Laser-chemical Composite Regulation of the Superhydrophobic Surface of &#x003b2; Titanium Alloys

WANG Shenao; FU Xiuli; MENG Ying; PAN Yongzhi; SONG Shuqin; MEN Xiuhua

doi:10.16490/j.cnki.issn.1001-3660.2026.10.017

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Surface Technology ›› 2026, Vol. 55 ›› Issue (10) : 208-222. DOI: 10.16490/j.cnki.issn.1001-3660.2026.10.017

Functional Surfaces and Technology

Laser-chemical Composite Regulation of the Superhydrophobic Surface of β Titanium Alloys

WANG Shenao¹, FU Xiuli^1,2,*, MENG Ying¹, PAN Yongzhi¹, SONG Shuqin¹, MEN Xiuhua¹

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Abstract

Titanium alloys have attracted extensive attention in the biomedical field due to their outstanding properties, including high specific strength, excellent corrosion resistance, and good biocompatibility. However, when titanium alloy surfaces come into direct contact with blood, they may induce thrombus formation, which significantly limits their clinical applications. To address this issue, the work aims to propose the construction of a superhydrophobic surface to improve the hemocompatibility of titanium alloys and reduce the risk of thrombosis during implantation. In this work, a β titanium alloy TB9 was selected as the substrate material. Femtosecond laser processing was employed to fabricate micro-scale surface textures on the TB9 alloy, followed by chemical modification to reduce the surface free energy. The effects of different laser processing parameters on surface ablation morphology and texture dimensions were systematically investigated through scanning electron microscopy (SEM) and laser confocal microscopy. To achieve superhydrophobicity, the sample surfaces underwent chemical modification to reduce surface energy. The laser-etched samples were immersed in a 2wt.% solution of 1H,1H,2H,2H- Perfluorodecyltrimethoxysilane (FAS-17) at room temperature for 2 hours, followed by thermal curing in a constant temperature drying oven at 120 ℃ for 120 minutes. The wettability of the processed surfaces was evaluated by contact angle measurements under varying processing conditions. Furthermore, the surface chemical composition and functional groups were characterized with X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy to confirm the successful chemical modification. To assess the durability of the fabricated superhydrophobic surface, linear friction tests were conducted to evaluate its mechanical robustness. In addition, hemolysis tests and platelet adhesion experiments were performed to investigate the hemocompatibility of the modified surfaces. The results demonstrated that by optimizing the femtosecond laser parameters and combining them with appropriate chemical modification, a stable superhydrophobic surface was successfully fabricated on the TB9 titanium alloy. The obtained surface exhibited a water contact angle of up to 164.2° and a low sliding angle of 1.8°, indicating excellent water repellency. The superhydrophobic surface also showed remarkable anti-blood adhesion performance. The wettability analysis revealed that the formation of the superhydrophobic state was attributed to the synergistic effect between the hierarchical microstructures generated by laser ablation and the low surface energy materials introduced during chemical modification. Surface chemical characterization confirmed that fluorosilane molecules were successfully deposited onto the TB9 substrate, contributing to the reduced surface energy. The durability tests indicated that the superhydrophobic surface maintained its water-repellent properties even after 20 cycles of linear friction, demonstrating good mechanical stability. The hemolysis rate of the superhydrophobic surface was measured to be 0.248 1%, which met the requirements for biomedical materials in direct contact with blood. Moreover, the platelet adhesion experiments showed that there was no significant platelet attachment observed on the superhydrophobic surface, indicating excellent resistance to platelet adhesion and activation. In summary, a robust and stable superhydrophobic surface is successfully fabricated on TB9 titanium alloy through a combination of femtosecond laser ablation and chemical modification. The prepared surface not only exhibits excellent wettability and mechanical durability but also significantly improves hemocompatibility by reducing hemolysis and inhibiting platelet adhesion. This work provides a simple, efficient, and low-cost strategy for constructing superhydrophobic surfaces on titanium alloys, thereby expanding their potential applications in the biomedical field, particularly for blood-contacting implants and devices.

Key words

femtosecond laser / superhydrophobic / TB9 titanium alloy / surface texture / chemical modification / hemocompatibility

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WANG Shenao, FU Xiuli, MENG Ying, PAN Yongzhi, SONG Shuqin, MEN Xiuhua. Laser-chemical Composite Regulation of the Superhydrophobic Surface of β Titanium Alloys[J]. Surface Technology. 2026, 55(10): 208-222

