Abstract
The superhydrophobic surface was prepared on biomedical Ti–6Al–4V alloy by hydrothermal treatment coupled with subsequent hydrophobic treatment. The surface morphologies, surface roughness, phase and elemental compositions, water contact angle and hemocompatibility of the superhydrophobic samples were investigated. The results show that the hydrothermally treated sample is mainly composed of Na2Ti6O13 phase with some –OH groups. The surface morphologies of the hydrothermally treated samples change from feather-like structure to grass-like structure, and the surface roughness gradually increases with increasing the concentrations of NaOH solution. After hydrophobic treatment, the surface roughness of samples slightly decreases, and the water contact angles increase first, reaching the maximum value of 159.24° ± 1.89° at 3.75 mol/L, and then decrease with increasing the NaOH concentrations. The –C8H4F13 low surface energy fluorides are grafted onto the surface of hydrothermally treated sample by a self-assembly dehydration reaction, resulting in the formation of the superhydrophobic surface. The superhydrophobic surface effectively decreases the hemolysis ratio and platelets adhesion, and prolongs the dynamic coagulation time, indicating that it greatly improves the hemocompatibility of the biomedical Ti–6Al–4V alloy.
Graphical Abstract

This is a preview of subscription content, access via your institution.









References
- 1
Kaur M, Singh K (2019) Review on titanium and titanium based alloys as biomaterials for orthopaedic applications. Mater Sci Eng C 162:844–862
- 2
Garnica P, Macías R, Chávez J, Bouvard D, Jiménez O, Olmos L, Arteaga D (2020) Fabrication and characterization of highly porous Ti6Al4V/xTa composites for orthopedic applications. J Mater Sci 55:16419–16431. https://doi.org/10.1007/s10853-020-05166-5
- 3
Sevostyanov MA, Kolmakov AG, Sergiyenko KV, Kaplan MA, Baikin AS, Gudkov SV (2020) Mechanical, physical–chemical and biological properties of the new Ti–30Nb–13Ta–5Zr alloy. J Mater Sci 55:14516–14529. https://doi.org/10.1007/s10853-020-05020-8
- 4
Wu W, Song Y, Wang Z, Ning S, Hua L (2020) Solid phase transformation of Ti–6.6Al–3.4Mo alloy induced by electroshocking treatment. J Mater Sci. 55:2245–2255
- 5
Sevost’yanov MA, Nasakina EO, Baikin AS, Sergienko KV, Konushkin SV, Kaplan MA, Seregin AV, Leonov AV, Kozlov VA, Shkirin AV, Bunkin NF, Kolmakov AG, Simakov SV, Gudkov SV (2018) Biocompatibility of new materials based on nano-structured nitinol with titanium and tantalum composite surface layers: experimental analysis in vitro and in vivo. J Mater Sci-Mater Med 29:33
- 6
Xu JL, Tao SC, Bao LZ, Luo JM, Zheng YF (2019) Effects of Mo contents on the microstructure, properties and cytocompatibility of the microwave sintered porous Ti–Mo alloys. Mater Sci Eng C 97:156–165
- 7
Asri RIM, Harun WSW, Samykano M, Lan NAC, Ghani SAC, Tarlochan F, Raza MR (2017) Corrosion and surface modification on biocompatible metals: a review. Mater Sci Eng C 77:1261–1674
- 8
Mzyk A, Imbir G, Trembecka-Wójciga K, Lackner JM, Plutecka H, Jasek-Gajda E, Kawalko J, Major R (2020) Rolling or two-stage aggregation of platelets on the surface of thin ceramic coatings under in vitro simulated blood flow conditions. ACS Biomater Sci Eng 6:898–911
- 9
Xu L, Zhang K, Wu C, Lei X, Ding J, Shi X, Liu C (2017) Micro-arc oxidation enhances the blood compatibility of ultrafine-grained pure titanium. Mater 10:1446
- 10
Huang CW, Cheng CH, Chiu Y, Lin YC, Lin JC (2017) A facile novel fluorocarbon copolymer solution coating process for improving platelet compatibility of titanium. Mater Sci Eng C 80:584–593
