properties of polypyrrole electropolymerised onto aluminium in the presence of molybdate and nitrate. Electrochimica Acta,2006,51(16):3249-3255
[76]Hammache H, Makhloufi L, Saidani B. Corrosion protection of iron by polypyrrole modified by copper using the cementation process. Corrosion Science,2003,45(9):2031-2042
[77]Attarzadeh N, Raeissi K, Golozar M A. Effect of saccharin addition on the corrosion resistance of polypyrrole coatings. Progress in Organic Coatings,2008, 63(2):167-174
[78]Arenas M A, Bajos L G Damborenea J J, et al. Synthesis and electrochemical evaluation of polypyrrole coatings electrodeposited onto AA-2024 alloy. Progress in Organic Coatings,2008,62(1):79-86
[79]Rajagopalan R, Iroh J O. Pretreatment and coating of low carbon steel using constant potential electrochemical process. Surface Engineering,2002,18(1): 53-58
[80]Truong V T, Lai P K, Moore B T, et al. Corrosion protection of magnesium by electroactive polypyrrole/paint coatings. Synthetic Metals.2000,110(1):7-15
[81]Montemor M F, Ferreira M G S. Analytical characterization of silane films modified with cerium activated nanoparticles and its relation with the corrosion protection of galvanised steel substrates. Progress in Organic Coatings,2008, 63(3),330-337
[82]Deflorian F, Rossi S, Fedrizzi L, et al. Integrated electrochemical approach for the investigation of silane pre-treatments for painting copper. Progress in Organic Coatings,2008,63(3),338-344
[83]Li Y S, Tran T, Xu Y, et al. Spectroscopic studies of trimetoxypropylsilane and bis(trimethoxysilyl)ethane sol-gel coatings on aluminum and copper. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2006, 65(3-4):779
[84]Zhu D Q. Corrosion protection of metals by silane surface treatment:[PhD thesis]. University of Cincinnati, Cincinnati, USA,2005
[85]胡吉明,刘惊,张金涛,等.铝合金表面BTESPT硅烷化处理研究.金属学报,2004,40(11)：1189-1194
[86]Kouisni L. Azzi M, Dalard F, et al. Phosphate coatings on magnesium alloy AM60 Part 2:Electrochemical behaviour in borate buffer solution. Surface and coatings technology,2005,192(2-3):239-246
[87]Pardo A, Merino M C, Coy A E, et al. Corrosion behaviour of magnesium/ aluminium alloys in 3.5 wt.% NaCl. Corrosion Science,2008,50(3):823-834
[88]Zhao M C, Liu M, Song G L, et al. Influence of pH and chloride ion concentration on the corrosion of Mg alloy ZE41. Corrosion Science,2008, 50(11):3168-3178
[89]Zhu D Q, van Ooij W J. Enhanced corrosion resistance of AA 2024-T3 and hot-dip galvanized steel using a mixture of bis-[triethoxysilylpropyl]tetrasulde and bis-[trimethoxysilylpropyl]amine. Electrochimica Acta,2004,49(7): 1113-1125
[90]Liu X L, Zhang T, Shao Y W, et al. Effect of alternating voltage treatment on the corrosion resistance of pure magnesium. Corrosion Science,2009,51(8): 1772-1779
[91]曹楚南,张鉴清.电化学阻抗谱导论.北京：科学出版社,2002：151-191
[92]印仁和,赵亚萍,戴迎春,等.水杨酸钠对电镀锌钢板上电聚合吡咯的作用.金属学报,2004,40(2)：168-172
[93]Trueba M, Trasatti S P. Pyrrole-based silane primer for corrosion protection of commercial Al alloys Part Ⅰ:Synthesis and spectroscopic characterization. Progress in Organic Coatings,2009,66(3):254-264
