邵蓉,黎敏,刘永壮,曹建平,李学涛.锌铝镁镀层不同表面处理体系成分分析及耐蚀性研究[J].表面技术,2023,52(9):253-264.
SHAO Rong,LI Min,LIU Yong-zhuang,CAO Jian-ping,LI Xue-tao.Composition Analysis and Corrosion Resistance of Different Surface Treatment Systems for Zn-Al-Mg Coating[J].Surface Technology,2023,52(9):253-264
锌铝镁镀层不同表面处理体系成分分析及耐蚀性研究
Composition Analysis and Corrosion Resistance of Different Surface Treatment Systems for Zn-Al-Mg Coating
投稿时间:2022-07-19  修订日期:2022-12-12
DOI:10.16490/j.cnki.issn.1001-3660.2023.09.022
中文关键词:  无铬钝化  三价铬钝化  锌铝镁  耐蚀性
英文关键词:Cr-free passivation  Cr3+ passivation  Zn-Al-Mg coating  corrosion resistance
基金项目:
作者单位
邵蓉 首钢集团有限公司技术研究院,北京 100041;绿色可循环钢铁流程北京市重点实验室,北京 100043 
黎敏 首钢集团有限公司技术研究院,北京 100041;绿色可循环钢铁流程北京市重点实验室,北京 100043 
刘永壮 首钢集团有限公司技术研究院,北京 100041;绿色可循环钢铁流程北京市重点实验室,北京 100043 
曹建平 首钢集团有限公司技术研究院,北京 100041;绿色可循环钢铁流程北京市重点实验室,北京 100043 
李学涛 首钢集团有限公司技术研究院,北京 100041;绿色可循环钢铁流程北京市重点实验室,北京 100043 
AuthorInstitution
SHAO Rong Research Institute of Technology of Shougang Group Co., Ltd., Beijing 100041, China;Beijing Key Laboratory of Green Recyclable Process for Iron & Steel Production Technology, Beijing 100043, China 
LI Min Research Institute of Technology of Shougang Group Co., Ltd., Beijing 100041, China;Beijing Key Laboratory of Green Recyclable Process for Iron & Steel Production Technology, Beijing 100043, China 
LIU Yong-zhuang Research Institute of Technology of Shougang Group Co., Ltd., Beijing 100041, China;Beijing Key Laboratory of Green Recyclable Process for Iron & Steel Production Technology, Beijing 100043, China 
CAO Jian-ping Research Institute of Technology of Shougang Group Co., Ltd., Beijing 100041, China;Beijing Key Laboratory of Green Recyclable Process for Iron & Steel Production Technology, Beijing 100043, China 
LI Xue-tao Research Institute of Technology of Shougang Group Co., Ltd., Beijing 100041, China;Beijing Key Laboratory of Green Recyclable Process for Iron & Steel Production Technology, Beijing 100043, China 
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中文摘要:
      目的 分析锌铝镁镀层不同表面处理体系的成分,考察表面处理膜层的耐蚀性,明晰不同表面处理方式的防腐机制。方法 通过白光干涉仪和扫描电镜(SEM)对3种表面处理方式下锌铝镁钢板不同表面微观形貌进行观察,通过辉光光谱(GDS)、X射线衍射(XRD)、X射线光电子能谱(XPS)以及傅里叶变换红外反射吸收光谱(FTIR)对表面处理膜膜层厚度及成分结构等进行表征,并结合家电板实际使用条件,考察不同钝化膜层的耐蚀性。结果 涂油样品表面存在约10 nm厚、以烃类基础油和钙盐缓蚀剂等成分为主的油膜。三价铬钝化膜为厚度约50 nm,以Cr2O3、Cr(OH)3及ZnO为主的致密不溶性氧化物膜层,无铬钝化膜为厚度约3 μm、以氨基硅烷-树脂为主成膜物质的有机钝化膜。XPS及FTIR结果表明,硅烷-树脂在钢板表面发生了交联反应,形成了三维立体网状结构,同时钝化膜与镀层Zn之间形成了强化学键作用。电化学试验结果表明,三价铬钝化以及无铬钝化样品具有更小的自腐蚀电流密度及更大的电化学阻抗。在中性盐雾环境中,三价铬钝化膜具有更好的平面耐蚀性。无铬钝化膜具有更优异的划叉耐蚀性。结论 三价铬钝化处理以及无铬钝化处理锌铝镁板的腐蚀倾向均小于涂油处理锌铝镁板的,相关研究可为锌铝镁镀层材料在家电板市场的推广应用提供理论支撑。
英文摘要:
      The purpose of this study is to analyze the composition of different surface treatment systems of Zn-Al-Mg coatings, investigate the corrosion resistance of surface treatment films, clarify the anti-corrosion mechanisms of different surface treatment methods, and explore the essential reasons for the difference in corrosion resistance. In this study, the surface morphologies of Zn-Al-Mg steel plates under different surface treatments were observed by white light interferometer and scanning electron microscopy (SEM). The thicknesses, element compositions and structures of surface treatment films were characterized by glow spectrometer (GDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared reflection and absorption spectrometer (FTIR). At the same time, the corrosion resistance of the three samples was analyzed by neutral salt spray test, Tafel test and electrochemical impedance spectroscopy (EIS). The results indicate that the anti-rust oil film was only about 10 nm thick and mainly consisted of hydrocarbon base oil and corrosion inhibitor. The anti-corrosion mechanism mainly relied on the physical adsorption of the polar head of the anti-rust agent on the surface of the coating to form a single molecule or multi-molecule adsorption layer. The adsorption layer could prevent the contact between the coating surface and oxygen and water. Cr3+ passivation film was mainly composed of chromium phosphate and silica-containing organic additives (silane, etc.) with a thickness of about 50 nm. The passivation mechanism was through the dissolution of Zn on the surface to form Zn2+, and then the Cr3+ in the solution reacted with Zn2+ and OH–. A dense insoluble oxide film layer mainly composed of Cr2O3, Cr(OH)3 and ZnO was precipitated on the surface of the coating. A small amount of organic silicon additives in the passivation film formed a physical barrier to the corrosion factors, and then improved the corrosion resistance. Cr-free passivation film mainly adopted amino silane and water-based resin as film forming materials, which had a thickness of about 3 μm. XPS and FTIR results indicated that Si-O-Si, Si-O, Si-C, Si-O-Zn, C-O and other forms existed in the passivation film, which proved that silane and resin cross-link on the surface of the steel plate formed a three-dimensional network structure. It also formed strong chemical bonds between silane and Zn-Mg-Al coating. The electrochemical tests showed that compared with the oiling treatment sample, the Cr3+ passivation sample and Cr-free passivation sample had smaller self-corrosion current densities and larger electrochemical impedance. In the neutral salt spray environment, compared with the chromium-free passivation film, the Cr3+ passivation film layer was denser, so it showed better planar corrosion resistance. The white rust area was less than 5% after 360 h. When the passivation film was destroyed, the inorganic salt corrosion inhibitor in the Cr-free passivation film re-dissolved and migrated to the damaged film layer, and reacted with the substrate to form a new oxide film. Thus, Cr-free passivation film showed better self-healing ability and more excellent scratch corrosion resistance. After 360 h, the white rust in the crossing part no longer increased. These results proved that the corrosion tendency of Zn-Al-Mg coated plates with Cr3+ passivation film or Cr-free passivation film was much smaller than that with anti-rust oil film. This work provides a theoretical support for the application and popularization of Zn-Al-Mg coating materials in the home appliance board market.
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