| 引用本文: | 石西尧,朱志平,曹洁,汤甜,武梦婷.响应面分析法在绿色快速磷化工艺研发中的应用*[J].中国表面工程,2023,36(3):223~234 |
| SHI Xiyao,ZHU Zhiping,CAO Jie,TANG Tian,WU Mengting.Application of Response Surface Analysis in the Research on the Green and Rapid Phosphating Process[J].China Surface Engineering,2023,36(3):223~234 |
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| 摘要: |
| 长期处于户外的输电杆塔容易遭受锈蚀而受损，传统的涂料涂覆处理无法起到同时除锈和防腐的作用，因此亟须探索一种适合输电杆塔的绿色磷化处理工艺。基于电化学与响应面分析法，以磷酸与氧化锌为基础磷化液，研究植酸、复合钝化剂 BM1、硝酸锰三种促进剂的浓度对锌系磷化膜成膜质量的影响，以硫酸铜点滴时间评判其耐蚀性。采用扫描电子显微镜观察添加不同促进剂的磷化液所形成磷化膜的表面形貌。通过响应面分析法对磷化液的成膜耐腐蚀效果进行优化，得到硫酸铜点滴时间的二次响应方程。各因素影响次序为硝酸锌＞复合钝化剂(BM1)＞植酸＞硝酸锰，通过优化获得硫酸铜点滴时间为 101 s 的磷化液配方，即氧化锌 15 g / L、磷酸 100 g / L、复合钝化剂 BM1 1.7 g / L、植酸 11.7 mL / L、硝酸锌 52.4 g / L、硝酸锰 5.9 g / L、OP-10 乳化剂适量。通过响应面优化参数得到的磷化液配方在具有除锈功能的同时能有效提高 Q235 低碳钢的耐腐蚀性能，可为磷化液新配方的性能预测和浓度优化提供方法与理论指导。 |
| 关键词: 绿色磷化 耐蚀性 锰系磷化膜 磷化工艺 响应曲面法 |
| DOI：10.11933/j.issn.1007?9289.20220222003 |
| 分类号:TG174 |
| 基金项目:湖南省科技计划重点资助项目(2013GK2016) |
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| Application of Response Surface Analysis in the Research on the Green and Rapid Phosphating Process |
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SHI Xiyao, ZHU Zhiping, CAO Jie, TANG Tian, WU Mengting
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School of Chemistry and Chemical Engineering, Changsha University of Technology, Changsha 410114 , China
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| Abstract: |
| Although transmission towers have been in use outdoors for a long time, they are easily damaged by corrosion, especially in areas with heavy industrial pollution. Additionally, traditional coating treatments cannot simultaneously remove rust and prevent corrosion. However, the use of a phosphating film can inhibit the formation of microbatteries on the steel surface, improve the corrosion resistance of steel, extend the service life, and significantly improve the adhesion between the substrate and coating. Nonetheless, most traditional phosphating methods employ high- or medium-temperature phosphating, which consumes a lot of fossil energy and promotes environmental pollution. To ensure safety during power transmission and distribution, it is crucial to develop a fast and green phosphating process suitable for the high-altitude operations on transmission towers. Based on electrochemical and response surface analyses, a phosphating coating was prepared on Q235 low-carbon steel using a mixture of phosphoric acid and zinc oxide as the basic phosphating solution. The effect of the concentration of phytic acid, composite passivation agent BM1, and manganese nitrate on the quality of zinc-based phosphating films was then studied, and the corrosion resistance of the coating was evaluated based on the time of copper sulfate test. The fixed phosphating process conditions were as follows: the pH value of the phosphating solution was 2.3-3.0, phosphating temperature was 25 ℃, and phosphating time was 40 min. The corrosion resistance of the phosphating film was analyzed using an electrochemical polarization curve and electrochemical impedance spectroscopy, and the results showed that the phosphating film had a better corrosion resistance when an accelerant was added to the phosphating solution. Moreover, the current density was less than half of that of the pure phosphating solution, and the maximum coating resistance was 2 561 ?·cm2 , which was approximately 4 times higher than that of the pure phosphating solution. With an increase in the accelerator concentration, the corrosion resistance of the phosphating film first increased before decreasing. The surface morphology of the phosphating film formed by phosphating solutions with diffrenet accelerant was observed using scanning electron microscopy (SEM), and the results showded that the basic phosphating solution contained many pores and had a large phosphating grain size whose distribution was uneven. After adding manganese nitrate, the phosphate grains on the surface of the phosphating film became arranged more densely and uniformly, covering all surfaces. Response surface analysis was used to optimize film-forming and improve the corrosion resistance of the phosphating solution, and a quadratic response equation for the time of copper sulfate test was obtained. The order of the effect was follows: zinc nitrate ＞ composite passivator (BM1) ＞ phytic acid ＞ manganese nitrate. Through optimization, the phosphating solution formula under a time of copper sulfate test of 101s was obtained, that is, zinc oxide = 15 g / L, phosphoric acid = 100 g / L, composite passivator BM1 = 1.7 g / L, phytic acid = 11.7 mL / L, zinc nitrate = 52.4 g / L, manganese nitrate = 5.9 g / L, and an appropriate amount of OP-10 emulsifier. Therefore, the proposed phosphating solution obtained through response surface optimization employs low-temperature phosphating, does not contain the hexavalent chromium that is harmful to the environment, and uses an efficient green accelerator to accelerate phosphating,which can support rust remove while effectively improving the corrosion resistance of Q235 low-carbon steel; thereby providing technical support for the green and rapid of transmission towers. |
| Key words: green phosphating corrosion resistance manganese phosphating film phosphating process response surface method |
