Surface & Coatings Technology 198 (2005) 247 252 www.elsevier.

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Microstructural characterization of biomedical titanium oxide film fabricated by electrochemical method

Han-Jun Oha, Jong-Ho Leeb, Yongsoo Jeongc, Young-Jig Kimd, Choong-Soo Chie,*
Dept. of Materials Science, Hanseo University, Seosan 352-820, South Korea b Dept. of Chemistry, Hanseo University, Seosan 352-820, South Korea c Korea Institute of Machinery and Materials, Changwon 641-010, South Korea d Dept. of Metallurgical Engineering, Sungkyunkwan University, Suwon 440-746, South Korea e School of Advanced Materials Engineering, Kookmin University, Seoul 136-702, South Korea Available online 18 November 2004
a

Abstract For an application as biomedical materials of high performance with a good biocompatibility, the anodic TiO2 layer on Ti substrate has been fabricated by electrochemical method, and the characteristics of anodic titania film have been investigated. X-ray diffraction (XRD) results indicate that the titania film formed in acidic electrolyte with additives is mainly composed of anatase structure containing rutile. From the analysis of chemical states of the anodic film using X-ray photoelectron spectroscopy (XPS), phosphorus and sulfur were observed in the anodic film, which were penetrated from the electrolyte into the oxide layer during anodic process. From the result of biological evaluation in simulated body fluid (SBF), the anodic TiO2 film was effective for bioactive property. D 2004 Elsevier B.V. All rights reserved.
Keywords: Anodizing; Titanium oxide; X-ray diffraction; Photoelectron spectroscopy

1. Introduction In biomedical implants and dental fields, titanium has been widely utilized for excellent corrosion-resistance and biocompatibility. However, Ti and its alloys are nonbioactive after being implanted in bone. Thus, for further improvement in biocompatibility the various implant surface modifications have been investigated. These surface modifications have included sandblasting [1], acid etching [2], combination of sandblasting and acid etching [3], sol gel technique [46], deposition of Ti coatings using plasma spraying, and deposition of calcium phosphate or hydroxyapatite (HA) coatings [711]. In this study, for the purpose of improvement in biocompatibility the anodic TiO2 layer on Ti substrate was fabricated by electrochemical method in acidic solution, and the characteristics of anodic titania film has been examined. And the biological evaluation of the

anodic TiO2 films formed in acidic solution was performed in a simulated body fluid.

2. Experimental A commercial grade pure titanium (99.6 wt.%) was used for anodization. The titanium specimens with dimensions of 8100.5 mm were mechanically polished and degreased in n-hexane for 6 min, and then washed and dried. After the pretreatment, the titanium oxide films for application of biomaterials were prepared by anodizing at a constant voltage of 180 V in 1.5 M H2SO4, 0.3 M H3PO4 and 0.3 M H2O2 mixture solution. For the comparison of bioactive test, the etched titanium without anodization was prepared by pickling in 30 vol.% nitric acid and 3 vol.% of hydrofluoric acid. The microstructures of anodic TiO2 film and thickness were observed using a scanning electron microscope (JSM5410/EDS). Identification of the phase of anodic TiO2 films was carried out using an XRD (Philips, PW1710). The analysis of chemical states by X-ray photo-

* Corresponding author. Tel.: +82 2 910 4666; fax: +82 2 910 4320. E-mail address: cschi@kookmin.ac.kr (C.-S. Chi). 0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2004.10.029

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Fig. 1. Surface morphologies of anodic TiO2 films with anodizing time at 180 V in 1.5 M H2SO4, 0.3 M H3PO4 and 0.3 M H2O2 mixture solution.

electron spectroscopy (XPS, PHI 5700) was performed at an accelerating voltage of 15 kV and current of 30 mA with a magnesium Ka radiation. After the anodic oxidation, the TiO2 films were soaked in 50 mL of simulated body fluid (SBF) with ion concentration (Na+: 142, K+: 5.0, Mg2+: 1.5, Ca2+: 1.5, Cl: 147.8, 2 2 HCO3: 4.2, HPO4 : 1.0, and SO4 : 0.5 mM) nearly equal to human blood plasma, which was developed by Kokubo et al. [12]. The SBF was prepared by dissolving reagent grade chemicals of NaCl, KCl, NaHCO3, K2HPO4, MgCl2, CaCl2 and Na2SO4 into distilled water, and buffered at pH 7.40 with tris (hydroxymethyl) aminomethane and 1 M HCl at 37 8C. After the immersion in a SBF solution at 37 8C in the normal incubator for 5 days, surface of sample was observed by SEM.