[94]沈腊珍,乔永生,杨国臣.绝缘环氧模塑料表面导电聚吡咯薄膜的化学聚合与表征.山西大同大学学报,2009,25(4)：32-35
[95]Thieblemont J C, Gabelle J L, Planche M F. Polypyrrole overoxidation during its chemical synthesis. Synthetic Metals,1994,66(3):243-247
[96]安颢瑗,任丽,王立新.磺酸系掺杂剂对聚吡咯结构与导电性能的影响.云南大学学报(自然科学版),2005,27(5A)：425-428
[97]冉奋,孔令斌,罗永春,等.化学氧化法合成超级电容器电极用聚吡咯及其工艺优化.兰州理工大学学报,2007,33(6)：27-32
[2]陈晓阳,曾大本.镁合金铸件的应用现状及发展前景.铸造,1999,11：53-55
[3]宋光龄.镁合金腐蚀与防护.北京：化学工业出版社,2006
[4]王渠东,吕宜振,曾小勒.镁合金在电子器材壳体中的应用.材料导报,2000,14(6)：22-24
[5]李光玉.镁合金表面涂层和化学镀层的研究：[博士学位论文].吉林：吉林大学,2006
[6]孟岩,潘建亮.汽车轻量化材料的应用.技术与应用,2010,18(5)：24-27
[7]李卫平,朱立群.镁及其合金表面防护性涂层国外研究进展,材料保护2005,38(2)：41-46
[8]蒋百灵,张淑芬,吴国建,等.镁合金微弧氧化陶瓷层显微缺陷与相组成及其耐蚀性.中国有色金属学报,2002,12(3)：454-457
[9]李鑫庆,陈迪勤,余静琴.化学转化膜技术与应用.北京：机械工业出版社,2005
[10]郭洪飞,安茂忠,刘荣娟.镁及其合金表面化学转化处理技术.轻合金加工技术,2003,31(8)：35-41
[11]程英亮,吴海兰,李玲玲,等.ZK6镁合金磷酸盐及锡酸盐化学转化膜.中国有色金属学报,2007,17(5)：676-682
[12]Gray J E, Luan B. Protective coatings on magnesium and its alloys—a critical review. Journal of Alloys and Compounds,2002,336:88-113
[13]徐以兵.铝合金和镁合金的表面硅烷化处理研究[硕士学位论文].长沙：湖南大学,2008
[14]Van Ooij W J, Child T. Protecting metals with silane coupling. Chemical technology,1998,28(2):26-35
[15]Van Ooij W J, Zhu D Q, Palanivel V, et al. The potential of silanes for chromate replacement in metal finishing industries. Silicon Chemistry,2006,3(1-2):11-30
[16]Zhu D Q, van Ooij W J. Surface modification of metals by silanes in Adhesion aspects of polymeric coatings. Utrecht:VSP,2003,2:81-89
[17]Van Ooij W J, Zhu D Q, Stacy M, et al. Corrosion protection properties of organofunctional silanes—An Overview. Tsinghua Science and Technology, 2005,10(6):639-664
[18]Zucchi F, Frignani A, Grassi V, et al. Organo-silane coatings for AZ31 magnesium alloy corrosion protection. Materials Chemistry and Physics,2008, 110(2-3):263-268
[19]Montemor M F, Ferreira M G S. Analytical and microscopic characterisation of modified bis-[triethoxysilylpropyl] tetrasulphide silane films on magnesium AZ31 substrates. Progress Organic Coatings,2007,60(3):228-237
[20]Montemor M F, Ferreira M G S. Electrochemical study of modified bis-[triethoxysilylpropyl] tetrasulfide silane films applied on the AZ31 Mg alloy. Electrochimica Acta,2007,52(27):7486-7495
[21]Chen M A, Xie X, Xu G F, et al. Structural characterization and corrosion properties of BTESPT silane films on Surface of 2024-T6 aluminium alloy. Materials Science Forum,2007,546-549:1111-1116
[22]路学斌,郭照辉,黄荣,等.紫铜表面3-巯丙基三乙氧基硅烷薄膜的制备与耐蚀性能.物理化学学报,2010,27(1)：108-112
[23]陈明安,谢玄,戚海英,等.2A12-T6铝合金表面双-(γ-三乙氧基硅丙基)四硫化物薄膜的特性.物理化学学报,2006,22(8)：1025-1029
[24]陈明安,杨汐,张新明,等Mg-Gd-Y-Zr合金表面含硫硅烷薄膜的结构与耐蚀性能.中国有色金属学报,2008,18(1)：24-29
[25]王雪明,李爱菊,李国丽,等.金属表面制备KH-560硅烷膜涂层的工艺研究.中国表面工程,2004,6：27-31
[26]王雪明,李爱菊,李国丽,等.硅烷偶联剂在防腐涂层金属预处理中的应用研究材.料科学与工程学报,2005,23(1)：146-150
[27]沈腊珍.电磁屏蔽用导电聚吡咯薄膜的研究：[博士学位论文].天津：天津大学,2006
[28]Arkles B. Tailoring surfaces with silanes. Chemical Technology,1977,7: 766-778
[29]龚建民.金属表面硅烷膜的制备及耐蚀性能研究：[硕士学位论文].安徽：合肥工业大学,2009
[30]乔红斌,佘金阳,古绪鹏,等.硅烷偶联剂在涂料与涂装中的应用进展.安徽工业大学学报,2008,25(4)：379-382
[31]王雪明.硅烷偶联剂在金属预处理及有机涂层中的应用研究：[硕士学位论文].山东：山东大学,2005
[32]Vignesh P, Zhu D Q, van Ooij W J. Nanoparticle-filled silane films as chromate replacements for aluminum alloys. Progess in Organic Coatings,2003,47(4): 384-392
[33]Van Ooij,傅德生,傅原.硅烷偶联剂在金属上的应用.表面技术,1998,28(4)：37-40
[34]Trabelsi W, Triki E, Dhouibi L, et al. The use of pre-treatments based on doped silane solutions for improved corrosion resistance of galvanised steel substrates. Surface and Coatings Technology,2006,200(14-15):4240-4250
[35]Montemor M F, Ferreira M G S. Cerium salt activated nanoparticles as fillers for silane films:Evaluation of the corrosion inhibition performance on galvanised steel substrates. Electrochimica Acta,2007,52(24):6976-6987
[36]Trabelsi W, Cecilio P, Ferreira M G S, et al. Surface evaluation and electrochemical behaviour of doped silane pre-treatments on galvanised steel substrates. Progress in Organic Coatings,2007,59(3):214-223
[37]Sundararajan G P, van Ooij W J. Silane based pretreatments for automotive steels. Surface Engineering,2000,16(4):315-320
[38]Zucchi F, Grassi V, Frignani A, et al. Octadecyl-trimethoxy-silane film formed on copper in different conditions. Materials Chemistry and Physics,2007, 103(2-3),340-344
[39]Cabral A M, Duarte R G, Montemor M F, et al. A comparative study on the corrosion resistance of AA2024-T3 substrates pre-treated with different silane solutions--Composition of the films formed. Progress in Organic Coatings,2005, 54(4):322-331
[40]Cabral A M, Duarte R G, Montemor M F, et al. Analytical characterisation and corrosion behaviour of bis-[triethoxysilylpropyl]tetrasulphide pre-treated AA2024-T3. Corrosion Science,2005,47(3):869-881
[41]郭增昌,王云芳,王汝敏.铝合金表面自组装膜层的表征及耐蚀性研究.材料保护,2007,40(7)：1-5
[42]郭增昌,王云芳,王汝敏.铝合金表面不同硅烷化预处理的耐蚀性研究.中国腐蚀与防护学报,2007,27(3)：172-175
[43]Song G, Atrens A, Stjohn D, et al. The electrochemical corrosion of pure magnesium in 1 N NaCl. Corrosion Science,1997,39(5):855-875
[44]张微,龙军峰,张津,等.硅烷增强镁合金防腐有机涂层的研究.表面技术,2009,38(6)：51-53
[45]Sutar D S, Padma N, Aswal D K, et al. Preparation of nanofibrous polyaniline films and their application as ammonia gas sensor. Sensors and Actuators B: Chemical, 2007,128(1):286-292
[46]Cecchetto L, Denoyelle A, Delabouglise D, et al. A silane pre-treatment for improving corrosion resistance performances of emeraldine base-coated aluminium samples in neutral environment. Applied Surface Science,2008, 254(6):1736-1743
[47]Van Ooij W J. Metal substrate with enhanced corrosion resistance and improved paint adhesion[P]. United States Patent,5,539,031,1996
[48]Franquet A, Le Pen C, Terryn H, et al. Effect of bath concentration and curing time on the structure of non-functional thin organosilane layers on aluminium. Electrochimica Acta,2003,48(9):1245-1255
[49]何天白,胡汉杰.功能高分子与新技术.北京：化学工业出版社,2001
[50]邢存章,于跃芹.有机化学.济南：山东大学出版社,2001
[51]阎实.制备工艺影响多孔基底上沉积PPy导电薄膜性能的研究[硕士学文论文].天津：天津大学,2004
[52]陈世刚.导电聚合物对金属腐蚀防护的机理研究[硕士学位论文].青岛：中国海洋大学,2008
[53]靳承铀.聚吡咯膜的制备、表征和离子交换性能的研究[博士学位论文].大连：大连理工大学,2006
[54]尹五生.聚吡咯导电材料合成方法的进展.功能材料,1996,27(2)：97-102
[55]王杰,徐友龙,陈曦,等.电化学法制备高密度导电聚吡咯的性能研究.物理学报,2007,56(7)：4256-4261
