Preparation and Bioactivity of Micro-Nano Structure on Ti6Al4V Surface
GAO Han1,2(), LIU Li1,2, ZHOU Xiaoyu1,2, ZHOU Xinyi1,2, CAI Wenjun1,2, ZHOU Hongling1,2
1.Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials, Ministry of Education, Shandong University, Jinan 250061, China 2.School of Materials Science and Engineering, Shandong University, Jinan 250061, China
Cite this article:
GAO Han, LIU Li, ZHOU Xiaoyu, ZHOU Xinyi, CAI Wenjun, ZHOU Hongling. Preparation and Bioactivity of Micro-Nano Structure on Ti6Al4V Surface. Acta Metall Sin, 2023, 59(11): 1466-1474.
Titanium (Ti) and its alloys have been widely used in the medical field for dental and orthopedic surgeries owing to their excellent mechanical and biological properties. However, much effort has been devoted to the surface modification on Ti-based implants for better biological response in medical applications. Bioactive layers with micro- and nano-scale structures and morphologies can increase the specific surface area of the implants and facilitate rapid osseointegration, which has shown good biological behaviors both in the laboratory and clinical setting. Sandblasting and acid-etching (SLA) technology has become one of the most commonly used surface modification processes for currently marketed dental implants, since it can be easily operated and is efficient. However, studies on etching behavior are still limited. In this study, concentrated hydrochloric acid ((36%-38%)HCl, mass fraction) and mixed diluted acid (20%HCl : 30%H2SO4 = 1 : 1, volume fraction) were used to etch Ti6Al4V, and an ultrasonic field was applied to the acid etching treatment. The influence of different etching parameters on the surface structure and morphology of Ti6Al4V was discussed, including the acid etching reagent, acid etching time, and ultrasonic field. Moreover, through the combination of SLA and induction heating treatment (IHT) oxidation, the micro- and nano-scale hierarchical structure was prepared on the surface of Ti6Al4V. The evolution of surface topography, chemistry, roughness, wettability, and bioactivity of the hierarchical structure was discussed. The micro-scale composite pores combing dozens of micron pores and several micron pores were obtained by SLA. Within a certain etching time range, with the prolonging of the etching time, the step structure on the inner wall of the micro-pores becomes more obvious, and ultrasound can accelerate the acid etching. After the IHT at 800oC, the micro- and nano-scale hierarchical surface with micro-scale composite pores and nanoscale oxide was obtained. Compared with the SLA surface, there was a decrease in surface roughness and an increase in wettability. Furthermore, after soaking in simulated body fluid (SBF) for 14 d, a homogeneous hydroxyapatite (HA) layer was formed on the micro- and nano-scale structured Ti6Al4V surface, suggesting high biological activity of the fabricated structure.
Fig.1 SEM images of Ti6Al4V after sandblasting (a) + (36%~38%)HCl acid etching for 10 min (b), 20 min (c), and 30 min (d) (Insets in Figs.1b-d show the corresponding high magnified images)
Fig.2 Low (a, b) and high (c, d) magnified SEM images of Ti6Al4V surface after sandblasting + 20%HCl : 30% H2SO4 = 1 : 1 (volume fraction) acid etching for 60 min without (a, c) and with (b, d) ultrasonic treatment
Fig.3 XRD spectra of Ti6Al4V after SLA + IHT and soaking in SBF for 14 d (SLA represents the process of sandblasting + (36%~38%)HCl acid etching for 10 min with ultrasonic treatment, SBF—simulated body fluid, IHT—induction heating treatment, HA—hydroxyapatite)
Fig.4 SEM images (a1-d1) and EDS results (a2-d2) of Ti6Al4V after SLA (a1, a2) and SBF soaking for 14 d (c1, c2), and after SLA + IHT (b1, b2) and SBF soaking for 14 d (d1, d2)
Fig.5 3D morphologies of Ti6Al4V after sandblasting (a) + acid etching with ultrasonic treatment (10 min) (b) + IHT (800oC) (c), and quantitative measurements of surface roughness (d)
Fig.6 Water droplet on the surfaces of Ti6Al4V after sandblasting (a) + acid etching with ultrasonic treatment (10 min) (b) + IHT (800oC) (c), and contact angles (d)
1
Dong H Q, Guo Z M, Mao X M, et al. Prospect of development trend of melting technology of titanium and/or its alloys with high efficiency and low energy consumption [J]. Mater. Rev., 2008, 22(5):68
