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Materials Science and Engineering C 27 (2007) 700 708 www.elsevier.

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Biomimetic calcium phosphate coatings on nitric-acid-treated titanium surfaces


Xiong Lu a,b,, Zhanfeng Zhao a , Yang Leng a
a

Department of Mechanical Engineering, Hong Kong University of Science and Technology, Kowloon, Hong Kong, China b Key Lab of Advanced Technologies of Materials, Ministry of Education, School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China Received 8 January 2006; accepted 26 June 2006 Available online 4 August 2006

Abstract This study describes biomimetic calcium phosphate (Ca-P) coatings formation under simulated physiological conditions on Ti surfaces that go through nitric acid treatment (NT). In the present study, nitric acid treatment was used to treat Ti specimens so that Ti specimens could have the ability to induce Ca-P formation. After careful selection of the NT parameters, Ca-P coatings success fully formed on the nitric-acid-treated Ti surfaces in a supersaturated calcium phosphate solution (SCPS) and in the simulated body fluid (SBF). Before NT, the Ti specimen should go through mixed acid etching to increase its surface roughness because rough surfaces lead to good adherence between coatings and substrates. Amorphous Ca-P coatings were formed on the Ti surfaces by immersing the NT Ti specimens in SBF, while octacalcium phosphate (OCP) coatings were formed in the SCPS after 3 days of immersion. The study firstly proved that nitric acid treatment is not only just for surface passivation but also is another bioactive treatment as an alternative to the alkaline treatment and two-step method. The experimental results also confirmed that the conventional nitric acid treatment of a titanium surface does not increase the titanium oxide on the Ti surfaces. However, extending the nitric acid treatment time and enhancing the nitric acid treatment temperature help to increase Ti surface ability of Ca-P induction in simulated physiological environments. Ti specimens that had 600 min of NT at 60 C had the best Ca-P induction ability under biomimetic conditions. 2006 Elsevier B.V. All rights reserved.
Keywords: Biomimetic; Nitric acid treatment; Calcium phosphate coatings; Titanium

1. Introduction Titanium and titanium alloy implants have become the most commonly used biomedical materials due to their biocompatibility, excellent corrosion resistance and good mechanical properties and lightness. Generally speaking, titanium without any surface treatment is bioinert, not bioactive. Various techniques have been developed to deposit bioactive calcium phosphate (Ca-P) coatings on Ti substrates, such as plasma spraying [1,2], electrochemical deposition [3], solgel deposition [4], sputtering [5] and pulsed laser deposition [6]. Recently, bio Corresponding author. Key Lab of Advanced Technologies of Materials, Ministry of Education, School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China. Tel.: +86 28 87634023; fax: +86 28 87601371. E-mail address: luxiong@home.swjtu.edu.cn (X. Lu). 0928-4931/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.msec.2006.06.030

mimetic methods to produce Ca-P coatings on Ti surfaces have attracted considerable research attention [710]. The biomimetic methods produce Ca-P coatings by immersing metal implants in aqueous solutions containing calcium and phosphate ions at physiological temperatures and pH. This alternative coating technique offers several advantages, such as the ability to produce coatings on porous surfaces [1113], processing at ambient temperatures suitable for polymer substrates [1416] and the possibility to incorporate bioactive agents and proteins [1719]. Biomimetic coating requires pretreatment of Ti surfaces because untreated Ti surfaces cannot induce Ca-P nucleation in simulated physiological environments or in supersaturated aqueous solutions. So far, several methods to treat Ti surfaces to give them Ca-P induction ability have been introduced. The most widely known one is alkaline treatment, through which a TiOH layer is formed on titanium surfaces and therefore Ca-P

