李庆余,范海林,陈家荣,陈肇开,王红强,黄有国.硫脲对 304 不锈钢镀镍层抗腐蚀性能的影响[J].表面技术,2015,44(7):16-22.
LI Qing-yu,FAN Hai-lin,CHEN Jia-rong,CHEN Zhao-kai,WANG Hong-qiang,HUANG You-guo.Effect of Thiourea on Corrosion Resistance of Ni Coatings on the Surface of 304 Stainless Steel[J].Surface Technology,2015,44(7):16-22
硫脲对 304 不锈钢镀镍层抗腐蚀性能的影响
Effect of Thiourea on Corrosion Resistance of Ni Coatings on the Surface of 304 Stainless Steel
投稿时间:2015-02-06  修订日期:2015-07-20
DOI:10.16490/j.cnki.issn.1001-3660.2015.07.004
中文关键词:  304 不锈钢  电镀镍  硫脲  晶粒尺寸  耐腐蚀性能  腐蚀机理
英文关键词:304 stainless steel  Ni plating  thiourea  grain size  corrosion resistance  corrosion mechanism
基金项目:国家自然科学基金(21473042,51474077,51474100,51364004);广西自然科学基金重点项目(2013GXNSFDA019027);广西自然科学基金(2012GXNSFAA053214,2013GXNSFAA019032)
作者单位
李庆余 1. 百色学院 化学与生命科学系, 广西 百色 533000; 2. 广西师范大学 化学与药学学院,广西 桂林 541004 
范海林 广西师范大学 化学与药学学院,广西 桂林 541004 
陈家荣 广西师范大学 化学与药学学院,广西 桂林 541004 
陈肇开 广西师范大学 化学与药学学院,广西 桂林 541004 
王红强 1. 广西师范大学 化学与药学学院,广西 桂林 541004; 2. 黄冈师范学院 化工学院, 湖北 黄冈 438000 
黄有国 广西师范大学 化学与药学学院,广西 桂林 541004 
AuthorInstitution
LI Qing-yu 1. Department of Chemistry and Life Science, Baise University, Baise 533000, China;2. School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China 
FAN Hai-lin School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China 
CHEN Jia-rong School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China 
CHEN Zhao-kai School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China 
WANG Hong-qiang 1. School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China;2. College of Chemical Engineering, Huanggang Normal University, Huanggang 438000, China 
HUANG You-guo School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China 
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中文摘要:
      目的 研究硫脲对电镀镍层形貌、晶型、晶粒尺寸以及抗腐蚀性能的影响。 方法 在添加和不添加硫脲两种条件下,对 304 不锈钢进行电镀镍。 通过 XRD 和 SEM 对比镀层的晶相结构、晶粒尺寸和微观形貌,通过 Tafel 曲线和 EIS 电化学阻抗谱对比分析样品的抗腐蚀性能。 结果 添加硫脲前后,镍镀层的择优生长方向从<200>晶面转变为<111>晶面,晶粒平均尺寸从 60. 2 nm 减小为 20. 7 nm。 由于硫脲吸附在金属表面,阻滞了溶液中金属离子放电,从而提高了阴极极化作用;同时,硫脲分子吸附在晶体生长的活性点上,有效抑制了晶体生长;因此,镍晶粒得到细化。 关于腐蚀性能,镀镍 304 不锈钢的耐腐蚀性能最好,其次是 304 不锈钢基体,最差的是含硫镀镍 304 不锈钢。 结论 硫脲能够改变镍镀层晶体的择优取向,并且细化晶粒。 硫脲影响电镀镍层抗腐蚀性能的机理是:阴极吸附的硫脲通过电化学还原产生 H2S,进一步与 Ni2+反应生成 NiS,NiS 再与富集的 Ni 反应生成 Ni3S2。 随着电镀的进行,Ni3S2 被更多地沉积在镍镀层的表面,降低了镍层表面钝化膜的致密性;而且,Ni3S2 与镍层存在电势差,故易发生原电池腐蚀。 此外,晶粒细化导致晶界和晶面的缺陷增加,也使得腐蚀加速。 故镀液中加入硫脲,镀层的耐腐蚀性能大大降低。
英文摘要:
      Objective To investigate the effect of thiourea on crystalline structure,grain sizes,morphology and corrosion resistance of Ni coatings. Methods Ni coatings were prepared on the surface of 304 stainless steel with or without thiourea. The crystalline structure,grain sizes and microscopic morphology of the coatings were characterized by XRD and SEM. The corrosion resistance of the samples was analyzed by Tafel and EIS. Results After adding thiourea, the preferred orientation of Ni coatings was changed from the <200> crystal plane to the <111> crystal planes and the average grain size of Ni coatings was reduced form 60. 2 nm to 20. 7 nm. Due to the adsorption of thiourea on the metal surface,the discharge of metal ions was blocked and the cathodic polarization was enhanced. Meanwhile,thiourea molecules were adsorbed on the active sites of the crystal growth,which effectively inhibited the crystal growth. Thus, the grain size of Ni coatings was refined. For corrosion resistance,304 stainless steel with Ni coatings was the best, followed by 304 stainless steel substrate; 304 stainless steel with nickel coatings containing Ni3 S2 was the worst. Conclusion The preferred orientation of Ni coatings was changed and the average grain size of Ni coatings was reduced by thiourea. The mechanism of thiourea influencing anti-corrosion resistance of Ni coatings was proposed. Thiourea which was adsorbed on the cathode was restored to H2 S by electrochemical reduction,then NiS was generated by the reaction of H2 S and Ni2+. Ni3 S2 was further generated by the reaction of the enrichment of Ni and NiS. With the deposition of Ni,Ni3 S2 was deposited on the surface of Ni coatings and reduced compactness of Ni passivation film. Meanwhile,due to the potential difference between Ni and Ni3 S2 , corrosion of the original cells may occur. In addition, grain refinement leaded to increased defects of grain boundaries and crystal plane, which would accelerate corrosion. Therefore,the corrosion resistance of the coatings with adding thiourea was greatly reduced.
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