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Article

Surface Microstructure and Performance of Anodized TZ30 Alloy in SBF Solution

1
College of Materials Science and Engineering, Hebei University of Engineering, Handan 056038, China
2
Hebei Key Laboratory of Wear-Resistant Metallic Materials with High Strength and Toughness, Hebei University of Engineering, Handan 056038, China
3
Hebei Engineering Research Centre for Rare Earth Permanent Magnetic Materials & Applications, Hebei University of Engineering, Handan 056038, China
*
Author to whom correspondence should be addressed.
Metals 2022, 12(5), 719; https://doi.org/10.3390/met12050719
Submission received: 16 March 2022 / Revised: 21 April 2022 / Accepted: 21 April 2022 / Published: 23 April 2022

Abstract

:
Anodization is performed on the Ti-30Zr-5Al-3V (TZ30) alloy to improve its surface performance. X-ray diffractometer (XRD), scanning electron microscopy (SEM), and Olympus microscope are used to determine the phase constitution, morphology, and thickness of the anodization film (AOF). Tribological tests and electrochemical corrosion experiments are carried out to measure, respectively, the wear behavior and corrosion resistance of AOFs in simulated body fluid (SBF) solution. The microstructure characteristic of the AOF anodized at low voltage (20 V) is composed of compact and loose regions. As the applied voltage increases to 60 V, the compact regions transform progressively into loose regions, and then grow into nanotube regions. Besides, an increase in thickness of the AOF from 8.6 ± 4.61 μm to 20.7 ± 2.18 μm, and a gradual increase in surface microhardness from 364.6 ± 14.4 HV to 818.4 ± 19.3 HV, are also exhibited as the applied voltage increases from 20 V to 60 V. Specimens anodized at 40 V and 60 V have a low friction coefficient (~0.15) and wear rate (~2.2 mg/N/m) in the SBF solution. The enhanced wearability originates from the high hardness and various wear mechanisms. Potentiodynamic polarization curves suggest that the corrosion resistance in the SBF solution of all anodized specimens is greatly improved, thanks to the protection from the anodized TiO2 film.

1. Introduction

Ti alloys are important and commonly used biomaterials thanks to their excellent properties, such as low modulus, good biocompatibility, non-toxicity, and so on. Because of the negative effects of the “stress shielding” effect [1], the development of metallic materials with a low elastic modulus has become a vital research focus. Lots of metallic materials with low Young’s modulus are developed as implants for hard tissues [2]. The Ti-Zr-Al-V (TZAV) series alloys were developed based on TC4 alloy and have low density, higher strength, ultra-high specific strength, and product of strength and plasticity [3,4]. Apart from those excellent properties, recent research proved that the TZAV series alloys also have low elastic modulus [5,6]. Among that series of alloys, the Ti-30Zr-5Al-3V (TZ30) alloy exhibits a very low Young’s modulus of 34 GPa [5], which is very close to biological bone (10–30 GPa). Such a low modulus for a bulk metallic material is important for eliminating the stress shielding effect. Thus, a low modulus of TZ30 alloy indicates a great application potential as an implant material for hard tissues.
As an implant material for hard tissues, especially moveable joints, the surface performances (such as surface hardness, wearability, and corrosion resistance) should be investigated and improved to meet the requirements of biomaterials before actual applications. Previous works [7,8] have investigated the hardness, tribological behavior, and corrosion resistance of the TZAV series alloys, and results showed that those surface performances are similar to the TC4 alloy. Therefore, the surface performances of TZ30 alloy should also be improved and systematically researched. There are some electrical anodization methods [9], such as traditional anodization [10], plasma electrolytic oxidation (also named micro-arc oxidation) [11], and low-plasma electrolytic oxidation [12]. The improvement of those late methods on wearability and corrosion resistance is similar to or even higher than traditional anodization [13]. However, these methods have some shortcomings in widespread commercialization. To realize and keep the micro-arc stage, these methods require high voltage and current. Thus, the consumption of electricity and energy are too high [14,15], so those methods are mainly used for small samples. Among the different methods, traditional anodization (referred to simply as anodization) is widely believed to be the most proficient method, which can create highly ordered porous nanoscale structures, particularly for large-size samples or workpieces. Furthermore, the size, microstructure characteristics, growth rate, and surface roughness can be easily controlled using the traditional anodization method [13,16,17]. During anodization, oxidation reactions occur on the surface of a specimen (as the anode) with the help of the applied electric field. An oxide layer/film forms on the treated surface. For Ti alloys, the ideal oxide layer should be the TiO2 nanotube layer. At the beginning stage of the anodization, a thin and dense TiO2 layer forms. During this stage, the positions of TiO2 product should be statistically distributed. Close to the dense oxide layer, local dissolution is sped up, and nucleation of pores occurs. Such pore nucleation occurs on nearly the entire surface. Visible destabilized stretches of the first compact oxide should appear at some sites. After this process, the location of pores should be random. As the process continues, a marked dissolution starts at pore bottoms. That marked dissolution deepens pores. After a period, the initial compact TiO2 layer on the surface is gradually consumed. Finally, the porous structure promptly grows into a nanotube structure, fully developing a self-organized nanotube layer [18,19]. Usually, that oxide layer/film has favored physicochemical and mechanical properties. Therefore, the surface performances, such as surface hardness, wearability, corrosion resistance, and even biological compatibility of metallic materials can be improved to some extent [19,20,21].
In this work, anodization at various applied voltages is employed to modify the surface of the TZ30 alloy, aiming to improve its surface performance. The microstructure, surface hardness, tribological behavior, and corrosion resistance in the SBF solution of anodized TZ30 specimens are investigated and discussed. The findings should be of help in promoting the actual applications of the TZ30 alloy as implants for hard tissues.