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can deposit on the surfaces through this TiOH layer [20,21]. There have been a number of reports about Ca-P deposition on alkali-treated titanium surfaces in simulated body fluid (SBF), which is the solution with ion concentrations nearly equal to human blood plasma [2023]. Another method was developed by de Groot's group. It consists of two steps to produce biomimetic Ca-P coatings on Ti surfaces [7,13,24,25]. In this method, the Ti surface is pretreated in a solution containing high concentrations of calcium and phosphate ions for a short period of time so that a thin amorphous Ca-P rich layer is pre-deposited on the Ti surfaces. Then, a thick and crystallized Ca-P coating can be easily deposited on the pretreated Ti surfaces in another supersaturated Ca-P solution. A more recent method is microarc anodic oxidation, which can produce a micro-porous layer of anatase on the surface of titanium metal, thereby accelerating the Ca-P inducing ability in SBF [2628]. In addition to these popular methods, H2O2, H2O2/HCl and simple heat passivate also have been employed to treat titanium although these treating effects are not as good as the previously described three methods according to the literature reports [2932]. In this paper, we report two types of biomimetic Ca-P coatings formation under simulated physiological environments on the Ti surfaces that only go through nitric acid treatment. Nitric acid passivation, recommended by ASTM, is a surface treatment that ensures passive Ti surfaces, not for inducing Ca-P formation [33]. Collen et al. found that nitric acid passivation actually reduces the oxide thickness on the Ti6Al4V alloy while having no significant effect on the pure Ti [34,35]. Chen et al. used nitric acid passivation as a pretreatment before alkaline treatment to form a bioactive layer on NiTi alloy [36]. Chang et al. studied the Ca and P adsorption on nitric acid passivation Ti surfaces immersed in Hank's solution and the thickness of the Ca and P containing layer is equivalent to 4.0 ionic monolayers even after as long as the 16-day immersion [37]. Although a variety of studies have been done on the nitric acid passivated Ti surfaces, none of these researches revealed that nitric acid passivated Ti surfaces have the ability to induce biomimetic CaP coatings after a short period of immersion. In the present study, we have found that nitric acid treatment can be used to prepare Ti surfaces for biomimetic Ca-P coating if the nitric acid treatment parameters are carefully selected. Amorphous Ca-P coatings and well-crystallized octacalcium phosphate (OCP, Ca8(HPO4)2 (PO4)45H2O) coatings are successfully formed on Ti surfaces that go through elaborated designed nitric acid treatments. Various characterization methods were used to characterize the as-treated Ti surfaces and the results show that the surface energy and the composition of the outermost layer of Ti substrates are critical for inducing Ca-P coatings formation. 2. Experimental 2.1. Specimen preparation The titanium specimens used in the present study were CP Grade 4 Ti (commercially pure titanium) from Baoji Special Iron and Steel Co. LTD, Baoji, Shaanxi, China. The titanium plates were cut into small squares (10 mm 10 mm 1 mm) and

ultrasonically cleaned by acetone and deionized water for 15 min each before being used. The following four types of Ti surface treatment were used for our comparative study. 2.1.1. Acid etching (AE) The specimens are etched with a mixed acid solution (a volume ratio of 98% H2SO4:36% HCl:H2O = 1:1:1) at 60 C for 1 h, then immersed in deionized water for ultrasonic cleaning for 15 min and dried in the air. Acid etching removes the natural titanium oxide and generates rough surfaces. 2.1.2. Nitric acid treatment (AE + NT) Some of the specimens that had AE treatment were further immersed in nitric acid (a volume ratio of 65% HNO3:H2O = 1:1) at 20 C and 60 C to study the temperature effects. The treatment time was 20, 60, 300, and 600 min to study the processing time effect. Note that 20 min is a standard surface preparation processing time recommended for passivation by ASTM-F86 [33]. Before immersion in the Ca-P solution, the as-treated specimens were cleaned with deionized water using ultrasonic vibration for 15 min to bring the pH value to neutral. They were then dried in the air. 2.1.3. Polished Ti The as-received Ti specimens were only polished without going through acid etched. The specimens were first ground with the silicon carbide papers with grits of 600, 2400 and 4000, polished with the 0.05 m alumina powder, and then cleaned with the deionized water. 2.1.4. Polished + NT Some of the specimens that had been polished were further immersed in nitric acid (a volume ratio of 65% HNO3:H2O = 1:1) at 60 C for 600 min and then cleaned with deionized water using ultrasonic vibration. 2.2. Ca-P deposition A revised SBF recipe that was proposed by Kokubo et al. was used in the present study to deposit amorphous Ca-P coatings on titanium substrate [38,39]. The SBF was prepared by dissolving the following chemicals in the sequence of NaCl (5.403 g), NaHCO3 (0.736 g), Na2CO3 (2.036 g), KCl (0.225 g), K2HPO4 (0.182 g), MgCl26H2O (0.559 g), HEPES (2-(4-(2-hydroxyethyl)-1-piperazinyl) ethane sulfonic acid) (11.928 g), CaCl2 (0.276 g), Na2SO4 (0.072 g), and 1 M NaOH. They were buffered at pH 7.40, 37 C with HEPES and 1 M-NaOH. In order to simulate the in vivo process more closely, as-treated titanium plates were immersed in a sealed SBF glass container, which was kept in 37 C water bath. The SBF was refreshed every 3 days in order to keep the ion concentration stable. A simple supersaturated calcium and phosphate solution (SCPS) with high calcium and phosphate ion concentrations was used for another biomimetic coating study. SCPS was prepared by dissolving NaCl (7.714 g), CaCl2 (1.387 g), Na2HPO42H2O (0.89 g) and 1 M HCl 50 ml in 1 l of deionized