3. Results and discussion 3.1. Characteristics of anodic TiO2 film To obtain the anodic TiO2 layer an anodic constant current of 35 mA/cm2 was applied on titanium surface, and

then the anodic potential was increased slowly. When the anodizing potential reached a value of 180 V, anodizing process was carried out at a constant potential of 180 V. During anodizing process the variations of surface morphology of titanium is exhibited in Fig. 1. At the early stage of anodization the anodic TiO2 layer was uniform and less porous than that of anodic film formed at higher potentials. At higher potential than 90 V the anodizing process was led to increased gas evolution and also frequent sparking phenomena. At the same time, anodic pore cell structure began to nucleate at the surface, and the irregular arrays of cell structure have gradually changed to regular morphology. Under constant potential of 180 V the pore cell size increased with the anodic time The anodic titanium oxide film formed by electrochemical method at 180 V for 30 min in 1.5 M H2SO4, 0.3 M H3PO4 and 0.3 M H2O2 mixture solution is shown in Fig. 2a. The analyses of pore distribution were performed using Image analyzer (Image Proplus, Media Cybernetics), and thickness was observed using SEM, and the results are shown in Fig. 2b. Fig. 2a shows the variation of pore diameters of TiO2 cell structure with anodic time. At an early stage of anodization the diameters of the pores are smaller and distributions are

Fig. 2. Electron micrograph of cross sectioned TiO2 film (a) and the relationship between average pore diameter and anodic film thickness with anodizing time at 180 V in 1.5 M H2SO4, 0.3 M H3PO4 and 0.3 M H2O2 mixture solution (b).

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more scattered. As can be seen in Fig. 2a, the growth of pore diameter of cell structure with anodic time increases rapidly in the beginning stage of anodizing, which indicates average pore diameter of 0.32 Am for 5 min, 0.56 Am for 30 min, and then growth of pore diameter increases linearly. Therefore the cell structure on anodic oxide film revealed a normal frequency distribution by gradual growth of early generated micropores, and the thickness of TiO2 film increased linearly with anodic time. The pore diameter and layer thickness of anodic TiO2 increase with anodic time, and the anodic film thickness is dependent on anodic time with a rate of 3.15102 Am/min at 180 V. Fig. 3 shows the X-ray diffraction (XRD) patterns of the anodic titania film with anodic time. The anatase phase with rutile revealed in XRD results in early stage of anodization. And titanium peak observed in pattern is due to the titanium substrate. As the anodic reaction increased, the X-ray peak intensities of anatase gradually increased, and the crystalline phase of anodic films was predominantly anatase. It is well known that the TiO2 has three crystal structures such as anatase, rutile and brookite, and the anatase TiO2 is more reactive than the rutile [13]. Fig. 4 shows XPS wide scan spectrum of an anodic TiO2 layer formed at 180 V for 30 min. From the analysis of narrow scan of XPS spectrum, the chemical states of O-1s, P-2p, S-2p, and Ti-2p were 2 identified in the forms of P2O5, SO4 , TiO2 (anatase, rutile), Ti2O3. Therefore, during anodization in the electrolyte of H2SO4, H3PO4 and H2O2 mixture solution, it is found that P and S were incorporated into the anodic oxide layer. And also it can be described that P migrates inward across the TiO2 layer in the initial stage of anodization, and S in the later stage of it. Fig. 5 shows depth profile of anodic titania obtained from the XPS analysis. In Fig. 5, the phosphorus is infiltrated throughout the oxide films, while sulfur is detected in oxide films close to the electrolyte/ oxide interface. This suggests that during anodization the inward diffusion of phosphorus or phosphate ion in

Fig. 4. XPS spectrum of anodic TiO2 formed at 180 V for 30 min in 1.5 M H2SO4, 0.3 M H3PO4 and 0.3 M H2O2 mixture solution.

electrolyte to the oxide/electrolyte interface is dominant rather than that of sulfur. 3.2. Effect of electrolytes The anodic oxide films on titanium are formed by anodization in electrolyte, for which anodic reaction in combination with electrical-field driven metal and oxygen ion diffusion lead to the formation of an oxide film at the anode surface, which can be written as: Ti4 ox 4H2 OaqfTiOH4 ox 2H2 fTiO2x OH2x 2 xH2 O In these reactions the structure and morphology of anodic oxides can be varied by controlling the process parameters, such as electrolyte composition. To observe the effects of electrolytes on the microstructure of anodic TiO2 film, the anodization was performed at 180 V for 30 min in various electrolyte solutions. The electrolytes were 1.5 M H2SO4 solution, 1.5 M H2SO4/0.3 M H2O2 mixture, 1.5 M H2SO4/ 0.3 M H3PO4 mixture, and 1.5 M H2SO4/0.3 M H3PO4/0.3 M H2O2 mixture solution.

Fig. 3. X-ray diffraction pattern of the TiO2 film with anodizing time.

Fig. 5. Depth profile of anodic TiO2 film formed at 180 V for 30 min.

