锌表面镨盐/酸刻蚀埃洛石复合涂层的自修复及耐蚀性研究

Self-healing and corrosion resistance of praseodymium salt/acid-etched halloysite composite coating on zinc surface

摘要

[目的] 传统防腐涂层一旦损坏，自身无法修复，为实现主动修复，设计了一种负载硝酸镨的埃洛石纳米管(HNTs)自修复涂层。[方法] 采用真空负压法将硝酸镨缓蚀剂负载到硫酸刻蚀改性埃洛石纳米管(S-HNTs)上，得到新型 S-HNTs-Pr 智能载体，然后均匀分散在水解的双-[3-(三乙氧基硅)丙基]-四硫化物(即 Si69 偶联剂)中，制成 S-HNTs-Pr 质量分数分别为 0%、1%、3%和 5%的涂层，用于锌的防腐蚀研究。[结果] 傅里叶变换红外光谱和 BET 测试证明缓蚀剂硝酸镨负载成功，且酸刻蚀没有破坏 HNTs 的管状结构。经机械刺激释放硝酸镨并在 3.5% NaCl 溶液中浸泡 72 h 后，从动电位极化曲线和电化学阻抗谱图可知 S-HNTs-Pr 质量分数为 3%的涂层的腐蚀电流密度比锌基体下降 3 个数量级，划伤后浸泡 72 h 内出现了自愈合现象。[结论] 在 Si69 涂层中添加适量 S-HNTs-Pr 能显著提高对锌的防护能力，且在受到机械划伤时可以实现自修复。

Abstract

[Objective] Traditional anticorrosion coatings cannot repair themselves once damaged. To achieve autonomous repair, a self-healing coating of halloysite nanotubes (HNTs) loaded with praseodymium nitrate was designed. [Method] Praseodymium nitrate as a corrosion inhibitor was loaded onto sulfuric acid-etched HNTs (S-HNTs) via a vacuum negative pressure method, preparing a novel S-HNTs-Pr intelligent carrier. The S-HNTs-Pr was then uniformly dispersed in fully hydrolyzed Si69 coupling agent (i.e. bis-[3-(triethoxysilyl)propyl]-tetrasulfide) to fabricate coatings with different mass fractions (0%, 1%, 3%, and 5%) of S-HNTs-Pr for corrosion protection of zinc. [Result] Fourier-transform infrared spectroscopy and BET tests confirmed the successful loading of praseodymium nitrate, and acid etching did not damage the tubular structure of HNTs. After release of praseodymium nitrate by mechanical stimulation and immersion in 3.5% NaCl solution for 72 hours, the results of potentiodynamic polarization measurements and electrochemical impedance spectroscopy showed that the coating with 3% S-HNTs-Pr exhibited a corrosion current density three orders of magnitude lower than that of the bare zinc substrate, and self-healing behavior was observed within 72 hours after scratching. [Conclusion] Adding an appropriate amount of S-HNTs-Pr to Si69 coating can significantly enhance the protective performance for zinc and enable self-repair upon mechanical scratching.

关键词

埃洛石 / 酸刻蚀 / 硝酸镨 / 硅烷偶联剂 / 自修复涂层 / 机械刺激响应 / 耐蚀性

Key words

halloysite / acid etching / praseodymium nitrate / silane coupling agent / self-healing coating / mechanical stimulus response / corrosion resistance

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基金资助

宁夏回族自治区自然科学基金项目(2025AAC030023)

北方民族大学研究生创新项目(CYX25152)

北方民族大学中央高校基本科研业务费专项资金资助(2025BG172)