- 11
Zhang K, Chen JY, Qin W, Li JA, Guan FX, Huang N (2016) Constructing bio-layer of heparin and type IV collagen on titanium surface for improving its endothelialization and blood compatibility. J Mater Sci-Mater Med 27:81
- 12
Jiang JY, Xu JL, Liu ZH, Deng L, Sun B, Liu SD, Wang L, Liu HY (2015) Preparation, corrosion resistance and hemocompatibility of the superhydrophobic TiO2 coatings on biomedical Ti–6Al–4V alloys. Appl Surf Sci 347:591–595
- 13
Yang Y, Lai Y, Zhang Q, Wu K, Zhang L, Lin C, Tang P (2010) A novel electrochemical strategy for improving blood compatibility of titanium-based biomaterials. Colloids Surf B 79:309–313
- 14
Huang Q, Yang Y, Hu R, Lin C, Sun L, Vogler EA (2015) Reduced platelet adhesion and improved corrosion resistance of superhydrophobic TiO2-nanotube-coated 316L stainless steel. Colloids Surf B 125:134–141
- 15
Mohamed AMA, Abdullah AM, Younan NA (2015) Corrosion behavior of superhydrophobic surfaces: a review. Arab J Chem 8:749–765
- 16
Celia E, Darmanin T, de Givenchy ET, Amigoni S, Guittard F (2013) Recent advances in designing superhydrophobic surfaces. J Colloid Interface Sci 402:1–18
- 17
Hooda A, Goyat MS, Pandey JK, Kumar A, Gupta R (2020) A review on fundamentals, constraints and fabrication techniques of superhydrophobic coatings. Prog Org Coat 142:105557
- 18
Varshney P, Mohapatra SS, Kumar A (2016) Superhydrophobic coatings for aluminum surfaces synthesized by chemical etching process. Int J Smart and Nano Mater 7:248–264
- 19
Wang J, Wu Y, Zhang D, Li L, Wang T, Duan S (2020) Preparation of superhydrophobic flexible tubes with water and blood repellency based on template method. Colloids Surf A 587:124331
- 20
Nakayama K, Hiraga T, Zhu C, Tsuji E, Aoki Y, Habazaki H (2017) Facile preparation of self-healing superhydrophobic CeO2 surface by electrochemical processes. Appl Surf Sci 423:968–976
- 21
Tuo Y, Chen W, Zhang H, Li P, Liu X (2018) One-step hydrothermal method to fabricate drag reduction superhydrophobic surface on aluminum foil. Appl Surf Sci 446:230–235
- 22
Zang J, Yu S, Zhu G, Zhou X (2019) Fabrication of superhydrophobic surface on aluminum alloy 6061 by a facile and effective anodic oxidation method. Surf Coat Technol 380:125078
- 23
Liu AH, Xu JL (2018) Preparation and corrosion resistance of superhydrophobic coatings on AZ31 magnesium alloy. Trans Nonferrous Metals Soc China 28:2287–2293
- 24
Ou J, Liu M, Li W, Wang F, Xue M, Li C (2012) Corrosion behavior of superhydrophobic surfaces of Ti alloys in NaCl solutions. Appl Surf Sci 258:4724–4728
- 25
Lakshmi RV, Bharathidasan T, Basu BJ (2011) Superhydrophobic sol–gel nanocomposite coatings with enhanced hardness. Appl Surf Sci 257:10421–10426
- 26
Kavale MS, Mahadik DB, Parale VG, Wagh PB, Gupta SC, Rao AV, Barsilia HC (2011) Optically transparent, superhydrophobic methyltrimethoxysilane based silica coatings without silylating reagent. Appl Surf Sci 258:158–162
- 27
Song J, Xu W, Liu X, Lu Y, Wei Z, Wu L (2012) Ultrafast fabrication of rough structures required by superhydrophobic surfaces on Al substrates using an immersion method. Chem Eng J 211–212:143–152
- 28
Ghashghaee M, Fallah M, Rabiee A (2016) Superhydrophobic nanocomposite coatings of poly (methyl methacrylate) and stearic acid grafted CuO nanoparticles with photocatalytic activity. Prog Organic Coat 136:105270
- 29
Xu JL, Zhang JL, Bao LZ, Lai T, Luo JM, Zheng YF (2018) Preparation and bioactive surface modification of the microwave sintered porous Ti-15Mo alloys for biomedical application. Sci China Mater 61:545–556
- 30