2. Materials and Methods

The TZ30 alloy was cut into disks with a size of Φ 30 mm × 3 mm. After grinding and polishing, all disks were ultrasonically cleaned in acetone and anhydrous ethanol for 10 minutes each. After those processes, the disks, as the anode, underwent anodization for 3 h in a glycol solution containing 0.3 wt.% NH4F and 2 vol% water [22], with a graphite rod as the cathode. Several applied voltages of 20, 40, and 60 V [23] were used to prepare anodization films (AOFs) on the TZ30 substrate. The specimens anodized at applied voltages of 20, 40, and 60 V are respectively referred to as A20V, A40V, and A60V. Anodized specimens underwent irrigation using distilled water, were tumble dried, and then were annealed at 450 °C for 2 h in the argon atmosphere.
X-ray diffractometer (XRD, Rigaku Corporation, Tokyo, Japan), scanning electron microscopy (SEM, Rigaku Corporation, Tokyo, Japan), and Olympus 3D opto-digital microscope (Olympus Corporation, Beijing, China) were employed to determine the phase constitution, morphology, and composition. A Vickers microhardness tester (Shanghai Shangcai Testermachine Co., Ltd., Shanghai, China) at a total load of 0.245 N (25 gf) was employed to test the surface hardness. The tribological behavior and wearability were investigated on the MMW-1 vertical omnipotence friction wear testing machine (Time Group INC., Beijing, China) using ball-on-disk wear pairs in Ringer’s solution (Self preparation), as a simulated body fluid (SBF) solution. The composition of Ringer’s solution is 8.5 g/L of NaCl and 0.2 g/L of KCl, CaCl2, and CaHCO3. Tribological tests were carried out based on the standard ASTM E1911-19 [24]. Specimens with a size of Φ 30 mm × 2 mm were used as the disk, and standard steel balls with Φ 10 mm were used as the counter friction pair. Throughout the entire tribological test, the specimen disk and balls are always immersed in the SBF solution. The diameter of the friction path is approximately 25.4 mm. All tribological tests were performed by an applied normal load of 5 N at a sliding velocity of ~0.3 m/s (200 R/min) for 3600 s. The wear weight loss of specimens was measured to calculate the wear rate of weight (WWR), the weight loss per Newton per meter. Corrosion performance in terms of potentiodynamic polarization curve was measured with a TZ30 specimen as the working electrode, a saturated calomel electrode (SCE) as the reference electrode, and a platinum sheet as the counter electrode, respectively. The corrosion test electrolyte was also Ringer’s solution of pH 7.2. The potentiodynamic polarization curve was measured from −1.0 V (vs. SCE) in the anodic direction with a scan rate of 0.5 mV/s. Although a potential scan rate of 0.5mV/s was adopted in this stage of the experimentation, no substantial distortions in the polarization curves were attained, as previously reported [25,26,27,28].
For the accuracy and repeatability of measured data, all the above tests are repeated at least three times. The data shown in this work are the average or most representative results.

