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

doi:10.11900/0412.1961.2023.00066

Acta Metall Sin

2025, Vol. 61

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

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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

Cite this article:

ZHOU Xiaowei, Guo Yun, JING Xueyan, WANG Yuxin. Biologically Inspired Xanthium-Like Spherical Texture in Superhydrophobic Ni-Co-Zn Coatings and Their Anti-Icing Performances. Acta Metall Sin, 2025, 61(5): 783-796.

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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

Received: 18 February 2023

ZTFLH:

TB332

Fund: National Natural Science Foundation of China(51605203);Natural Science Foundation of Jiangsu Province(BK20211344)

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

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	ZHOU Xiaowei
	Guo Yun
	JING Xueyan
	WANG Yuxin

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https://www.ams.org.cn/EN/10.11900/0412.1961.2023.00066 OR https://www.ams.org.cn/EN/Y2025/V61/I5/783

Fig.1 SEM images (a, c, e) and correspongding pore size distributions (b, d, f) of the honeycomb-like porous surfaces of Ti matrix during anodizing at direct current voltages of 140 V (a, b), 160 V (c, d), and 180 V (e, f)

Fig.2 Cyclic voltammetry (CV) curves for Ni-Co-Zn bath under Na₃Cit additions of 0 g/L (a), 3 g/L (b), 5 g/L (c), and 10 g/L (d) at Zn²⁺ concentration of 50 g/L (j—current density, E—potential, SCE—saturated calomel electrode)

Fig.3 SEM images showing surface features of Ni-Co-Zn coating with Zn²⁺concentrations of 0 g/L (a), 25 g/L (b), 50 g/L (c), and 100 g/L (d) under Na₃Cit addition of 5 g/L (Insets in Figs.3b and c show the locally enlarged images)

Fig.4 XRD spectra showing textural growth of Ni-Co-Zn coating with Zn²⁺ concentrations of 0 g/L (a), 25 g/L (b), 50 g/L (c), and 100 g/L (d) under Na₃Cit addition of 5 g/L (Insets in Figs.4c and d show the locally enlarged spectra)

Fig.5 OM images showing the scratched tracks for Ni-Co-Zn coating with Zn²⁺ concentrations of 0 g/L (a), 25 g/L (b), 50 g/L (c), and 100 g/L (d) under Na₃Cit addition of 5 g/L

Table 1 Results of water contact angle (WCA) and sliding angle (SA) for Ni-Co-Zn coating after 14 d of natural aging with different Zn²⁺ concentrations in bath under Na₃Cit addition of 5 g/L

Fig.6 Relationships between WCA and exposing time of Ni-Co-Zn coating aged at different tempera-tures within Zn²⁺concentrations of 25 g/L (a), 50 g/L (b), and 100 g/L (c) under Na₃Cit addition of 5 g/L

Table 2 Effects of aging temperature on WCA for Ni-Co-Zn coating within different Zn²⁺ concentrations in bath under Na₃Cit addition of 5 g/L

Fig.7 SEM images showing surface features of Ni-Co-Zn coatings aging at room temperature (25 ^oC) (a), 100 ^oC (b), 200 ^oC (c), and 300 ^oC (d) and then exposing to air for 14 d under Zn²⁺ concentration of 50 g/L and Na₃Cit addition of 5 g/L (Insets show the locally enlarged images)

Fig.8 OM images of anti-icing (icing) performance tests at -10 ^oC on surfaces of Ti substrate (a); OM images of anodized porous template (b) and Ni-Co-Zn coatings aged at 25 ^oC (c), 100 ^oC (d), 200 ^oC (e), and 300 ^oC (f) under Zn²⁺ concentration of 50 g/L and Na₃Cit addition of 5 g/L

Fig.9 Schematic of xanthium-like spherical textures for superhydrophobic Ni-Co-Zn coatings

Fig.10 Low (a, b) and high (a1, b1) magnified SEM images showing the surface features of Ni-Co-Zn coatings with multi-antenna structure after natural aging (a, a1) and xanthium-like spherical texture by ZnO whiskers after artificial aging at 200 ^oC (b, b1) under Zn²⁺ concentration of 50 g/L and Na₃Cit addition of 5 g/L (Inset in Fig.12b show the EDS result of square area)