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water. Trishydroxymethyl aminomethane (TRIS) was used to adjust the pH value to 6.2 in order to maintain the chemical stability of the solution. In SCPS, Mg2+ and HCO3 , which are generally regarded as Ca-P crystallization inhibitors, were removed [40]. The ion concentrations in SBF and SCPS are listed in Table 1. 2.3. Characterization The surface roughness Ra of the as-treated titanium plates was measured by a three-dimensional optical surface profiler (WYKO NT3300, Veeco Instruments Inc, USA). The morphology of various treated titanium surfaces was observed with scanning electron microscopy (SEM) (JSM-6300, JEOL, Japan). The phases of the different titanium surfaces were identified using a thin-film X-ray diffractometer (TF-XRD) (X'pert pro-MPD, PANalytical, The Netherlands). The TF-XRD measurements were performed using a Cu-K (wavelength = 1.54056 ) X-ray source with a grazing incident angle of 0.5 and a step rate of 0.01 per second. The chemical composition of the outmost layer of the variously treated titanium specimens was determined by X-ray Photoelectron Spectroscopy (XPS). The XPS analyses were conducted with a multi-technique surface analysis system (PHI 5600, Physical Electronics, USA) equipped with a monochromatic Al-K excitation source (h = 1486.6 eV). The examined areas were elliptical in shape with a short axis of 800 m. The sample was positioned at the electron take-off angle of 45 with respect to the analyzer, which worked at a pass energy of 187.85 eV for the survey spectra and 58.7 eV for the high-resolution scans. Survey spectra (01400 eV) and high-resolution spectra of the O1s and Ti2p were obtained. The binding energy (BE) scale was referenced to the C1s peak of adventitious carbon (BE = 285.0 eV). The accuracy of the BE measurements was 0.2 eV. The surface energies of the treated Ti surfaces were determined from contact angle measurements, which were carried out with a Digidrop instrument (GBX Scientific Instrumentation, France) through the sessile-drop technique. The liquid droplets were dropped onto the solid surfaces by a microsyringe. The contact angles were measured having a base diameter from 5 to 10 mm to avoid any effect of drop size on the measured contact angle values. Ten specimens were tested for each type of chemically treated surface. The surface energies were calculated based on the OwensWendt (OW) method [41].
Table 1 Ion concentrations of human blood plasma, SBF and SCPS Ion Concentration (mM/l) Blood plasma Na K+ Mg2+ Ca2+ Cl HCO 3 HPO2 4 2 SO4
+

Fig. 1. SEM micrographs of Ti surfaces: (a) after AE; (b) after NT for 600 min at 60 C.

According to the OW method, the surface energy of a solid is related to the contact angle () as follows: q q p d 1 coshgL 2 gd 1 gp S gL S gL
d p and L are its where L is the liquid surface tension and L d p dispersion and polar components, respectively; and S and S are the dispersion and polar components of the solid surface tension, respectively. The final surface energy of the solid (S) is equal to d p the sum of its dispersion (S ) and polar (S ) components. The two

SBF 142.0 5.0 1.5 2.5 103.0 27.0 1.0 0.5

SCPS 142.0 12.5 217.0 5.0

142.0 5.0 1.5 2.5 103.0 27.0 1.0 0.5

Fig. 2. Surface roughness (Ra) comparison of various titanium surfaces.