[56]Saidman S B. The effect of pH on the electrochemical polymerisation of pyrrole on aluminium. Journal of Electroanalytical Chemistry,2002,534(1):39-45
[57]Saidman S B, Vela M E. Electropolymerisation of pyrrole onto aluminium from alkaline solutions containing a surfactant. Thin Solid Films,2005,493(1-2): 96-103
[58]Lehr I L, Saidman S B. Corrosion protection of iron by polypyrrole coatings electrosynthesised from a surfactant solution. Corrosion Science,2007,49(5): 2210-2225
[59]Lehr I L, Saidman S B. Morphology and properties of polypyrrole electrosynthesized onto iron from a surfactant solution. Synthetic Metals,2009, 159(15-16):1522-1528
[60]Flamini D O, Saidman S B. Electrodeposition of polypyrrole onto NiTi and the corrosion behaviour of the coated alloy. Corrosion Science,2010,52(1):229-234
[61]蒋永锋,郭兴伍,翟春泉,等.导电高分子在金属防腐领域的研究进展.功能高分子学报,2002,15(4)：473-479
[62]李倩倩,黄健涵,刘素琴,等.对甲苯磺酸掺杂聚吡咯的合成、表征及其对金属镁的防腐蚀性能研究.化学学报,2008,66(5)：571-575
[63]’李倩倩,黄健涵,刘素琴,等.聚吡咯的化学氧化合成及其对金属镁的防腐蚀性能研究.功能材料,2008,39(3)：526-528
[64]DeBerry D W. Modification of the electrochemical and corrosion behavior of stainless steels with an electroactive. Journal of the Electrochemical society, 1985,132(5):1022-1026
[65]Beck F, Haase V, Schroetz M. Polyheteroaromatic layers on commodity metals (CIPL)-passivation, corrosion protection. AIP Conference Proceedings,1996, 354(1):115-136
[66]刘勇平,刘长久,吕慧丹.导电高分子聚吡咯在防腐领域的研究进展.化工新型材料,2007,35(10)：22-24
[67]Evrim Hur, Gozen Bereket, Yucel Sahin. Corrosion performance of self-doped sulfonated polypyrrole coatings on stainless steel. Materials Chemistry and Physics,2006,100(1):19-25
[68]陈世刚,赵文元,孙常志,等.电化学合成聚吡咯及其腐蚀防护性能研究.腐蚀科学与防护技术,2009,21(3)：269-272
[69]Hermas A A, Nakayama M, Ogura K. Formation of stable passive film on stainless steel by elect rochemical deposition of polypyrrole. Electrochimica Acta, 2005,50(18):3640-3647
[70]Malik M A, Wlodarczyk R, Kulesza P J, et al. Protective properties of hexacyanofer rate containing polypyrrole films on stainless steel. Corrosion Science,2005,47(3):771-783
[71]Paliwoda-Porebska G, Stratmann M, Rohwerder M, et al. On the development of polypyrrole coatings with self-healing properties for iron corrosion protection. Corrosion Science,2005,47(12):3216-3233
[72]张爱勤,郭兴蓬Al/Al2O3/PPY的制备及其在含氯离子溶液中的阻抗特征.腐蚀与防护,2003,24(10)：428-431
[73]杨庆浩,宁方平,胡海军.聚吡咯及其共聚物功能化环氧树脂基防腐涂料制备研究.功能材料,2009,40：568-571
[74]Bereket G, Hur E. The corrosion protection of mild steel by single layered polypyrrole and multilayered polypyrrole/poly(5-amino-l-naphthol) coatings. Progress in Organic Coatings,2009,65(1):116-124
[75]Lehr I L, Saidman S B. Characterisation and corrosion protection properties of polypyrrole electropolymerised onto aluminium in the presence of molybdate and nitrate. Electrochimica Acta,2006,51(16):3249-3255
[76]Hammache H, Makhloufi L, Saidani B. Corrosion protection of iron by polypyrrole modified by copper using the cementation process. Corrosion Science,2003,45(9):2031-2042