1	Wang Y X, Guan L L, He Z, et al. Preparation and characterisation of AAO/Ni/Ni superhydrophobic coatings on aluminium alloys [J]. Surf. Eng., 2021, 37: 1246
2	Lian F, Zang L P, Xiang Q K, et al. Tribological performance of super hydrophobic titanium alloy surface in artificial seawater [J]. Acta Metall. Sin., 2016, 52: 592
	连峰, 臧路苹, 项秋宽等. 超疏水钛合金表面在人工海水中的摩擦性能 [J]. 金属学报, 2016, 52: 592
3	Kang Z X, Guo M J. Fabrication of superhydrophobic Ti surface by thermal oxidation and its anticorrosion property [J]. Acta Metall. Sin., 2013, 49: 629 doi: 10.3724/SP.J.1037.2013.00027
	康志新, 郭明杰. 热氧化法制备超疏水Ti表面及其耐腐蚀性 [J]. 金属学报, 2013, 49: 629 doi: 10.3724/SP.J.1037.2013.00027
4	Shibuichi S, Onda T, Satoh N, et al. Super water-repellent surfaces resulting from fractal structure [J]. J. Phys. Chem., 1996, 100: 19512
5	Zhou X, Yu S R, Zang J, et al. Colorful nanostructured TiO₂ film with superhydrophobic-superhydrophilic switchable wettability and anti-fouling property [J]. J. Alloys Compd., 2019, 798: 257
6	Jiang L, Wang R, Yang B, et al. Binary cooperative complementary nanoscale interfacial materials [J]. Pure Appl. Chem., 2000, 72: 73
7	Xi W J, Qiao Z M, Zhu C L, et al. The preparation of lotus-like super-hydrophobic copper surfaces by electroplating [J]. Appl. Surf. Sci., 2009, 255: 4836
8	Wang G W, Song D, Qiao Y X, et al. Developing super-hydrophobic and corrosion-resistant coating on magnesium-lithium alloy via one-step hydrothermal processing [J]. J. Magnes. Alloy., 2023, 11: 1422
9	Shang W, Wu F, Jiang S Q, et al. Effect of hydrophobicity on the corrosion resistance of microarc oxidation/self-assembly/nickel composite coatings on magnesium alloys [J]. J. Mol. Liq., 2021, 330: 115606
10	Hashjin R R, Ranjbar Z, Yari H, et al. Tuning up sol-gel process to achieve highly durable superhydrophobic coating [J]. Surf. Interfaces, 2022, 33: 102282
11	Liu Q W, Liu G D, Li Z H, et al. Preparation and properties of superhydrophobic surface of magnesium alloy by nanosecond laser [J]. Laser Optoelectron. Prog., 2022, 59: 224
	刘祁文, 刘国东, 李子航等. 纳秒激光制备镁合金超疏水表面及其性能研究 [J]. 激光与光电子学进展, 2022, 59: 224
12	Liu Y H, Wang Z K. Superhydrophobic porous networks for enhanced droplet shedding [J]. Sci. Rep., 2016, 6: 33817 doi: 10.1038/srep33817 pmid: 27644452
13	She Z X, Li Q, Wang Z W, et al. Highly anticorrosion, self-cleaning superhydrophobic Ni-Co surface fabricated on AZ91D magnesium alloy [J]. Surf. Coat. Technol., 2014, 251: 7
14	Peng Y J, Li P C, Li H, et al. Theoretical and experimental study of spontaneous adsorption-induced superhydrophobic Cu coating with hierarchical structures and its anti-scaling property [J]. Surf. Coat. Technol., 2022, 441: 128557
15	Wang L, Teng C, Liu J, et al. Robust anti-icing performance of silicon wafer with hollow micro-/nano-structured ZnO [J]. J. Ind. Eng. Chem., 2018, 62: 46
16	Xue C R, Dong L H, Liu T, et al. Preparation and anticorrosion performance of superhydrophobic TiO₂ nanotube arrays on pure Ti [J]. Corros. Sci. Prot. Technol., 2012, 24: 37
	薛超瑞, 董丽华, 刘通等. TiO₂纳米阵列超疏水膜的制备及耐腐蚀性能 [J]. 腐蚀科学与防护技术, 2012, 24: 37
17	Sökmen M, Tatlıdil İ, Breen C, et al. A new nano-TiO₂immobilized biodegradable polymer with self-cleaning properties [J]. J. Hazard. Mater., 2011, 187: 199
18	Zheng J X, Liu R, Liu D D, et al. Slippery liquid infused porous surfaces with anti-icing performance fabricated by direct laser interference lithography [J]. Prog. Org. Coat., 2023, 175: 107308
19	Tian Y, Xu Y C, Zhu Z T, et al. Hierarchical micro/nano/porous structure PVDF/hydrophobic GO photothermal membrane with highly efficient anti-icing/de-icing performance [J]. Colloids Surf., 2022, 651A: 129586
20	Guo P, Zheng Y M, Wen M X, et al. Icephobic/anti-icing properties of micro/nanostructured surfaces [J]. Adv. Mater., 2012, 24: 2642
21	Bhat R S, Shet V B. Development and characterization of Zn-Ni, Zn-Co and Zn-Ni-Co coatings [J]. Surf. Eng., 2020, 36: 429 doi: 10.1080/02670844.2019.1680037
22	Kapusta-Kołodziej J, Syrek K, Pawlik A, et al. Effects of anodizing potential and temperature on the growth of anodic TiO₂ and its photoelectrochemical properties [J]. Appl. Surf. Sci., 2017, 396: 1119