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Fig. 6 shows microstructures of anodic titania prepared at 180 V for 30 min in various solution. The anodic TiO2 films formed in 1.5 M H2SO4 solution and 1.5 M H2SO4/ 0.3 M H2O2 mixture represent smaller cell structures than those formed in 1.5 M H2SO4/0.3 M H3PO4 mixture and 1.5 M H2SO 4/0.3 M H3PO4/0.3 M H2O2 mixture. However, considerable changes in the surface morphology are not seen only with addition of hydrogen peroxide as additive. From the results of thickness measurement the average thickness of anodic titania film formed in 1.5 M H2SO4 was 2.5 Am, 2.8 Am for H2SO4/H2O2 mixture, 3.2 Am for H2SO4/H 3PO4, and 3.6 Am for H 2SO4/H 3PO 4/H2O 2 mixture. These results indicate that due to the addition of hydrogen peroxide, the film thickness increases slightly by about 12%, but for addition of phosphoric acid, the thickness increased significantly. In general, during anodization for valve metal the oxidation takes place at metal/ oxide interface; on the other hand, oxide surface/electrolyte interface dissolves in acid electrolyte. Therefore surface morphology and layer thickness can be strongly associated with electrolyte. In aluminum anodization for fabrication of nanopore arrays in anodic alumina, Li et al. [1416] showed that anodic alumina surface with larger cell structure was observed by using phosphoric acid solution rather than sulfuric acid as electrolyte. However, for an addition of hydrogen peroxide, oxide layer can be more grown without substantial change in morphology, due to migration of oxygen containing ions from H2O2 in electrolyte. The chemical reaction of the titanium surface

Fig. 7. XRD patterns of anodic TiO2 film thickness formed at 180 V for 30 min in 1.5 M H2SO4 solution (a), 1.5 M H2SO4/0.3 M H2O2 mixture (b), 1.5 M H2SO4/0.3 M H3PO4 mixture (c), and 1.5 M H2SO4/0.3 M H3PO4/ 0.3 M H2O2 mixture solution (d).

with peroxides has been proposed by Tengvall et al. [17]. From the results of Fig. 6 and thickness measurements we therefore assume that differences in the morphology and thickness of anodic films are concerned mostly with the addition of phosphoric acid, and for the addition of hydrogen peroxide the anodic film thickness was affected slightly.

Fig. 6. SEM images showing surface oxide morphology formed at 180 V for 30 min in 1.5 M H2SO4 solution (a), 1.5 M H2SO4/0.3 M H2O2 mixture (b), 1.5 M H2SO4/0.3 M H3PO4 mixture (c), and 1.5 M H2SO4/0.3 M H3PO4/0.3 M H2O2 mixture solution (d).

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Fig. 8. SEM photographs of specimens soaked in SBF for 5 days. Morphologies of pure titanium surface etched in HF/HNO3 (a) and (b), anodized in 1.5 M H2SO4/0.3 M H3PO4/0.3 M H2O2 mixture solution (c) and (d). Original magnification, 1000 (a), 10,000 (b), 1000 (c), 10,000 (d).

Fig. 7 shows the X-ray diffraction patterns of the anodic titania film formed at 180 V for 30 min in various solutions. The phase of the titania films was basically anatase, and the rutile was also observed together with titanium peaks from the substrate. And it is exhibited that crystalline phase of the anodic oxide was dependent on the electrolytic compositions, especially for the film in Fig. 7d, indicating that anatase structure was predominant. The biological evaluation of these anodic TiO2 films formed in 1.5 M H2SO4/0.3 M H3PO4/0.3 M H2O2 mixture solution was performed in a simulated body fluid. After the immersion in a SBF solution at 37 8C in 5 days, the surface of anodic film was observed by SEM with energy dispersive spectroscopy analysis (EDS). For the comparison of biocompatibility, etched titanium specimen prepared in HNO3/HF mixture was performed in

SBF. Fig. 8 shows the morphologies of etched titanium and anodic TiO2 surface after immersion in SBF for 5 days. These results suggest that the particles were precipitated on the surface of anodic film in SBF, but no apparent changes appeared on the surface of the etched titanium, as can be seen in Fig. 8b and d, respectively. From the result of EDS analysis, as shown in Fig. 9, the precipitated particles on the surface of anodic film is revealed as Ca-rich compounds, which will be steadily converted to hydroxyapatite crystalline phase that is similar in composition and structure to bone apatite. The anodic TiO2 film formed by electrochemical method has a porous and relatively rough morphology, and composes of anatase and rutile structure. From the results in Figs. 8 and 9, it is clearly suggested that these microporous

Fig. 9. SEM micrograph and line profiles for precipitation particles on surface of anodic layer soaked in SBF for 5 days. The precipitated particles indicates Carich compound by EDS analysis.

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surface features and titanium oxide structure are all effective for biocompatibility.

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4. Conclusions The anodic titanium oxide film for biomedical applications was synthesized by anodic oxidation in acid solution, and the surface characteristics of anodic TiO2 layer has been evaluated. The major structure of anodic TiO2 film was revealed to anatase, and surface morphology exhibited a porous cell structure. For the effects of electrolytes on the microstructure of anodic TiO2 film, the differences in the morphology and thickness of anodic films concerned mostly with the addition of phosphoric acid. And for the addition of hydrogen peroxide the anodic film thickness was affected slightly. The component elements of the electrolyte, P and S, were found in the oxide layer, which were incorporated from the electrolyte into the oxide. From the result of biological evaluation in simulated body fluid, the TiO2 anodic film was effective for bioactive property.

Acknowledgments This work has been supported by the Kookmin University.