周亚茹,朱泽洁,聂林林,张鉴清,曹发和.氯离子浓度对 Ni-P 合金涂层失效过程影响的SECM 实验和 COMSOL 模拟研究[J].表面技术,2016,45(7):8-16.
ZHOU Ya-ru,ZHU Ze-jie,NIE Lin-lin,ZHANG Jian-qing,CAO Fa-he.The Effect of Chloride Ion on Corrosion Behavior of Ni-P Alloy Coating Using SECM Experiment and COMSOL Simulation[J].Surface Technology,2016,45(7):8-16
氯离子浓度对 Ni-P 合金涂层失效过程影响的SECM 实验和 COMSOL 模拟研究
The Effect of Chloride Ion on Corrosion Behavior of Ni-P Alloy Coating Using SECM Experiment and COMSOL Simulation
投稿时间:2016-02-10  修订日期:2016-07-20
DOI:10.16490/j.cnki.issn.1001-3660.2016.07.002
中文关键词:  Ni-P 合金涂层  SECM  COMSOL 模拟  活性点  分辨率
英文关键词:Ni-P coating  SECM  COMSOL simulation  active site  resolution
基金项目:国家自然科学基金项目(51171172, 51131005);浙江省自然科学基金杰出青年项目(LR16E010001);中央高校基本研究经费(2015QNA3011)
作者单位
周亚茹 浙江大学 化学系,杭州 310027 
朱泽洁 浙江大学 化学系,杭州 310027 
聂林林 浙江大学 化学系,杭州 310027 
张鉴清 浙江大学 化学系,杭州 310027 
曹发和 浙江大学 化学系,杭州 310027 
AuthorInstitution
ZHOU Ya-ru Department of Chemistry, Zhejiang University, Hangzhou 310027, China 
ZHU Ze-jie Department of Chemistry, Zhejiang University, Hangzhou 310027, China 
NIE Lin-lin Department of Chemistry, Zhejiang University, Hangzhou 310027, China 
ZHANG Jian-qing Department of Chemistry, Zhejiang University, Hangzhou 310027, China 
CAO Fa-he Department of Chemistry, Zhejiang University, Hangzhou 310027, China 
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中文摘要:
      目的 发展具有空间分辨的腐蚀电化学研究方法。 方法 用电沉积方法在铜基体上制备 Ni 和Ni-P 涂层,应用扫描电镜和 XRD 检测涂层表面形貌和晶体结构,采用扫描电化学显微镜(SECM)研究 Ni 和 Ni-P 涂层在不同浓度 NaCl 溶液中的失效行为,并结合 COMSOL 多物理场软件建立二维和三维模型,模拟量化活性点大小和反馈机制。 结果 低浓度 Cl?对于纯 Ni 涂层具有活化作用,增加 Cl?浓度会促进腐蚀发生。 Ni-P 合金涂层在低浓度 NaCl 溶液中,短时间内保持良好的稳定性,浸泡 6 h 后,低 P合金涂层出现典型的活性点和腐蚀产物,而高 P合金涂层在浸泡 24 h后出现腐蚀产物和活性区域。0.1 mol/L 的 NaCl 溶液促进低 P 合金涂层局部腐蚀的发生,而涂层在 0.3 mol/L NaCl 溶液中则以发生均匀腐蚀为主。逼近曲线及其模拟结果表明, 腐蚀产物对于 FcMeOH 的电化学过程完全失活,而新鲜 Cu表面对 FcMeOH 氧化还原过程受扩散控制。三维模拟结果显示,低 P 合金涂层失效过程中活性点大小接近 10 μm。 结论 Ni 和 Ni-P 合金涂层的失效过程中活性点的形成、 腐蚀产物的生成和累积过程与SECM 面扫描图谱中正负反馈效应相关, Cl-促进腐蚀发生,其浓度影响腐蚀类型。 COMSOL 多物理场模拟明确反馈效应与探针和基底的距离有关, Ni-P 涂层失效活性点大小在微米级。
英文摘要:
      Objective To develop corrosion electrochemistry method with spatial resolution. Methods Pure Ni and Ni-P alloy coatings on copper substrates were fabricated by electrodeposition. Scanning Electron Microscopy (SEM) and XRD were applied to check surface morphology and crystal structure of the alloy coatings. Scanning Electrochemical Microscopy (SECM) research was applied to monitor the failure behavior of typical Ni and Ni-P coating in different concentration of NaCl solution. Combined with COMSOL Multiphysics simulation, 2D and 3D models were built to quantify activity point size and feedback mechanism. Results The low concentration of chloride ion had the activation effect for pure Ni coating, while higher chloride ion concentration promoted corrosion occurrence. Ni-P alloy coating maintained good stability in a short immersion time in low concentration of chloride in the solution. After 6 hours soaking, there were typical active points and corrosion products for low P alloy coating, while after 24 hours soaking for high P alloy coating. The corrosion type for low P alloy coating in 0.1 mol/L NaCl solution was localized corrosion and uniform corrosion in 0.3 mol/L NaCl solution. The simulation results of approaching curve showed that the electrochemical process of corrosion products for FcMeOH was completely inert and fresh Cu surface was electrochemical activity. 3D simulation results showed that active points of Ni-P coating failure process were close to 10 micron. Conclusion The failure process including the formation of active points, the generation and accumulation of corrosion production of Ni and Ni-P coating in NaCl solution is dependent on the positive and/or negative feedback effect of SECM mapping. Chloride ion promotes occurrence of corrosion process, and its concentration has a strong effect on the corrosion type for Ni-P coating. COMSOL multiphysics simulation results indicate that the feedback effect is strongly dependent on the distance between the tip and the substrate, and the size of active point for Ni-P coating is micron level.
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