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中国腐蚀与防护学报  2016, Vol. 36 Issue (1): 52-58    DOI: 10.11902/1005.4537.2015.109
  本期目录 | 过刊浏览 |
铜合金表面巯基官能有机硅溶胶-凝胶涂层中TEOS含量对其防腐性能的影响
睢文杰1,2,赵文杰2(),张星1(),秦立光1,2,彭叔森2,乌学东2,薛群基2
1. 中北大学材料科学与工程学院 太原 030051
2. 中国科学院宁波材料技术与工程研究所 中国科学院海洋新材料与应用技术重点实验室 浙江省海洋材料与防护技术重点实验室 宁波 315201
Influence of TEOS Content on Anti-corrosion Property of Mercapto Functional Organic Silane Based Sol-gel Coatings on Copper Alloy Surface
Wenjie SUI1,2,Wenjie ZHAO2(),Xing ZHANG1(),Liguang QIN1,2,Shusen PENG2,Xuedong WU2,Qunji XUE2
1. School of Materials Science and Engineering, North University of China, Taiyuan 030051, China
2. Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
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摘要: 

以巯基丙基三甲氧基硅烷 (MPTMS) 为有机前驱体,以正硅酸四乙酯 (TEOS) 为无机前驱体,盐酸为催化剂,经水解-缩合反应在Cu合金H62表面制备了高固含量的有机-无机杂化溶胶-凝胶涂层.利用红外光谱仪,动态光散射粒度分析仪对涂层的化学成分和溶胶粒子的平均直径进行表征,利用SEM观察涂层的表面和截面形貌,利用拉脱法附着力测试仪和电化学工作站对涂层的附着力和耐蚀性进行表征.结果表明:TEOS的加入有利于提高涂层的热稳定性.随着TEOS含量的增加,溶胶粒子的尺寸呈上升趋势,过量的TEOS会使涂层表面和内部产生孔洞和裂纹等缺陷.当TEOS和MPTMS的摩尔比为0.6时,涂层的交联密度较大且涂层缺陷较少,涂层的耐蚀性最佳.
关键词 ： 铜合金,  溶胶-凝胶涂层,  交联,  耐蚀性能,  热稳定性    
Abstract：

Organic-inorganic hybrid sol-gel coatings with high solid content were prepared on copper surface by means of hydrolysis-condensation reaction. 3-Mercaptopropyltrimethoxysilane (MP-TMS), tetraethylorthosilicate (TEOS) and hydrochloric acid were used as organic precursor, inorganic precursor and catalysts respectively. The chemical composition, and the average size of sol particles and the surface- and cross section-morphology of sol-gel coatings were characterized by Fourier transform infrared spectroscopy, dynamic light scattering particle size analyzer and field emission scanning electron microscopy respectively. The adhesion and corrosion performance of sol-gel coatings were investigated by pull-off adhesion tester and electrochemical workstation. The results showed that the thermo-stability of the coatings was significantly improved due to the addition of TEOS. However, the average size of sol particles increased with the increase of TEOS content. Excessive addition of TEOS can induce holes and cracks on the surface of coatings or within the coatings. The coatings owned the best corrosion resistance when the molar ratio of TEOS to MPTMS was 0.6 due to their larger crosslinking density and fewer defects.
Key words： Cu alloy    sol-gel coating    crosslinking    corrosion resistance    thermo-stability
    
基金资助:国家重点基础研究发展计划项目 (2014CB643305),国家自然科学基金项目 (51202263和51335010),浙江省"海洋防护材料与工程技术"科技创新团队项目 (2011R50006)及宁波市自然科学基金项目 (2014A610132) 资助
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睢文杰
赵文杰
张星
秦立光
彭叔森
乌学东
薛群基

引用本文:

睢文杰,赵文杰,张星,秦立光,彭叔森,乌学东,薛群基. 铜合金表面巯基官能有机硅溶胶-凝胶涂层中TEOS含量对其防腐性能的影响[J]. 中国腐蚀与防护学报, 2016, 36(1): 52-58.
Wenjie SUI, Wenjie ZHAO, Xing ZHANG, Liguang QIN, Shusen PENG, Xuedong WU, Qunji XUE. Influence of TEOS Content on Anti-corrosion Property of Mercapto Functional Organic Silane Based Sol-gel Coatings on Copper Alloy Surface. Journal of Chinese Society for Corrosion and protection, 2016, 36(1): 52-58.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2015.109      或      https://www.jcscp.org/CN/Y2016/V36/I1/52