23	Zhou X W, Lu Z, Jing X Y. Pinning growth of TiN films toward porous Ti matrix [J]. J. Mater. Sci, 2022, 57: 18949
24	Zhou X W, Wu F J, Ouyang C. Electroless Ni-P alloys on nanoporous ATO surface of Ti substrate [J]. J. Mater. Sci, 2018, 53: 2812
25	Abou-Krisha M M, Rageh H M, Matter E A. Electrochemical studies on the electrodeposited Zn-Ni-Co ternary alloy in different media [J]. Surf. Coat. Technol., 2008, 202: 3739
26	Kazimierczak H, Ozga P, Socha R P. Investigation of electrochemical co-deposition of zinc and molybdenum from citrate solutions [J]. Electrochim. Acta, 2013, 104: 378
27	Eliaz N, Venkatakrishna K, Hegde A C. Electroplating and characterization of Zn-Ni, Zn-Co and Zn-Ni-Co alloys [J]. Surf. Coat. Technol., 2010, 205: 1969
28	Dikici T, Culha O, Toparli M. Study of the mechanical and structural properties of Zn-Ni-Co ternary alloy electroplating [J]. J. Coat. Technol. Res., 2010, 7: 787
29	Abou-Krisha M M. Influence of Ni²⁺ concentration and deposition potential on the characterization of thin electrodeposited Zn-Ni-Co coatings [J]. Mater. Chem. Phys., 2011, 125: 621
30	Jiang J W, Shen Y Z, Wang Z, et al. Anti/de-icing performance of the one-step electrodeposited superhydrophobic surfaces: Role of surface polarity regulated by hydrocarbon radical length [J]. Chem. Eng. J., 2022, 431: 133276
31	Yan Y X, Wang J H, Gao J, et al. TiO₂-based slippery liquid-infused porous surfaces with excellent ice-phobic performance [J]. Colloids Surf., 2022, 654A: 129994
32	Shen Y Z, Wu Y, Tao J, et al. Spraying fabrication of durable and transparent coatings for anti-icing application: Dynamic water repellency, icing delay, and ice adhesion [J]. ACS Appl. Mater. Interfaces, 2019, 11: 3590
33	Khorasani M T, Mirzadeh H, Kermani Z. Wettability of porous polydimethylsiloxane surface: Morphology study [J]. Appl. Surf. Sci., 2005, 242: 339
34	Fu Q T, Wu X H, Kumar D, et al. Development of sol-gel icephobic coatings: Effect of surface roughness and surface energy [J]. ACS Appl. Mater. Interfaces, 2014, 6: 20685
35	Wei F F, Xiang T F, Liu J, et al. Fabrication of superhydrophobic surface by combination of electrodeposition and hydrothermal synthesis and its self-cleaning and anti-icing properties [J]. Electroplat. Finish., 2022, 41: 502
	魏菲菲, 项腾飞, 刘剑等. 电沉积-水热法构建超疏水表面及其自清洁和防结冰性能 [J]. 电镀与涂饰, 2022, 41: 502
36	Huang Y, Sarkar D K, Chen X G. Superhydrophobic nanostructured ZnO thin films on aluminum alloy substrates by electrophoretic deposition process [J]. Appl. Surf. Sci., 2015, 327: 327
37	Zhou X W, Guo Y, Lu Z. 3D Xanthium-like of Ni-Co-Zn ternary alloys as superhydrophobic coatings toward porous Ti surface for its anti-icing performances [J]. Surf. Coat. Technol., 2023, 473: 130034
38	Wang Z H, Li Y C, Zhang G J. Fabrication of superhydrophobic Zn-Ni coatings on LA43M magnesium alloy [J]. J. Mater. Eng. Perform., 2022, 31: 5333
39	Huang L J, Huang H, Guo W, et al. 3D urchin-like of Zn-Ni-Co ternary oxide microspheres as high-performance electrodes for supercapacitors [J]. Electrochim. Acta, 2022, 434: 141317
40	Wu C, Cai J J, Zhang Q B, et al. Hierarchical mesoporous zinc-nickel-cobalt ternary oxide nanowire arrays on nickel foam as high-performance electrodes for supercapacitors [J]. ACS Appl. Mater. Interfaces, 2015, 7: 26512
41	Zhu D Y, Dai P Q, Luo X B, et al. Novel characterization of wetting properties and the calculation of liquid-solid interface tension (I) [J]. Sci. Technol. Eng., 2007, 7: 3057
	朱定一, 戴品强, 罗晓斌等. 润湿性表征体系及液固界面张力计算的新方法(Ⅰ) [J]. 科学技术与工程, 2007, 7: 3057

[1]	Tingting ZHAO, Zhixin KANG, Xiayu MA. Fabricating Superhydrophobic Copper Meshes by One-Step Electrodeposition Method and Its Anti-Corrosion and Oil-Water Separation Abilities[J]. 金属学报, 2018, 54(1): 109-117.
[2]	KANG Zhixin, GUO Mingjie. FABRICATION OF SUPERHYDROPHOBIC Ti SURFACE BY THERMAL OXIDATION AND ITS ANTICORROSION PROPERTY[J]. 金属学报, 2013, 49(5): 629-634.

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