Lin C W, Ju C P, Lin J H C. A comparison of the fatigue behavior of cast Ti-7.5Mo with c.p. titanium, Ti-6Al-4V and Ti-13Nb-13Zr alloys [J]. Biomaterials, 2005, 26: 2899
doi: 10.1016/j.biomaterials.2004.09.007
3
Zhao L C, Cui C X, Huang N. Design and performance study on two new low elastic modulus metastable β titanium alloys for biomedical application [J]. Tianjin Metall., 2009, (2): 13
Rao S, Ushida T, Tateishi T, et al. Effect of Ti, Al, and V ions on the relative growth rate of fibroblasts (L929) and osteoblasts (MC3T3-E1) cells [J]. Bio-Med. Mater. Eng., 1996, 6: 79
5
Walker P R, LeBlanc J, Sikorska M. Effects of aluminum and other cations on the structure of brain and liver chromatin [J]. Biochemistry, 1989, 28: 3911
pmid: 2752000
6
Sumitomo N, Noritake K, Hattori T, et al. Experiment study on fracture fixation with low rigidity titanium alloy: Plate fixation of tibia fracture model in rabbit [J]. J. Mater. Sci.: Mater. Med., 2008, 19: 1581
doi: 10.1007/s10856-008-3372-y
7
Ferraris S, Spriano S. Antibacterial titanium surfaces for medical implants [J]. Mater. Sci. Eng., 2016, C61: 965
8
Geetha M, Singh A K, Asokamani R, et al. Ti based biomaterials, the ultimate choice for orthopaedic implants—A review [J]. Prog. Mater. Sci., 2009, 54: 397
doi: 10.1016/j.pmatsci.2008.06.004
9
Ning C Q, Zhou Y. Development and research status of biomedical titanium alloys [J]. Mater. Sci. Technol., 2002, 10: 100
Málek J, Hnilica F, Veselý J, et al. Microstructure and mechanical properties of Ti-35Nb-6Ta alloy after thermomechanical treatment [J]. Mater. Charact., 2012, 66: 75
doi: 10.1016/j.matchar.2012.02.012
11
Ren B, Wan Y, Wang G S, et al. Effects of surface morphology and composition of medical titanium alloys on biocompatibility [J]. Surf. Technol., 2018, 47(4): 160
Zhao X F, Niinomi M, Nakai M, et al. Beta type Ti-Mo alloys with changeable Young's modulus for spinal fixation applications [J]. Acta Biomater., 2012, 8: 1990
doi: 10.1016/j.actbio.2012.02.004
pmid: 22326686
13
Elahinia M H, Hashemi M, Tabesh M, et al. Manufacturing and processing of NiTi implants: A review [J]. Prog. Mater. Sci., 2012, 57: 911
doi: 10.1016/j.pmatsci.2011.11.001
14
Mendonça G, Mendonça D B S, Aragão F J L, et al. Advancing dental implant surface technology—From micron- to nanotopography [J]. Biomaterials, 2008, 29: 3822
doi: 10.1016/j.biomaterials.2008.05.012
pmid: 18617258
15
Jiao Y. Surface treatment and microstructure of biomedical titanium alloy [D]. Dalian: Dalian University of Technology, 2013
焦 岩. 生物医用钛合金表面处理及其微结构 [D]. 大连: 大连理工大学, 2013
16
Liu X Y, Chu P K, Ding C X. Surface modification of titanium, titanium alloys, and related materials for biomedical applications [J]. Mater. Sci. Eng., 2004, R47: 49
17
Hung K Y, Lin Y C, Feng H P. The effects of acid etching on the nanomorphological surface characteristics and activation energy of titanium medical materials [J]. Materials, 2017, 10: 1164
doi: 10.3390/ma10101164
18
Petersen A G, Klenerman D, Hedges W M, et al. Effect of cavitation on carbon dioxide corrosion and the development of a test for evaluating inhibitors [J]. Corrosion, 2002, 58: 216
doi: 10.5006/1.3279872
19
Hori N, Iwasa F, Ueno T, et al. Selective cell affinity of biomimetic micro-nano-hybrid structured TiO2 overcomes the biological dilemma of osteoblasts [J]. Dent. Mater., 2010, 26: 275
doi: 10.1016/j.dental.2009.11.077
20
Gittens R A, McLachlan T, Olivares-Navarrete R, et al. The effects of combined micron-/submicron-scale surface roughness and nanoscale features on cell proliferation and differentiation [J]. Biomaterials, 2011, 32: 3395
doi: 10.1016/j.biomaterials.2011.01.029
pmid: 21310480
21
Li N B. Biological behaviors of micro/nano-scale bioactive oxide coatings prepared by induction heating on medical titanium and its alloys [D]. Jinan: Shandong University, 2018
Verheul M, Drijfhout J W, Pijls B G, et al. Non-contact induction heating and SAAP-148 eliminate persisters within MRSA biofilms mimicking a metal implant infection [J]. Eur. Cell. Mater., 2021, 42: 34
doi: 10.22203/eCM
23
Kokubo T, Takadama H. How useful is SBF in predicting in vivo bone bioactivity? [J]. Biomaterials, 2006, 27: 2907
doi: 10.1016/j.biomaterials.2006.01.017
pmid: 16448693
24
Wang H Y, Zhu R F, Lu Y P, et al. Structures and properties of layered bioceramic coatings on pure titanium using a hybrid technique of sandblasting and micro-arc oxidation [J]. Appl. Surf. Sci., 2013, 282: 271
