利用微热压印与光刻蚀硅模在钛合金表面构建耐久超疏水结构

doi:10.3901/JME.2025.16.116

摘要/Abstract

摘要： 仿生微纳结构的超疏水表面具有独特的非润湿性和自清洁特性，应用前景广阔，但是已报道的微纳结构普遍存在机械耐久性差的问题。因此，构建兼具良好机械耐久性的超疏水表面成为目前超疏水表面的重点研究方向。在应用广泛的TC4(Ti6Al4V)钛合金表面构建仿生微纳结构，首先通过光刻蚀法(光刻+湿法刻蚀)制备出具有微米级金字塔结构的硅模板作为模具，接着通过微热压印在钛合金表面压制出连续倒金字塔形微米框架结构；之后采用水热法在倒金字塔形微腔中原位生长TiO₂纳米结构，并进行低表面能物质修饰，获得钛合金超疏水表面。全面评估了不同环境对所构建微纳复合结构超疏水性能的影响。结果表明，在700 ℃、60 kN压印条件下，硅模板金字塔微结构能够精确地复制到钛合金表面，水热反应生成的TiO₂纳米结构能够均匀铺满倒金字塔型微腔表面。倒金字塔形微米框架结构对TiO₂纳米结构提供了有效保护和力学支撑，获得的钛合金超疏水表面具有良好的耐久性能、耐腐蚀性能和自清洁性能。

关键词: TC4钛合金, 超疏水, 耐久性, 微纳结构, 光刻蚀, 微热压

Abstract: Superhydrophobic surface with a bionic micro-nano structure has a wide application prospect because of its unique non-wetting and self-cleaning properties. However, the so far reported micro-nano structures generally have a poor mechanical durability. Therefore, constructing superhydrophobic surfaces with a good mechanical durability has been the important research direction at present. The bionic micro-nano structure is constructed on the widely used TC4 (Ti6Al4V) titanium alloy. Firstly, a silicon template with pyramid micro-structure is fabricated by photoetching (photolithography+wet etching) as a mold, then a continuous inverted pyramid micro frame is pressed on the surface of titanium alloy by micro hot embossing; then the TiO₂ nano-struture is in situ grown in the inverted pyramid microcavities through hydrothermal method, after low surface energy material modification, the superhydrophobic surface is obtained on the surface of titanium alloy. The infuences of different environments on the superhydrophobicity property of the prepared micro-nano composite structure are evaluated comprehensively. The results show that under the pressing condition of 700 ℃、 60 kN, the pyramid micro-structure of the silicon mold can be accurately replicated to the surface of titanium alloy, and the TiO₂ formed by hydrothermal reaction can uniformly spread over the surface of the inverted pyramid microcavities. The inverted pyramid micro frame structure can provide effective protection and mechanical support for the TiO₂ nano-structure, thus a superhydrophobic surface of titanium alloy with good durability, corrosion resistance and self-cleaning property is obtained.

Key words: TC4 titanium alloy, superhydrophobicity, durability, micro-nano structure, photoetching, micro hot embossing

中图分类号:

TG376

章雨, 艾如玉, 高岩. 利用微热压印与光刻蚀硅模在钛合金表面构建耐久超疏水结构[J]. 机械工程学报, 2025, 61(16): 116-128.

ZHANG Yu, AI Ruyu, GAO Yan. Construction of Durable Superhydrophobic Structure on Titanium Alloy by Using Micro Hot Embossing and Photoetched Silicon Mold[J]. Journal of Mechanical Engineering, 2025, 61(16): 116-128.