X. Lu et al. / Materials Science and Engineering C 27 (2007) 700708 Table 2 Contact angle measurement results Ti surface AE Polished Polished + NT AE + NT Water drop 89.2 3.5 42.2 4.1 35.9 3.7 0

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Glycerol drop 82.1 4.7 52.6 3.1 55.6 3.2 0

Note: here NT means immersed in nitric acid for 600 min at 60 C.

substrates. The as-prepared coatings on the titanium surfaces were also examined using a TF-XRD (Model X'pert pro-MPD). 3. Results 3.1. Titanium surface characterization
Fig. 3. XRD spectra of AE and NT surfaces: (a) AE; (b) AE + NT for 20 min at 25 C; (c) AE + NT for 600 min at 25 C; (d) AE + NT for 20 min at 60 C; (e) AE + NT for 60 min at 60 C; (f) AE + NT for 300 min at 60 C; (g) AE + NT for 600 min at 60 C.

testing liquids used in the present study were deionized water ( = 72.8 mJ/m2, p = 51.0 mJ/m2, d = 21.8 mJ/m2) and glycerol ( = 63.4 mJ/m2, p = 26.4 mJ/m2, d = 37.0 mJ/m2) [41,42]. The morphology of the Ca-P coatings on the various treated titanium surfaces was examined with SEM (JSM-6300, Japan). Transmission electron microscopy (TEM) (JEOL 2010, JEOL, Tokyo, Japan) was used to examine the morphology and crystal structures of the calcium phosphates extracted from the Ti

3.1.1. Surface morphology and roughness The SEM examinations revealed that the morphologies of the surfaces with acid etching (AE) and of the surfaces with further nitric acid treatment (AE + NT) were quite similar (Fig. 1). The AE process made the grain boundaries visible on the rough surfaces. AE + NT seems not to have contributed significantly to surface roughening, as revealed in a comparison of Fig. 1a and b. Three-dimensional optical surface profiler examinations demonstrated that the surface roughness difference between the AE surface and the AE + NT surface was only about 10% (Fig. 2). This difference is minor compared with the roughness difference between the polished surface and the AE surface (Fig. 2). 3.1.2. TF-XRD and XPS examinations Fig. 3 shows the TF-XRD spectra of the titanium specimens after various treatments. The spectra show the same diffraction peaks of the titanium (-Ti) phase in the AE and the AE + NT specimens, which include specimens treated for different NT time at 25 C or 60 C. However, these spectra do not exhibit diffraction of titanium oxides. These results indicate that the surface oxide layers were too thin to be detected by the thin film X-ray diffraction examinations. XPS, which is able to detect the chemistry within 5 to 10 nm from a surface, provided us with the information on the oxides on the Ti surfaces. Fig. 4 shows the XPS spectra of Ti binding energies from which Ti chemical environments can be determined. The XPS spectra of the Ti surfaces show Ti4+ peaks corresponding to Ti in TiO2 and Ti0 peaks corresponding to Ti metal on the AE and the AE + NT surfaces including those treated for different NT duration time at 25 C or 60 C [11,43]. The visible Ti0 peak implies that the thickness of the TiO2 layer on either the AE or
Table 3 Surface energies of titanium surfaces calculated via the OW method (mJ/m2) Ti surface AE Polished Polished + NT AE + NT d S 15.84 3.90 0.66 p S 6.72 57.47 75.60 S 22.56 61.37 76.26

Fig. 4. High resolution XPS spectra of various titanium surfaces: (a) AE; (b) AE + NT for 20 min at 25 C; (c) AE + NT for 600 min at 25 C; (d) AE + NT for 20 min at 60 C; (e) AE + NT for 60 min at 60 C; (f) AE + NT for 300 min at 60 C; (g) AE + NT for 600 min at 60 C.

Note: here NT means immersed in nitric acid for 600 min at 60 C. AE + NT surface has a too large surface energy to be measured by OW method.

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Fig. 5. SEM micrographs of globule-like Ca-P formed in SBF: (a) AE surface, after 10 days of SBF immersion; (b) NT for 300 min at 60 C, after 1 day of SBF immersion; (c) NT for 600 min at 60 C, after 1 day of SBF immersion; (d) NT for 600 min, at 60 C, after 10 days of SBF immersion.

NT surfaces was limited to 510 nm. This implies that the NT process after AE treatment did not increase the oxide thickness on the Ti substrates even after increasing the NT temperature and duration. Our XPS results are consistent with those obtained by Callen et al. [34,35]. They followed ASTM-F86 protocol to passivated Ti6Al4V using nitric acid and found that the treatment actually reduced the oxide thickness on the alloy.