图1  TEOS和MPTMS的红外光谱
图2  不同涂层的红外光谱
图3  涂层样品的溶胶粒子尺寸
图4  溶胶-凝胶涂层的表面及截面形貌
图5  溶胶-凝胶涂层与Cu基底的附着力
图6  烘烤前后铜合金样品的宏观形貌
图7  未涂覆及涂覆溶胶-凝胶涂层的铜合金样品在3.5%NaCl溶液中的动电位极化曲线
Sample Icorr / Acm-2 Ecorr / mV η / %
Bare 2.250×10-6 -327 ---
T0 5.964×10-9 -412 99.73
T4 4.251×10-9 -352 99.81
T6 5.360×10-10 -445 99.97
T8 1.492×10-8 -451 99.34
T10 2.952×10-7 -498 86.88
表1  由极化曲线获得的未涂覆及涂覆溶胶-凝胶涂层的铜合金试样的电化学参数
图8  不同样品的频率-阻抗图和频率-相位角图
图9  不同样品的Nyquist图
图10  EIS数据拟合等效电路
Electrode Qfilm / Ω-1sncm-2 nfilm Rfilm / Ωcm2 Qdl / Ω-1sncm-2 ndl Rct / Ωcm2 W / Ω-1s0.5cm-2 Equivalent / circuit
Bare --- --- --- 2.238×10-5 0.8 4.382×103 1.652×10-3 R(Q(RW))
T0 5.324×10-7 0.9235 1.704×104 6.485×10-6 0.7462 3.128×105 --- R(Q(R(QR)))
T4 1.797×10-8 0.8524 2.330×104 5.916×10-7 0.7565 8.752×105 --- R(Q(R(QR)))
T6 1.290×10-9 0.8638 3.400×104 1.360×10-6 0.7454 1.205×106 --- R(Q(R(QR)))
T8 1.089×10-8 0.8 1.746×104 8.126×10-6 0.6515 2.079×105 --- R(Q(R(QR)))
T10 3.567×10-9 0.9338 2.054×104 6.690×10-6 0.7449 1.440×105 --- R(Q(R(QR)))
表2  阻抗谱等效电路各元件的值
[1] Wu J, Li X G, Dong C F, et al.Initial corrosion behavior of copper and brass in tropical maritime atmospheric environment[J]. J. Chin.Soc. Corros. Prot., 2012, 32(1): 70
[1] (吴军, 李晓刚, 董超芳等. 紫铜T2和黄铜H62在热带海洋大气环境中早期腐蚀行为[J]. 中国腐蚀与防护学报, 2012, 32(1): 70)
[2] Peng S S, Zeng Z X, Han J, et al.Progress of anticorrosion of silane based sol-gel coating[J]. Mater. China, 2014, 33(2): 77
[2] (彭叔森, 曾志翔, 韩金等. 有机硅溶胶-凝胶防腐蚀涂层研究进展[J]. 中国材料进展, 2014, 33(2): 77)
[3] Song S F, Hu D D, Shen S K, et al.Research progress of self-assembly behavior of organosiloxane during sol-gel process[J]. Chem. Ind. Eng. Prog., 2014, 33(8): 2101
[3] (宋少飞, 胡道道, 沈淑坤等. 溶胶-凝胶过程中有机硅氧烷的自组装行为研究进展[J]. 化工进展, 2014, 33(8): 2101)
[4] Beccaria A M, Bertolotto C.Inhibitory action of 3-trimethoxysilylpropanethiol-1 on copper corrosion in NaCl solutions[J]. Electrochim. Acta, 1997, 42(9): 1361
[5] Tremont R, Cabrera C R.Electrochemical and surface analysis study of copper corrosion protection by 1-propanethiol and propyltrimethoxysilane: A comparison with 3-mercaptopropyltrimethoxys-ilane[J]. J. Appl. Electrochem., 2002, 32(7): 783
[6] Zhang L, Li S Y, Fan H Q, et al.Corrosion resistance of brass modified with self-assembled silane films in NaCl solution[J]. Electroplat. Finish., 2011, 30(12): 48
[6] (张琳, 李淑英, 范洪强等. 黄铜表面硅烷自组装膜在氯化钠溶液中的耐蚀性[J]. 电镀与涂饰, 2011, 30(12): 48)
[7] Fan H Q, Li S Y, Zhao Z C, et al.Inhibition of brass corrosion in sodium chloride solutions by self-assembled silane films[J]. Corros. Sci., 2011, 53(12): 4273
[8] Chen M A, Lu X B, Guo Z H, et al.Influence of hydrolysis time on the structure and corrosion protective performance of (3-mercaptopropyl) triethoxysilane film on copper[J]. Corros. Sci., 2011, 53(9):2793