doi: 10.1016/j.apsusc.2013.05.119
25
Jung S C, Lee K, Kim B H. Biocompatibility of plasma polymerized sandblasted large grit and acid titanium surface [J]. Thin Solid Films, 2012, 521: 150
doi: 10.1016/j.tsf.2011.12.089
26
Saldaña L, Barranco V, González-Carrasco J L, et al. Thermal oxidation enhances early interactions between human osteoblasts and alumina blasted Ti6Al4V alloy [J]. J. Biomed. Mater. Res., 2007, 81A: 334
doi: 10.1002/jbm.a.v81a:2
27
Gobbato L, Arguello E, Martin I S, et al. Early bone healing around 2 different experimental, HA grit-blasted, and dual acid-etched titanium implant surfaces. A pilot study in rabbits [J]. Implant Dent., 2012, 21: 454
doi: 10.1097/ID.0b013e3182611cd7
pmid: 23149502
28
Szmukler-Moncler S, Perrin D, Ahossi V, et al. Biological properties of acid etched titanium implants: Effect of sandblasting on bone anchorage [J]. J. Biomed. Mater. Res., 2004, 68B: 149
doi: 10.1002/(ISSN)1097-4636
29
Vanzillotta P S, Sader M S, Bastos I N, et al. Improvement of in vitro titanium bioactivity by three different surface treatments [J]. Dent. Mater., 2006, 22: 275
pmid: 16054681
30
Le Guéhennec L, Soueidan A, Layrolle P, et al. Surface treatments of titanium dental implants for rapid osseointegration [J]. Dent. Mater., 2007, 23: 844
doi: 10.1016/j.dental.2006.06.025
pmid: 16904738
31
Aparicio C, Padrós A, Gil F J. In vivo evaluation of micro-rough and bioactive titanium dental implants using histometry and pull-out tests [J]. J. Mech. Behav. Biomed. Mater., 2011, 4: 1672
doi: 10.1016/j.jmbbm.2011.05.005
pmid: 22098868
32
Chauhan P, Koul V, Bhatnagar N. Effect of acid etching temperature on surface physiochemical properties and cytocompatibility of Ti6Al4V ELI alloy [J]. Mater. Res. Express, 2019, 6: 105412
doi: 10.1088/2053-1591/ab3ac5
33
Park J Y, Davies J E. Red blood cell and platelet interactions with titanium implant surfaces [J]. Clin. Oral Implants Res., 2000, 11: 530
doi: 10.1034/j.1600-0501.2000.011006530.x
34
Ren B, Wan Y, Wang G S, et al. Influence of different acid-etching time on the surface morphology and corrosion resistance of TC4 titanium alloys after sandblasting [J]. J. Shandong Univ. (Eng. Sci.), 2017, 47(3): 139
Ooi S K, Biggs S. Ultrasonic initiation of polystyrene latex synthesis [J]. Ultrason. Sonochem., 2000, 7: 125
pmid: 10909731
38
Suslick K S, Hammerton D A, Cline R E. Sonochemical hot spot [J]. J. Am. Chem. Soc., 1986, 108: 5641
doi: 10.1021/ja00278a055
39
Rohanizadeh R, Al-Sadeq M, LeGeros R Z. Preparation of different forms of titanium oxide on titanium surface: Effects on apatite deposition [J]. J. Biomed. Mater. Res., 2004, 71A: 343
doi: 10.1002/(ISSN)1097-4636
40
Paital S R, Dahotre N B. Wettability and kinetics of hydroxyapatite precipitation on a laser-textured Ca-P bioceramic coating [J]. Acta Biomater., 2009, 5: 2763
doi: 10.1016/j.actbio.2009.03.004
pmid: 19362524
41
Li N B, Zhao X C, Geng S N, et al. Microstructures of Ti6Al4V matrices induce structural evolution of bioactive surface oxide layers via cold compression and induction heating [J]. Appl. Surf. Sci., 2021, 552: 149504
doi: 10.1016/j.apsusc.2021.149504
42
Wang W M, Lin S H, Li L, et al. Composition, microstructure and mechanical properties of Ti6Al4V (ELI) alloy bars for surgical implants [A]. The 14th National Titanium and Proceedings of the Titanium Alloy Academic Exchange Conference (Volume 1) [C]. Shanghai: Shanghai Scientific and Technological Literature Press, 2010: 555
Singhvi R, Stephanopoulos G, Wang D I C. Effects of substratum morphology on cell physiology [J]. Biotechnol. Bioeng., 1994, 43: 764
pmid: 18615800
44
Kim H K, Jang J W, Lee C H. Surface modification of implant materials and its effect on attachment and proliferation of bone cells [J]. J. Mater. Sci.: Mater. Med., 2004, 15: 825
doi: 10.1023/B:JMSM.0000032824.62866.a1
45
Rønold H J, Ellingsen J E. Effect of micro-roughness produced by TiO2 blasting—Tensile testing of bone attachment by using coin-shaped implants [J]. Biomaterials, 2002, 23: 4211
pmid: 12194524
46
Ponsonnet L, Reybier K, Jaffrezic N, et al. Relationship between surface properties (roughness, wettability) of titanium and titanium alloys and cell behaviour [J]. Mater. Sci. Eng., 2003, C23: 551
47
Zhao X. Mechanism investigation on osteoblast adhesion affected by Ti6Al4V biological materials surface roughness [D]. Harbin: Harbin Institute of Technology, 2010