3.1.3. Surface energy The contact angles of glycerol and water drops on various Ti surfaces were measured and are listed in Table 2. The surface energies calculated from the contact angles using Eq. (1) are listed on Table 3. The contact angles on other surfaces were measured except for the one on the AE + NT surface, which were zero, indicating complete wettability with either glycerol

Table 4 Summary of Ca-P deposition on variously treated Ti surfaces in SBF that clearly indicates the effect of NT on the increasing of Ti surface Ca-P induction ability Ti surface Treatment temperature (C) 60 25 Treatment time (min) 300 20 60 300 600 20 60 300 600 600 SBF immersion (day) 1 X X X X X X X X X 3 X X X X X X X X 7 X X X X X X X 10 X X X X X X X

AE AE + NT

60

Polished Ti Polished + NT

60

Note: here represents the Ca-P formation on the as-treated surfaces while X represents the inverse case.

Fig. 6. The disproof the surface roughness importance that shows Ca-P coating formation on polished + NT Ti surface after 3 days SBF immersion. Due to the low surface roughness, the adhesion between the Ti substrate and the Ca-P coating was so weak that some of the coating films peeled off.

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on the surface of the 10-h NT treatment when the SBF immersion time was increased (Fig. 5d). The detailed examination results are summarized in Table 4, from which we note that the NT temperature and duration were critical factors affecting the Ca-P induction ability of the Ti surfaces. The Ti surfaces did not acquire the Ca-P formation ability with NT at 25 C, even when the treatment lasted for 10 h. However, the Ti surfaces with NT at 60 C could induce Ca-P deposition after only 1 h of treatment. The importance of treatment duration time is exhibited in a comparison of Ca-P formation among the specimens with NT at

Fig. 7. (a) Uniform OCP coatings on the Ti surface with 300 min NT at 60 C after 3 days of SCPS immersion. (b) Magnified image of (a) that reveals the plate-like OCP crystals.

or water. The non-zero contact angles enabled us to obtain the Ti surface energies as shown in Table 3. The zero contact angles on the AE + NT surfaces made the surface energy calculation impossible. However, we might estimate the surface energy of the AE + NT specimen that it should be, at least, larger than that of the polished + NT surfaces. Tables 2 and 3 indicate the different surface treatment effects on the contact angle measurement and, in turn, surface energy calculation. We might rank the surface energies of the various chemically treated surfaces AE b Polished b polished + NT b AE + NT. 3.2. Biomimetic Ca-P coatings 3.2.1. Ca-P coatings in SBF SEM examinations revealed the significant effects of NT on inducing Ca-P deposition in simulated physiological environments. Fig. 5 shows the differences in Ca-P formation ability of various chemically treated surfaces. No Ca-P deposition was found on the surface of AE specimens even after immersion in SBF for 10 days (Fig. 5a). Scattered Ca-P globules were found on the specimen that had 300 min of NT at 60 C after 1 day of immersion in SBF (Fig. 5b). A layer of Ca-P globules (about 1 5 m in diameter) covered the surface of the specimen that had 600 min of NT at 60 C after 1 day of immersion in SBF (Fig. 5c). These globules formed a uniform layer of Ca-P coating

Fig. 8. TEM micrographs of Ca-P crystal extracted from Ti surface: (a) bright field image of a single crystal; (b) its diffraction pattern.

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Fig. 9. TF-XRD spectrum of Ca-P deposited on Ti surface with NT.

60 C. A 20-min NT could not impart the Ca-P induction ability to Ti surfaces. Note that 20 min is the passivation treatment time recommended by ASTM-F86. The examination results show that at least 1 h of treatment is required for imparting the Ca-P induction ability to Ti surfaces. Table 4 clearly indicated that a long duration of NT at a higher temperature will be a suitable pretreatment of Ti surfaces to yield biomimetic Ca-P coatings. The results shown in Table 4 also indicate that the AE prior to NT is not necessary for Ca-P induction. AE however generates large surface roughness, which helps in adhesion between the Ca-P layer and Ti substrate. Fig. 6 is the disproof of the surface roughness effect on the coatings adhesion strength that shows the Ca-P coatings formation on the polished + NT Ti surfaces after 3 days of SBF immersion. As demonstrated in Fig. 6, the substrate is the polished surface that has a low surface roughness and the deposited Ca-P coatings peeled off from the substrate. Although NT imparts Ti surface Ca-P induction ability, the Ca-P layer is likely to peel off due to the weak adhesive strength between the coating and the substrate. Thus, the Ti specimen should go through mixed acid etching before NT to increase its surface roughness because rough surfaces lead to good adherence between coatings and substrates. Our previous study demonstrated that the Ca-P globules formed in SBF are OCP with a certain amount of gel-like amorphous Ca-P, even though they are often mistakenly identified as bone-like apatite [44]. The Ca-P deposition on NT surfaces in SCPS further supports our arguments in the following section. 3.2.2. Ca-P coatings in SCPS Ti specimens with NT at 60 C also exhibit Ca-P induction ability in SCPS. Fig. 7 shows that such specimens were covered with plate-like crystals with regular shape after 3 days of immersion in SCPS. These Ca-P crystals generated flower-like clusters on Ti substrate. Note that OCP crystals commonly exhibit this plate-like morphology [11,45]. The TEM examinations of the plate-like crystals confirmed their OCP structures. Fig. 8 shows the TEM image, and its diffraction pattern of plate-