References

[1] CUI Y W, WANG L Q, ZHANG L C.Towards Load- Bearing Biomedical Titanium-Based Alloys: From Essential Requirements to Future Developments[J]. Progress in Materials Science, 2024, 144: 101277.
[2] PENG Y M, CHEN C Y, ZHAO R X, et al.Strong and Ductile Metastable β Titanium Alloy via Laser Powder Bed Fusion through Nitrogen Interstitials and Tailored Microstructure[J]. Materials Characterization, 2025, 225: 115121.
[3] KURUP A, DHATRAK P, KHASNIS N.Surface Modification Techniques of Titanium and Titanium Alloys for Biomedical Dental Applications: A Review[J]. Materials Today: Proceedings, 2021, 39: 84-90.
[4] HAN X, MA J X, TIAN A X, et al.Surface Modification Techniques of Titanium and Titanium Alloys for Biomedical Orthopaedics Applications: A Review[J]. Colloids and Surfaces B: Biointerfaces, 2023, 227: 113339.
[5] CHEN L Y, CUI Y W, ZHANG L C.Recent Development in Beta Titanium Alloys for Biomedical Applications[J]. Metals, 2020, 10(9): 1139.
[6] LIU H, LI Y Q, SHI L Z, et al.Corrosion Behavior of Laser Powder Bed Fusion Prepared Cu-Bearing β Titanium Alloy under Simulated Inflammatory Conditions[J]. Electrochimica Acta, 2025, 533: 146533.
[7] MANIVASAGAM V K, SABINO R M, KANTAM P, et al.Surface Modification Strategies to Improve Titanium Hemocompatibility: A Comprehensive Review[J]. Materials Advances, 2021, 2(18): 5824-5842.
[8] MOVAFAGHI S, LESZCZAK V, WANG W, et al.Hemocompatibility of Superhemophobic Titania Surfaces[J]. Advanced Healthcare Materials, 2017, 6(4): 1600717.
[9] MANIVASAGAM V K, POPAT K C.Improved Hemocompatibility on Superhemophobic Micro-Nano-Structured Titanium Surfaces[J]. Bioengineering, 2023, 10(1): 43.
[10] CHENG Y, YANG Z W, GOU X D, et al.Heart Valve- Inspired Self-Lubricating Anticoagulant Surfaces[J]. Chemical Engineering Journal, 2023, 474: 145358.
[11] WANG N, XIONG D S.Superhydrophobic Membranes on Metal Substrate and Their Corrosion Protection in Different Corrosive Media[J]. Applied Surface Science, 2014, 305: 603-608.
[12] MANOJ T P, RASITHA T P, VANITHAKUMARI S C, et al.A Simple, Rapid and Single Step Method for Fabricating Superhydrophobic Titanium Surfaces with Improved Water Bouncing and Self Cleaning Properties[J]. Applied Surface Science, 2020, 512: 145636.
[13] PAKZAD H, LIRAVI M, MOOSAVI A, et al.Fabrication of Durable Superhydrophobic Surfaces Using PDMS and Beeswax for Drag Reduction of Internal Turbulent Flow[J]. Applied Surface Science, 2020, 513: 145754.
[14] ZHANG B B, XU W C, ZHU Q J, et al.Mechanically Robust Superhydrophobic Porous Anodized AA5083 for Marine Corrosion Protection[J]. Corrosion Science, 2019, 158: 108083.
[15] WANG Y X, ZHANG G F, HE Z, et al.Superhydrophobic Ni Nanocone Surface Prepared by Electrodeposition and Its Overall Performance[J]. Surface and Coatings Technology, 2023, 464: 129548.
[16] LAKSHMI R V, BHARATHIDASAN T, BASU B J.Superhydrophobic Sol-Gel Nanocomposite Coatings with Enhanced Hardness[J]. Applied Surface Science, 2011, 257(24): 10421-10426.
[17] GU S Y, GE H C, WEI H Y, et al.Study on the Regulation of Droplet Motion Behavior on Superhydrophobic Surfaces[J]. Chemical Engineering Journal, 2024, 498: 155282.
[18] ZAREEI POUR F, KARIMI H, MADADI AVARGANI V.Preparation of a Superhydrophobic and Superoleophilic Polyester Textile by Chemical Vapor Deposition of Dichlorodimethylsilane for Water-Oil Separation[J]. Polyhedron, 2019, 159: 54-63.
[19] WANG J Y, LI P H, YU P, et al.Efficient Photothermal Deicing Employing Superhydrophobic Plasmonic MXene Composites[J]. Advanced Composites and Hybrid Materials, 2022, 5(4): 3035-3044.
[20] 雍佳乐, 吴东. 飞秒激光仿生调控材料表面浸润性: 当前进展与挑战[J]. 中国激光, 2024, 51(1): 0102002.
YONG J (L/Y), WU D. Bioinspired Controlling the Surface Wettability of Materials by Femtosecond Laser: Current Progress and Challenges (Invited)[J]. Chinese Journal of Lasers, 2024, 51(1): 0102002.
[21] 吴东江, 刘成, 杨峰, 等. 飞秒激光加工参数对RB-SiC表面形貌的影响[J]. 表面技术, 2024, 53(3): 162-169.
WU D J, LIU C, YANG F, et al.Effect of Femtosecond Laser Processing Parameters on RB-SiC Surface Morphology[J]. Surface Technology, 2024, 53(3): 162-169.