3. Results and Discussion

3.1. Microstructure of AOFs

Figure 1 shows XRD results of TZ30 specimens after anodization at different applied voltages. XRD patterns in Figure 1. prove that all anodized specimens are composed of TiO2 (anatase, PDF file #21-1272) [29] and α-Ti (PDF file #44-1294). The peaks of α-Ti should be taken from the substrate. That is because the thickness of the coating is not enough to hide the penetration of the X-ray. Similar results were also reported in previous publications [30,31]. Figure 2 shows microstructure and EDS images of AOFs on anodized specimens. The microstructure image of the AOF on specimen A20V shows two dark and light major regions (Figure 2(a1)). The magnification of the light regions in Figure 2(a2) shows a loose and fluctuant structure. The dark region is compact and smooth, as Figure 2(a3) shows. Thus, the microstructure characteristic of specimen A20V is composed of compact regions (also named barrier-type regions [32,33]) and loose regions. As the applied voltage increases to 40 V, the proportion of dark regions in Figure 2(b1) decreases. Magnifying the light region in Figure 2(b1) gradually, nanotubes can be observed in Figure 2(b3). The feature of the upper part of Figure 2(b3), as the yellow circle shows, is like that of the light region in Figure 2(a2). As the applied voltage increases further to 60 V, only the light region can be observed (Figure 2(c1)). The microstructure is homogeneous, as Figure 2(c2) shows. The magnification microstructure in Figure 2(c3) shows that nanotubes grow completely, and the diameter of tubes is larger than in specimen A40V. Qin et al. [34] showed the diameter of tubes increased with the applied voltage from 2.5 to 20 V. Gong et al. [35] also proved the diameter and length of the titanium dioxide nanotube increased with applied voltage from 30 to 60 V. The growth mechanism of the AOF is that compact regions in the AOF change into loose regions and then grow into nanotubes (also named porous) [32,36,37]. As the above-mentioned formation process of TiO2 nanotubes shows, the formation process includes three stages: compact and dense oxide layer, pore formation, and nanotube formation [18,19]. In this work, although the duration didn’t increase, the increased applied voltage could also promote the formation of nanotubes. Some authors [38,39] also showed that the feature of AOFs on Ti alloys would vary with the electrolyte and/or process parameters, such as applied voltage. Therefore, the microstructure evolution of the AOF in this work also accords with the formation process of TiO2 nanotubes. The dark and compact regions in Figure 2(a3) could be the microstructure characteristic after the beginning stage, namely, the beginning compact and dense oxide layer/ barrier inner layer. The light regions could be the pores and/or nanotubes, depending on the formation process. At the early formation stage of pores, the light and loose regions in Figure 2(a2) and most regions in Figure 2(b2) could be the porous layer. As the applied voltage increases, the pores become deeper and grow into nanotubes, as Figure 2(c3) shows. EDS images of the AOF on various specimens are shown, respectively, in Figure 2(a4–c4). The composition of the AOF on all specimens also contains the elements Al and Zr, besides the main O and Ti. That means that oxidation not only occurred with Ti but also with Al and Zr. The content analysis of EDS spectra shows that the content ratio of O to the total of Ti, Al, and Zr of the AOF is approximately 1.93 ± 0.15 for A20V, 1.90 ± 0.13 for A40V, and 1.86 ± 0.15 for A60V. These values are slightly smaller than 2, the ratio of TiO2. This is because of the formation of a small amount of Al2O3. The content of Al2O3 also increases with the applied voltage, which is proved by the increased Al content in Figure 2(a4).
The cross-section images of the AOF on specimens are shown in Figure 3. The boundary of the AOF on specimens A20V and A40V is wavy but is flat on A60V. Furthermore, the thickness of the AOF varies with the applied voltage. The mean thickness (H_mean) values of specimens are shown in Figure 3d. The H_mean of the AOF increases with the applied voltage. Based on the hopping mechanism, the oxide ions transfer through oxide vacancy to the surface of the substrate. Concurrently, oxide vacancies transfer toward the interface between the film and substrate with the help of an electric field and concentration gradient [40]. After this process, the barrier layer grows onto the surface. As the process continues, the pores and nanotubes form gradually. The formation and growth rate of those microstructures depends on the concentration of oxide vacancies and ions, which increase with the applied voltage [41]. Hence, the thickness of the AOF increases with the applied voltage. Furthermore, as the applied voltage increases from 20 to 40 V, the mean thickness has a sharp jump from approximately 8.6 ± 4.61 to 18.3 ± 4.08 μm. However, as the applied voltage further increases to 60 V, the increase in thickness is relatively small, from 18.3 ± 4.08 to 20.7 ± 2.18 μm. That means the growth rate of the thickness decreases with the increase of applied voltage. A simar tendency was also reported in previous publications [23,42,43].