Su Y, Komasa S, Sekino T, Nishizaki H, Okazaki J (2016) Nanostructured Ti–6Al–4V alloy fabricated using modified alkali-heat treatment: characterization and cell adhesion. Mater Sci Eng C 59:617–623
- 31
Ho WF, Lai CH, Hsu HC, Wu SC (2009) Surface modification of a low-modulus Ti–7.5Mo alloy treated with aqueous NaOH. Surf Coati Technol 203:3142–3150
- 32
Lee BH, Kim YD, Lee KH (2003) XPS study of bioactive graded layer in Ti-In-Nb-Ta alloy prepared by alkali and heat treatments. Biomater 24:2257–2266
- 33
Escada ALA, Jr DR, Machado JPB, Alves Claro APR (2010) Surface characterization of Ti–7.5Mo alloy modified by biomimetic method. Surf Coat Technol 205:383–387
- 34
Kim HM, Miyaji F, Kokubo T, Nakamura T (1997) Apatite-forming ability of alkali-treated Ti metal in body environment. J Ceram Soc Jpn 105:111–116
- 35
Hsu HC, Wu SC, Hsu SK, Chang TY, Ho WF (2014) Effect of ball milling on properties of porous Ti–7.5Mo alloy for biomedical applications. J Alloys Compd 582:793–801
- 36
Li SJ, Yang R, Niinomi M, Hao YL, Cui YY (2004) Formation and growth of calcium phosphate on the surface of oxidized Ti–29Nb–13Ta–46Zr alloy. Biomater 25:2525–2532
- 37
Kačiulis S, Mattogno G, Napolia A et al (1998) Surface analysis of biocompatible coatings on titanium. J Electron Spectrosc Relat Phenom 95:61–69
- 38
Moulder JF, Stickle WF, Sobol PE, Keneth DB (1992) Handbook of X-ray photoelectron spectroscopy: a reference book of standard spectra for identification and interpretation of XPS data [M]. Perkin-Elmer Corporation, USA
- 39
Beamson G, Briggs D (1992) High resolution XPS of organic ploymer-the scienta ESCA300 database [M]. Wiley, UK
- 40
Viitala R, Simola J, Peltola T, Eahiala H, Linden M, Langlet M, Rosenholm JB (2001) In vitro bioactivity of aerosol-gel deposited TiO2 thin coatings. J Biomed Mater Res 54:109–114
- 41
Xu JL, Xiao QF, Mei DD, Zhong ZZ, Tong YX, Zheng YF, Li L (2017) Preparation and characterization of amorphous SiO2 coatings deposited by mirco-arc oxidation on sintered NdFeB permanent magnets. J Magn Magn Mater 426:361–368
- 42
Ren Y, Ye W, Liu A, Zhang L, Dong G, Bo W, Ling X (2018) Preparation and properties of superhydrophobic titanium alloy with hierarchical structure. Rare Metal Mater Eng 47:3748–3753
- 43
Xu JL, Zhong ZC, Yu DZ, Liu F, Luo JM (2012) Effect of micro-arc oxidation surface modification on the properties of the NiTi shape memory alloy. J Mater Sci-Mater Med 23:2839–2846
- 44
Bernhard H, Nico S, Sabine K, Ole G, Ines G, Stefan N, Sinem P, Friedrich J (2016) Influence of the blood exposure time in dynamic hemocompatibility testing on coagulation and C5a activation. J Cell Biotechnol 1:145–150
- 45
Sun T, Tan H, Tan D, Fu Q, Jiang L (2005) No platelet can adhere–largely improved blood compatibility on nanostructured superhydrophobic surfaces. Small 1:959–963
Acknowledgements
This work was funded by the National Natural Science Foundation of China (51101085, 51764041 and 51704167), the Opening Project of National Engineering Research Center for Powder Metallurgy of Titanium & Rare Metals, China (2019004) and the Jiangxi Provincial Natural Science Foundation (20202ACBL214011).
Author information
Affiliations
Corresponding authors
Ethics declarations
Conflicts of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Handling Editor: David Balloy.
Rights and permissions
About this article
Cite this article
Chen, J., Xu, J.L., Huang, J. et al. Formation mechanism and hemocompatibility of the superhydrophobic surface on biomedical Ti–6Al–4V alloy. J Mater Sci 56, 7698–7709 (2021). https://doi.org/10.1007/s10853-020-05696-y
Received:
Accepted:
Published:
Issue Date: