仿生苍耳球冠织构的<strong>Ni-Co-Zn</strong>超疏水合金涂层及其抗覆冰性能

doi:10.11900/0412.1961.2023.00066

金属学报

2025, Vol. 61

Issue (5): 783-796 DOI: 10.11900/0412.1961.2023.00066

研究论文

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仿生苍耳球冠织构的Ni-Co-Zn超疏水合金涂层及其抗覆冰性能

周小卫(

), 郭云, 荆雪艳, 王宇鑫

江苏科技大学材料科学与工程学院镇江 212003

Biologically Inspired Xanthium-Like Spherical Texture in Superhydrophobic Ni-Co-Zn Coatings and Their Anti-Icing Performances

ZHOU Xiaowei(

), Guo Yun, JING Xueyan, WANG Yuxin

School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China

引用本文:

周小卫, 郭云, 荆雪艳, 王宇鑫. 仿生苍耳球冠织构的Ni-Co-Zn超疏水合金涂层及其抗覆冰性能[J]. 金属学报, 2025, 61(5): 783-796.
Xiaowei ZHOU, Yun Guo, Xueyan JING, Yuxin WANG. Biologically Inspired Xanthium-Like Spherical Texture in Superhydrophobic Ni-Co-Zn Coatings and Their Anti-Icing Performances[J]. Acta Metall Sin, 2025, 61(5): 783-796.

全文: PDF(4691 KB) HTML

摘要:

抗覆冰超疏水涂层被广泛应用于航天器羽翼和风电叶扇等领域。受传统工艺的复杂性及氟碳聚合物疏水涂料耐候性差及与基体结合力差等因素影响，严重制约了超疏水涂层的工业化应用。本工作提出在蜂窝多孔Ti上电沉积纳米晶Ni_0.12Co_{0.88 -}_x Zn _x (x = 0~0.36，%，质量分数)合金涂层，经200 ℃时效处理，无需进行二次含F低表面能涂层修饰即可得到超疏水表面。通过SEM、XRD和润湿性实验对其微观形貌及其超疏水性能进行表征。结果表明，在Zn²⁺浓度50 g/L (x = 0.24)和络合剂(柠檬酸钠(Na₃Cit))添加量5 g/L等优化工艺下，涂层晶粒尺寸约为300 nm，且沿多孔Ti的孔道钉扎生长，显著提高了涂层与多孔Ti基体的界面结合能力。润湿性测试结果表明：多孔Ti基体和涂层均为亲水性，但经自然时效14 d后涂层表现出疏水特性，其水滴接触角最大为126.3°，滚动角最低为17.5°。研究了人工时效温度、时间与润湿性之间的关联性，结果表明，经200 ℃人工时效处理后，涂层的超疏水性最佳，水滴接触角高达153.2°且滚动角低于7.8°，这主要归因于该涂层所表现出的自组装行为属于热响应机制，人工时效加速了这一自组装演变进程，大量的ZnO枝晶在纳米晶Ni或Co球壳上择优生长，生成多触角ZnO枝晶的球冠织构，从而具备超疏水结构特征。在-10 ℃冷冻台上进行抗覆冰特性测试，结果表明，经200 ℃人工时效后的涂层试样，其表面水滴完全结冰所需时间最长，为1418 s，比多孔Ti基体的抑冰时间延长近20倍，表现出优异的抗覆冰性能。

关键词 ：超疏水, Ni-Co-Zn涂层, 仿生苍耳织构, 抗覆冰特性

Abstract：

Superhydrophobic surfaces are promising anti-icing solutions for industrial applications such as spacecraft wings and wind turbine fans. However, the complexity of traditional processes, poor durability, and low interfacial adhesion between the substrate and fluorocarbon polymer films restrict their widespread use. This study validates a one-step electroplating method for Ni_0.12Co_{0.88 -}_x Zn_x (x = 0-0.36, %, mass fraction) coatings on honeycomb porous Ti surfaces, achieving super hydrophobicity without secondary modifications. SEM, XRD, and wettability tests are employed to characterize the surface features and hydrophobic properties. Optimized conditions (50 g/L Zn²⁺ (x = 0.24) and 5 g/L Na₃Cit concentration) resulted in a compact microstructural texture and refined crystal size (300 nm), enhancing the interfacial bonding strength. The as-deposited coating exhibited hydrophobic features, with a maximum water contact angle (WCA) of 126.3° and a sliding angle (SA) of 17.5° after 14 d of natural aging. The textural evolution from Zn nanocrystals to ZnO dendrites with a multi-antenna structure was attributed to this phenomenon. Artificial aging at 100, 200, and 300 ^oC achieved a superhydrophobic surface in less than 7 d. The sample aged at 200 ^oC displayed a WCA exceeding 153.2° and an SA below 7.8° due to out-migration of the active ZnO phase and self-assembly evolution, forming xanthium-like spherical structures with nanocrystalline Ni or Co shells and multi-tentacle ZnO dendrites. Comparatively, anti-icing performances were assessed at -10 ^oC, showing a peach blossom ice shape on all coating samples. The sample aged at 200 ^oC exhibited an ice-resistant time of over 1418 s, 20 times longer than that of the porous Ti substrate, indicating excellent anti-icing performances. In summary, electroplating Ni-Co-Zn coatings onto porous Ti is a practical solution that meets the evolving requirements for superhydrophobic films in spacecraft shells for anti-icing and warship surfaces for anti-salt spray corrosion.

Key words： superhydrophobic Ni-Co-Zn coating xanthium-like texture anti-icing performance

收稿日期: 2023-02-18

ZTFLH:

TB332

基金资助:国家自然科学基金项目(51605203);江苏省自然科学基金项目(BK20211344)

通讯作者: 周小卫，zhouxiaowei901@just.edu.cn，主要从事纳米晶镀层性能的研究

Corresponding author: ZHOU Xiaowei, associate professor, Tel: (0511)84401188, E-mail: zhouxiaowei901@just.edu.cn

作者简介: 周小卫，男，1983年生，副教授，博士

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图1 不同直流电压下蜂窝多孔Ti表面的SEM像及其孔径分布

图2 Zn2+浓度为50 g/L时(x = 0.24)不同络合剂(柠檬酸钠(Na3Cit))添加量下Ni-Co-Zn镀液的循环伏安(CV)曲线

图3 络合剂Na3Cit添加量为5 g/L时不同Zn2+浓度下电沉积Ni-Co-Zn涂层表面形貌的SEM像

图4 络合剂Na3Cit添加量为5 g/L时不同Zn2+浓度下电沉积Ni-Co-Zn涂层织构的XRD谱

图5 络合剂Na3Cit添加量为5 g/L时不同Zn2+浓度下Ni-Co-Zn涂层附着力测试的OM像

表1 络合剂Na3Cit添加量为5 g/L时不同Zn2+浓度条件下Ni-Co-Zn涂层试样经自然时效14 d后表面水滴接触角(WCA)和滚动角(SA)测试结果 (°)

图6 络合剂Na3Cit添加量为5 g/L时不同Zn2+浓度条件下经不同温度时效后Ni-Co-Zn涂层试样的WCA与暴露在空气中时间的关系

表2 络合剂Na3Cit添加量为5 g/L时不同Zn2+浓度条件下Ni-Co-Zn涂层试样经不同时效处理后的WCA测量结果 (°)

图7 Zn2+和络合剂 Na3Cit浓度分别为50和5 g/L条件下Ni-Co-Zn涂层试样经不同温度时效后在干燥空气中暴露14 d后表面形貌的SEM像

图8 Ti基体、Zn2+和络合剂Na3Cit浓度分别为50和5 g/L条件下阳极氧化蜂窝多孔Ti和Ni-Co-Zn涂层经不同温度时效后的试样表面在-10 ℃下延迟结冰特性的OM像

图9 超疏水表面苍耳球冠结构的形成机理示意图

图10 Zn2+和络合剂 Na3Cit浓度分别为50和5 g/L条件下Ni-Co-Zn涂层经自然时效后的多触角乳突状和人工时效后的苍耳球冠织构SEM像

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