like crystals extracted from the Ti specimen surface. The diffraction pattern was indexed as that of OCP with the central electron beam direction as B = [110]. The plane spacing of 0) is a unique feature 0.938 nm corresponding to that of OCP (11 of the OCP structure. The XRD spectrum of Ca-P deposition in SCPS displays sharp diffraction peaks at 2 = 4.7 corresponding to (100) and at 2 = 25.5 corresponding to the (002) plane diffraction (Fig. 9). Both are the typical peaks of triclinic OCP crystals [7,46]. 4. Discussion This study clearly indicates that NT can cause a titanium surface to induce Ca-P deposition, regardless if the surface is polished or made rough with acid etching. Comparison of the CaP deposition on AE and AE + NT treated Ti surfaces proved that surface energy is the most critical factor for inducing Ca-P formation since the AE treated Ti surfaces have a much lower surface energy than of AE + NT treated Ti surfaces. This result further proved that NT effect is not for cleaning Ti surface from organic or inorganic contaminants because the AE procedure used in the present study is the standard surface cleaning procedure for Ti substrate. The significant effect of NT on Ti surfaces is an increase in surface energy, particularly the polar component of the surface energy. Ca-P formation on the Ti surfaces in supersaturated aqueous solutions is a heterogeneous nucleation process. In classical nucleation theory, the critical free energy (Gce:sup>/ ce:sup> heter) for heterogeneous nucleation depends on the supersaturation of the solution (S), the temperature (T), the surface energies of the substrate (S) and the nucleus (), and the interfacial energy of the substrate/nucleus (i) [47]:
DG heter DGhom

Dr 16pv2 r3 r ri rs d 2r 3k 2 T 2 lnS 2 2r

where k is the Boltzmann constant; is the net interfacial is the critical free energy for the homogenous energy; and Ghom

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nucleation. Reduction of the critical free energy, resulting in a lower energy barrier to heterogeneous nucleation, can be achieved by increasing the supersaturation and reducing the net interfacial energy. In this study, the solution supersaturation (S) was constant for all types of specimens. Apparently, G heter on the NT surface was reduced because the treatment increased S. Our observations revealed that Ca-P formation behavior on astreated Ti surfaces is well consistent with the classical heterogeneous nucleation theory. As described in the previous section, there was no Ca-P formation on the AE specimens which have the lowest surface energy, whereas a large amount of Ca-P nuclei appeared on the NT specimens which have the highest surface energies among the specimens. It should be pointed out that it is difficult to establish a quantitative relation between the ability of Ca-P deposition and surface energy. It is even difficult to compare the Ti surface energy obtained by us with that reported in literature because of differences in treatment conditions. For example, the surface energies of the NT surfaces presented here are much higher than the surface energies reported by Kilpadi's group [48]. Note that Kilpadi et al. found correlations between the titanium surface composition and the surface energy through statistical analysis [4850]. However, it seems that the ability of Ca-P deposition on Ti surfaces was solely controlled by the surface energy because we found no differences in the other chemical parameters among variously treated Ti surfaces in this study. 5. Conclusions This work firstly described biomimetic calcium phosphate (Ca-P) coatings formation on nitric acid treated Ti surfaces under simulated physiological conditions. The results firstly reveal that nitric acid treatment is another bioactive treatment that can induce Ca-P coatings formation as an alternative to the alkaline treatment and two-step method. However, the treating parameters should be carefully selected instead of just following ASTM-F86. A titanium surface treated with nitric acid for 10 h at 60 C exhibits excellent ability of inducing Ca-P coatings formation in simulated body fluid or in supersaturated aqueous solutions. Acknowledgements This project was financially supported by the Research Grants Council of Hong Kong (HKUST 6037/02E) and the Funds for High Impact Areas at Hong Kong University of Science and Technology. The characterization of the samples was conducted at the Materials Characterization and Preparation Facility at the Hong Kong University of Science and Technology. References
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