[77]Attarzadeh N, Raeissi K, Golozar M A. Effect of saccharin addition on the corrosion resistance of polypyrrole coatings. Progress in Organic Coatings,2008, 63(2):167-174
[78]Arenas M A, Bajos L G Damborenea J J, et al. Synthesis and electrochemical evaluation of polypyrrole coatings electrodeposited onto AA-2024 alloy. Progress in Organic Coatings,2008,62(1):79-86
[79]Rajagopalan R, Iroh J O. Pretreatment and coating of low carbon steel using constant potential electrochemical process. Surface Engineering,2002,18(1): 53-58
[80]Truong V T, Lai P K, Moore B T, et al. Corrosion protection of magnesium by electroactive polypyrrole/paint coatings. Synthetic Metals.2000,110(1):7-15
[81]Montemor M F, Ferreira M G S. Analytical characterization of silane films modified with cerium activated nanoparticles and its relation with the corrosion protection of galvanised steel substrates. Progress in Organic Coatings,2008, 63(3),330-337
[82]Deflorian F, Rossi S, Fedrizzi L, et al. Integrated electrochemical approach for the investigation of silane pre-treatments for painting copper. Progress in Organic Coatings,2008,63(3),338-344
[83]Li Y S, Tran T, Xu Y, et al. Spectroscopic studies of trimetoxypropylsilane and bis(trimethoxysilyl)ethane sol-gel coatings on aluminum and copper. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2006, 65(3-4):779
[84]Zhu D Q. Corrosion protection of metals by silane surface treatment:[PhD thesis]. University of Cincinnati, Cincinnati, USA,2005
[85]胡吉明,刘惊,张金涛,等.铝合金表面BTESPT硅烷化处理研究.金属学报,2004,40(11)：1189-1194
[86]Kouisni L. Azzi M, Dalard F, et al. Phosphate coatings on magnesium alloy AM60 Part 2:Electrochemical behaviour in borate buffer solution. Surface and coatings technology,2005,192(2-3):239-246
[87]Pardo A, Merino M C, Coy A E, et al. Corrosion behaviour of magnesium/ aluminium alloys in 3.5 wt.% NaCl. Corrosion Science,2008,50(3):823-834
[88]Zhao M C, Liu M, Song G L, et al. Influence of pH and chloride ion concentration on the corrosion of Mg alloy ZE41. Corrosion Science,2008, 50(11):3168-3178
[89]Zhu D Q, van Ooij W J. Enhanced corrosion resistance of AA 2024-T3 and hot-dip galvanized steel using a mixture of bis-[triethoxysilylpropyl]tetrasulde and bis-[trimethoxysilylpropyl]amine. Electrochimica Acta,2004,49(7): 1113-1125
[90]Liu X L, Zhang T, Shao Y W, et al. Effect of alternating voltage treatment on the corrosion resistance of pure magnesium. Corrosion Science,2009,51(8): 1772-1779
[91]曹楚南,张鉴清.电化学阻抗谱导论.北京：科学出版社,2002：151-191
[92]印仁和,赵亚萍,戴迎春,等.水杨酸钠对电镀锌钢板上电聚合吡咯的作用.金属学报,2004,40(2)：168-172
[93]Trueba M, Trasatti S P. Pyrrole-based silane primer for corrosion protection of commercial Al alloys Part Ⅰ:Synthesis and spectroscopic characterization. Progress in Organic Coatings,2009,66(3):254-264
[94]沈腊珍,乔永生,杨国臣.绝缘环氧模塑料表面导电聚吡咯薄膜的化学聚合与表征.山西大同大学学报,2009,25(4)：32-35
[95]Thieblemont J C, Gabelle J L, Planche M F. Polypyrrole overoxidation during its chemical synthesis. Synthetic Metals,1994,66(3):243-247
[96]安颢瑗,任丽,王立新.磺酸系掺杂剂对聚吡咯结构与导电性能的影响.云南大学学报(自然科学版),2005,27(5A)：425-428
[97]冉奋,孔令斌,罗永春,等.化学氧化法合成超级电容器电极用聚吡咯及其工艺优化.兰州理工大学学报,2007,33(6)：27-32