[9] Lu X B, Guo Z H, Huang R, et al.Preparation of a (3-Mercaptopropyl) triethoxylsilane film on copper and its corrosion protective performance[J]. Acta Phys.-Chim. Sin., 2011, 27(1): 108
[9] (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[J]. 物理化学学报, 2011, 27(1): 108)
[10] Huang L, Lin K F, Yang F Z, et al.Structure and corrosion electrochemical properties of self-assembled (3-mercaptopropyl) trimethoxysilanefimls on copper electrode[J]. Electrochemistry, 2005,11(2): 188
[10] (黄令, 林克发, 杨防祖等. 铜电极表面硅烷膜的自组装及其性能研究[J]. 电化学, 2005, 11(2): 188)
[11] Zhang L, Qian J H, Yu Z H.Characterization and corrosion inhibition ability of self-assembled γ-mercaptopropyltrimethoxysilane[J]. J. Bohai Univ.(Nat. Sci. Ed.), 2011, 32(4): 340
[11] (张蕾, 钱建华, 俞卓汗. γ-巯基丙基三甲氧基硅烷自组装膜的制备及其防腐蚀性能[J]. 渤海大学学报 (自然科学版), 2011, 32(4): 340)
[12] Peng S S, Zeng Z X, Zhao W J, et al.Performance evaluation of mercapto functional hybrid silica sol-gel coating on copper surface[J]. Surf. Coat. Technol., 2014, 251: 135
[13] Peng S S, Han J, Zhao W J, et al.The protection and degradation behaviors of mercapto functional sol-gel coating on copper surface[J]. J. Electrochem. Soc., 2015, 162(4): C1
[14] Zucchi F, Grassi V, Frignani A, et al.Inhibition of copper corrosion by silane coatings[J]. Corros. Sci., 2004, 46(11): 2853
[15] Chen G, Liu G M, Yao J, et al.Influence of TEOS content on property of silicone/SiO2 hybrid coatings[J]. Corros. Sci. Prot. Technol., 2010, 22(5): 418
[15] (陈刚, 刘光明, 姚敬等. TEOS含量对有机硅/SiO2杂化涂层性能的影响[J]. 腐蚀科学与防护技术, 2010, 22(5): 418)
[16] Peng S S, Zeng Z X, Zhao W J, et al.Synergistic effect of thiourea in epoxy functionalized silica sol-gel coating for copper protection[J]. Surf. Coat. Technol., 2012, 213: 175
[17] Rao B A, Lqbal M Y, Sreedhar B.Self-assembled monolayer of 2- (octadecylthio) benzothiazole for corrosion protection of copper[J]. Corros. Sci., 2009, 51(6): 1441
[18] ?ncül A, ?oban K, Sezer E, et al.Inhibition of the corrosion of stainless steel by poly-N-vinylimidazole and N-vinylimidazole[J].Prog. Org. Coat., 2011, 71(2): 167
[19] Roussi E, Tsetsekou A, Tsiourvas D, et al.Novel hybrid organo-silicate corrosion resistant coatings based on hyperbranched polymers[J]. Surf. Coat. Technol., 2011, 205(10): 3235
[20] Wang P, Liang C H, Wu B, et al.Protection of copper corrosion by modification of dodecanethiol self-assembled monolayers prepared in aqueous micellar solution[J]. Electrochim. Acta, 2010, 55(3): 878
[21] Huang L, Lin K F, Yang F Z, et al.Corrosion resistance of copper surface modified with (3-mercaptopropyl) trimethoxysilane in NaOH solution[J]. Mater. Prot., 2005, 38(11): 18
[21] (黄令, 林克发, 杨防祖等. 铜表面修饰硅烷膜在碱性溶液中的耐蚀性能研究[J]. 材料保护, 2005, 38(11): 18)
[22] Kear G, Barker B D, Walsh F C.Electrochemical corrosion of unalloyed copper in chloride media-A critical review[J]. Corros. Sci., 2004, 46(1): 109
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