[22] JOKINEN V, LEINIKKA M, FRANSSILA S.Microstructured Surfaces for Directional Wetting[J]. Advanced Materials, 2009, 21(47): 4835-4838.
[23] FASASI A Y, MWENIFUMBO S, RAHBAR N, et al.Nano-Second UV Laser Processed Micro-Grooves on Ti₆Al₄V for Biomedical Applications[J]. Materials Science and Engineering: C, 2009, 29(1): 5-13.
[24] GUO C F, ZHANG M J, HU J.Icing Delay of Sessile Water Droplets on Superhydrophobic Titanium Alloy Surfaces[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 621: 126587.
[25] YANG L, SHEN X D, YANG Q, et al.Fabrication of Biomimetic Anisotropic Super-Hydrophobic Surface with Rice Leaf-Like Structures by Femtosecond Laser[J]. Optical Materials, 2021, 112: 110740.
[26] LI P N, WANG S R, YU K, et al.Superhydrophobic Biomimetic Microstructures Prepared by Laser-Ablation for Drag Reduction[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 686: 133381.
[27] LI Z Y, LI S, SU X, et al.Anti-Icing Performance of Superhydrophobic Surfaces with Periodic Micro-Nano Structures Directly Induced by Femtosecond Laser[J]. Advanced Materials Interfaces, 2025, 12(9): 2400828.
[28] 王奔, 念敬妍, 铁璐, 等. 稳定超疏水性表面的理论进展[J]. 物理学报, 2013, 62(14): 362-376.
WANG B, NIAN J Y, TIE L, et al.Theoretical Progress in Designs of Stable Superhydrophobic Surfaces[J]. Acta Physica Sinica, 2013, 62(14): 362-376.
[29] AKHTARI M R, KARIMI N.Thermohydraulic Analysis of a Microchannel with Varying Superhydrophobic Roughness[J]. Applied Thermal Engineering, 2020, 172: 115147.
[30] VOLPE A, COVELLA S, GAUDIUSO C, et al.Improving the Laser Texture Strategy to Get Superhydrophobic Aluminum Alloy Surfaces[J]. Coatings, 2021, 11(3): 369.
[31] ZHANG Q C, YANG Z, DENG X Y, et al.Fabrication of a Gradient Hydrophobic Surface with Parallel Ridges on Pyrolytic Carbon for Artificial Heart Valves[J]. Colloids and Surfaces B: Biointerfaces, 2021, 205: 111894.
[32] ZHANG J, LI G L, LI D H, et al.In Vivo Blood-Repellent Performance of a Controllable Facile-Generated Superhydrophobic Surface[J]. ACS Applied Materials & Interfaces, 2021, 13(24): 29021-29033.
[33] WENZEL R N.Resistance of Solid Surfaces to Wetting by Water[J]. Industrial & Engineering Chemistry, 1936, 28(8): 988-994.
[34] YANG Y Z, MA Y X, LI W Q, et al.Anti-Corrosion Superhydrophobic Surface of LPBF- NiTi Alloy Fabricated by Nanosecond Laser Machining[J]. Optics & Laser Technology, 2023, 158: 108858.
[35] LIU W L, WANG S R, WANG G Q, et al.Investigation on the Differences of Surface Cleaning Properties of Series of Superhydrophobic Aluminum Alloys[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 651: 129614.
[36] OWENS D K, WENDT R C.Estimation of the Surface Free Energy of Polymers[J]. Journal of Applied Polymer Science, 1969, 13(8): 1741-1747.
[37] SHAO G F, WU X D, KONG Y, et al.Microstructure, Radiative Property and Thermal Shock Behavior of TaSi₂-SiO₂-Borosilicate Glass Coating for Fibrous ZrO₂ Ceramic Insulation[J]. Journal of Alloys and Compounds, 2016, 663: 360-370.
[38] NGUYEN H H, WAN S H, TIEU K A, et al.Rendering Hydrophilic Glass-Ceramic Enamel Surfaces Hydrophobic by Acid Etching and Surface Silanization for Heat Transfer Applications[J]. Surface and Coatings Technology, 2019, 370: 82-96.
[39] AIN Q T, BANO N, AL-MODLEJ A, et al.Study of a Saturation Point to Establish the Doping Density Limit of Silicon with Graphene Oxide[J]. Materials Science in Semiconductor Processing, 2019, 96: 116-121.
[40] 李松梅, 周思卓, 刘建华. 铝合金表面原位自组装超疏水膜层的制备及耐蚀性能[J]. 物理化学学报, 2009, 25(12): 2581-2589.
LI S M, ZHOU S Z, LIU J H.Fabrication and Anti- Corrosion Property of in Situ Self-Assembled Super- Hydrophobic Films on Aluminum Alloys[J]. Acta Physico- Chimica Sinica, 2009, 25(12): 2581-2589.

Funding

The National Natural Science Foundation of China (52175408,52405481); Natural Science Foundation of Shandong Province (ZR2021ME183); University of Jinan Disciplinary Cross-Convergence Construction Project 2024 (XKJC-202406); Young Talent of Lifting Engineering for Science and Technology in Shandong of China (SDAST2024QTA073)