添加纳米CeO<sub>2</sub>对聚氨酯涂层防腐性能的影响

doi:10.11902/1005.4537.2016.147

中国腐蚀与防护学报

2017, Vol. 37

Issue (5): 411-420 DOI: 10.11902/1005.4537.2016.147

研究报告

本期目录 | 过刊浏览

添加纳米CeO₂对聚氨酯涂层防腐性能的影响

蔡光义¹,王浩伟²,赵苇杭¹,董泽华¹(

)

1 华中科技大学化学与化工学院材料服役失效湖北省重点实验室武汉 430074
2 中航工业特种飞行器研究所荆门 448000

Effect of Nano-CeO₂ on Anticorrosion Performance for Polyurethane Coating

Guangyi CAI¹,Haowei WANG²,Weihang ZHAO¹,Zehua DONG¹(

)

1 Hubei Key Laboratory of Materials Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
2 AVIC Special Vehicle Research Institute, Jingmen 448000, China

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摘要:

采用盐雾和盐水浸泡加速实验,结合ATR-FTIR,SEM,AFM表面分析技术及EIS电化学分析技术,考察纳米CeO₂作为涂层颜料对聚氨酯涂层防腐性能的影响。结果表明,添加纳米CeO₂能改善涂层的防腐性能,延缓聚氨酯涂层的阻抗衰减进程,但同时会削弱涂层在金属基体上的附着力。当添加量较低时 (≤0.5%,质量分数),由于H₂O和侵蚀性离子渗入聚氨酯层,纳米CeO₂水解流失,导致涂层阻抗谱随时间降低较快;当添加量达到1.0%时,涂层阻抗在较长时间内保持较高值,这可能是由于纳米CeO₂在涂层微孔中发生水解膨胀,压缩了孔隙通道,同时Ce (III,IV) 迁移到铝合金/涂层界面,抑制了腐蚀活性位点,因而减缓了阻抗的衰减进程。然而,在盐雾实验后期,CeO₂进一步水解会导致Ce⁴⁺的溶解流失,造成微孔隙的再次疏通和涂层阻抗的快速下降。过量添加 (>1.0%) 还会削弱涂层在铝合金基体上的附着力。长期浸泡实验结果表明：添加1.0%CeO₂可基本实现Ce⁴⁺溶解和流失的平衡,增强聚氨酯涂层的防腐性能。

关键词 ：涂层, 纳米CeO₂, EIS, 防腐性能, AFM

Abstract：

Salt spray test and immersion test for two accelerated weathering tests were carried out to research the effects of nano-CeO₂ as a pigment to the corrosion resistance of polyurethane coating. According to EIS, ATR-FTIR, SEM and AFM characterized and analyzed the performance and micromorphology change of coating. The results show that as a pigment nano-CeO₂ could decrease the rate of resistance reduction of polyurethane coating. When the concentration of adding nano-CeO₂ was less than 0.5%(mass fraction), the EIS impedance spectrum dropped rapidly with acceleration time elapsed due to the electrolyte and H₂O penetration into coating quickly and nano-CeO₂ hydrolysis. While the corrosion resistance get markedly changed and maintained high impedance for a long time of the coating with additive 1.0% nano-CeO₂. This phenomenon may be due to CeO₂ hydrolysis in coating micro crack, reduced the pore channel, and Ce(III, IV) migrated to the Al alloy/coating interface, inhibiting the corrosion of active site, thus decreasing the attenuation process of impedance. At the later stage of salt spray test, CeO₂ further hydrolysis leaded to Ce ions dissolution erosion, which caused micro cracks expansion again and coating impedance reducing quickly. When the addition of nano-CeO₂excessed 1.0% would weaken the adhesion of coating on aluminum alloy matrix. Long time immersion test showed that 1.0% of nano-CeO₂ could achieve balance of Ce ions dissolution and migration, and increased the anticorrosion performance of PU coating.

Key words： coating nano-CeO₂ EIS anticorrosion performance AFM

收稿日期: 2016-09-08

基金资助:国家自然科学基金 (51371087)

作者简介: 蔡光义,男,1989年生,博士生

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引用本文:

蔡光义,王浩伟,赵苇杭,董泽华. 添加纳米CeO₂对聚氨酯涂层防腐性能的影响[J]. 中国腐蚀与防护学报, 2017, 37(5): 411-420.
Guangyi CAI, Haowei WANG, Weihang ZHAO, Zehua DONG. Effect of Nano-CeO₂ on Anticorrosion Performance for Polyurethane Coating. Journal of Chinese Society for Corrosion and protection, 2017, 37(5): 411-420.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2016.147 或 https://www.jcscp.org/CN/Y2017/V37/I5/411

图1 不同涂层在3.5%NaCl溶液中的Nyquist图

图2 涂层电阻和电容随纳米CeO2添加量的变化曲线及涂层等效电路

图3 不同涂层在3.5%NaCl溶液中浸泡不同时间的Nyquist图

图4 涂层不同失效阶段等效电路图

图5 不同涂层在3.5%NaCl溶液中浸泡时|Z0.01 Hz|随时间的变化曲线

图6 不同涂层在盐雾实验条件下不同时间的Nyquist图

图7 不同涂层的|Z0.01 Hz|随盐雾实验时间的变化曲线

图8 不同含量纳米CeO2涂层红外光谱图

图9 CeO2在涂层中的缓蚀机理示意图

图10 含不同添加量的纳米CeO2聚氨酯涂层的AFM相位图

图11 未处理涂层以及盐雾实验、全浸泡实验后涂层的相位粗糙度和高度粗糙度分布图

图12 纳米CeO2添加量不同的聚氨酯涂层划叉后盐雾实验120 h的形貌图

图13 未添加和添加1.0%纳米CeO2的聚氨酯涂层在浸泡158 h前后的SEM像

图14 含1.0%纳米CeO2的聚氨酯涂层在浸泡1和158 h后的EDS分析结果

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