参考文献

[1] 任露泉,梁云虹. 仿生学导论[M]. 北京:科学出版社, 2016. REN Luquan, LIANG Yunhong. The introduction of bionics[M]. Beijing: Science Press, 2016.
[2] NEINHUIS C, BARTHLOTT W. Characterization and distribution of water-repellent , self-cleaning plant surfaces[J]. Annals of Botany, 1997, 79(6): 667-677.
[3] BHUSHAN B, JUNG Y C. Natural and biomimetic artificial surfaces for superhydrophobicity, self-cleaning, low adhesion, and drag reduction[J]. Progress in Materials Science, 2011, 56(1): 1-108.
[4] FENG X J , JIANG L. Design and creation of superwetting/antiwetting surfaces[J]. Advanced Materials, 2006, 18(23): 3063-3078.
[5] ROACH P, SHIRTCLIFFE N J, NEWTON M I. Progress in superhydrophobic surface development[J]. Soft Matter., 2008, 4(2): 224-240.
[6] LI Z X, XING Y J, DAI J J. Superhydrophobic surfaces prepared from water glass and non-fluorinated alkylsilane on cotton substrates[J]. Applied Surface Science, 2008, 254(7): 2131-2135.
[7] FENG L, LI S H, LI Y S, et al. Super-hydrophobic surfaces : From natural to artificial[J]. Advanced Materials, 2002, 14(24): 1857-1860.
[8] FU H Q, LIU S, YI L L, et al. A durable and self-cleaning superhydrophobic surface prepared by precipitating flower-like crystals on a glass-ceramic surface[J]. Materials, 2020, 13(7): 1642-1654.
[9] LIU K S, JIANG L. Metallic surfaces with special wettability[J]. Nanoscale, 2011, 3(3): 825-838.
[10] ZHANG P, LV F Y. A review of the recent advances in superhydrophobic surfaces and the emerging energy-related applications[J]. Energy , 2015 , 82 : 1068-1087.
[11] SELIM M S, EL-SAFTY S A, SHENASHEN M A, et al. Progress in biomimetic leverages for marine antifouling using nanocomposite coatings[J]. Journal of Materials Chemistry B, 2020, 8(17): 3701-3732.
[12] 赵永庆. 国内外钛合金研究的发展现状及趋势[J]. 中国材料进展, 2010, 29(5): 1-8, 24. ZHAO Yongqing. Current situation and development trend of titanium alloys[J]. Materials China, 2010, 29(5): 1-8, 24.
[13] 刘全明,张朝晖,刘世锋,等. 钛合金在航空航天及武器装备领域的应用与发展[J]. 钢铁研究学报, 2015, 27(3): 1-4. LIU Quanming, ZHANG Zhaohui, LIU Shifeng, et al. Application and development of titanium alloy in aerospace and military hardware[J]. Journal of Iron and Steel Research, 2015, 27(3): 1-4.
[14] PENG C Y, CHEN Z Y, TIWARI M K. All-organic superhydrophobic coatings with mechanochemical robustness and liquid impalement resistance[J]. Nature Materials, 2018, 17(4): 355-360.
[15] BUTT H J, VOLLMER D, PAPADOPOULOS P. Super liquid-repellent layers: The smaller the better[J]. Advances in Colloid and Interface Science, 2015, 222: 104-109.
[16] WANG D H, SUN Q Q, HOKKANEN M J, et al. Design of robust superhydrophobic surfaces[J]. Nature, 2020, 582(7810): 55-59.
[17] SMILJANIC M M, LAZIC Z, RADJENOVIC B, et al. Evolution of Si crystallographic planes-etching of square and circle patterns in 25 wt % TMAH[J]. Micromachines, 2019, 10(2): 102-116.
[18] 田嘉彤,冯仕猛,王坤霞. 单晶硅表面金字塔生长过程的实验研究[J]. 光子学报, 2011, 40(10): 1505-1508. TIAN Jiatong, FENG Shimeng, WANG Kunxia, et al. Formation process of pyramids on single crystal Si surface[J]. Acta Photonica Sinica , 2011 , 40(10) : 1505-1508.
[19] ZHAO L, ZUO Y H, ZHOU C L, et al. Theoretical investigation on the absorption enhancement of the crystalline silicon solar cells by pyramid texture coated with SiNx: H layer[J]. Solar Energy, 2011, 85(3): 530-537.
[20] TANG Q T, SHEN H L, GAO K, et al. Efficient light trapping of quasi-inverted nanopyramids in ultrathin c-Si through a cost-effective wet chemical method[J]. Rsc Advances, 2016, 6(99): 96686-96692.
[21] DESHMUKH S S, GOSWAMI A. Hot embossing of polymers-A review[C]//Proceedings of the 10th International Conference of Materials Processing and Characterization (ICMPC), GLA Univ, Mathura, India, 2020: 405-414.
[22] PENG L F, DENG Y J, YI P Y, et al. Micro hot embossing of thermoplastic polymers : A review[J]. Journal of Micromechanics and Microengineering, 2014, 24(1): 013001.
[23] HO A Y Y, VAN E L, LIM C T, et al. Lotus bioinspired superhydrophobic , self-cleaning surfaces from hierarchically assembled templates[J]. Journal of Polymer Science Part B-Polymer Physics, 2014, 52(8): 603-609.
[24] XU J, XING G N, SHAN D B, et al. An evaluation of formability using micro-embossing on an ultrafinegrained magnesium AZ31 alloy processed by highpressure torsion[C]//Proceedings of the 4th International Conference on New Forming Technology (ICNFT), Glasgow, England, 2015: 09005.
[25] XU J, LI J W, SHAN D B, et al. Strain softening mechanism at meso scale during micro-compression in an ultrafine-grained pure copper[J]. AIP Advances, 2015, 5(9): 097147.
[26] XU J , SU Q , SHAN D B , et al. Sustainable micro-manufacturing of superhydrophobic surface on ultrafine-grained pure aluminum substrate combining micro-embossing and surface modification[J]. Journal of Cleaner Production, 2019, 232: 705-712.
[27] WANG C Y, GROENZIN H, SHULTZ M J. Molecular species on nanoparticulate anatase TiO2 film detected by sum frequency generation : Trace hydrocarbons and hydroxyl groups[J]. Langmuir, 2003, 19(18): 7330-7334.
[28] FINNIE K S, CASSIDY D J, BARTLETT J R, et al. IR spectroscopy of surface water and hydroxyl species on nanocrystalline TiO2 films[J]. Langmuir, 2001, 17(3): 816-820.
[29] GAO L C , MCCARTHY T J. The “lotus effect” explained : Two reasons why two length scales of topography are important[J]. Langmuir, 2006, 22(7): 2966-2967.