3.2. Surface Microhardness of AOFs

Figure 4 shows the microhardness of various anodized specimens. The trend of mean hardness (HV_mean) varies with the applied voltage. The mean hardness of the substrate is approximately 364.6 ± 14.4 HV, close to the previously reported value of TZAV series alloys [44,45]. After anodizing at 20 V, the specimen has a mean hardness of 400.9 ± 29.2 HV. This hardness is far lower than oxidized Ti alloys [44,46]. Two reasons should explain the obvious disparity. The first one is the thickness of the AOF. While the thickness of the AOF is not enough, the substrate could bear some loads from the indenter or the oxide layer could even be impaled. Therefore, the measured hardness would be much less than the actual value of the oxide layer, such as the microhardness of specimen A20V. As the thickness of the oxide layer increases, that weak effect should reduce and even disappear. As Figure 3d shows, the thickness of the oxide layer increases with the applied voltage. Therefore, the mean surface hardness increases gradually to 818.4 ± 19.3 HV as the applied voltage increases to 60 V. That tendency is the same as Guleryuz’s results [47]. The other reason could be the roughness of the AOF surface. The hardness error bars of different specimens are shown in Figure 4. The undulation of hardness values of different specimens is obviously different. Specimens A20V and A40V have a higher undulation than the other two. Those undulations could be caused by different roughness, apart from the measurement error. The undulation of the AOF surface would affect the measured indentation size and, therefore, the hardness value. The thickness of AOF in peaks and troughs on the surface must be different. The higher the roughness is, the higher the undulation will be. Based on the cross-section images in Figure 3, the roughness of specimens A20V and A40V are higher than A60V. Therefore, the undulation of hardness values of those two specimens is higher than A60V.

3.3. Tribological Behavior and Wear Mechanism in the SBF Solution

Figure 5 shows the wear performances of various anodized specimens in the SBF solution. Curves of friction coefficient (FC) vs. distance in Figure 5a show that the FC of all specimens is, on the whole, stable as the friction continues. The mean friction coefficient (FC_mean) and the WWR are shown in Figure 5b. The FC_mean of the substrate is approximately 0.21 ± 0.022. This FC_mean is smaller than the annealed Ti-20Zr-6.5Al-4V alloy (~0.35) [2]. That should be mainly because of the different testing environments. Lubrication is conducive to protecting friction materials [48,49]. Although the FC_mean of specimen A20V is 0.44 ± 0.029, double that of the substrate, a low FC_mean value is obtained for specimens A40V (0.14 ± 0.011) and A60V (0.16 ± 0.014). The WWR of the substrate is approximately (15.00 ± 1.85) × 10−4 mg/N/m; however, that of all anodized specimens is sharply decreased to approximately 2.0 × 10−4 mg/N/m, (1.91 ± 1.42) × 10−4 mg/N/m for A20V, (2.10 ± 1.42) × 10−4 mg/N/m for A40V, and (2.35 ± 0.91) × 10−4 mg/N/m for A60V. In brief, specimens anodized at 40 and 60 V have low values of friction coefficient and WWR, namely, they have better wear resistance than the TZ30 substrate. Thus, the AOF can improve the wear resistance of the TZ30 alloy in the SBF solution.
Figure 6 shows the worn track and profile graphs of specimens after friction and wear in the SBF solution. Profile graphs are extracted from the red line positions in Figure 6 (x2) (x = a, b, c, d). The worn track of the substrate is mainly characterized by grooves and some wavelike patterns (Figure 6(a2)). The grooves are formed during the abrasive wear process, as many previous publications have reported [7,50]. The wavelike patterns resulted from the plastic deformation during adhesive wear. Given that the shear stress component of the normal force was greater than the shear strength of the friction materials, shear deformation occurs, and wavelike patterns are formed [51,52]. Thus, the worn mechanism of the substrate is mainly the abrasive wear combined with the adhesive wear. The profile graph shows that the depth of grooves is comparatively uniform and the maximum difference in depth, Δh, in the whole measured profile graph is approximately 5.6 μm. The worn track of specimen A20V is uneven (Figure 6(b1)). Some zones are worn out (light zones), but others are not (to be exact, they don’t contact with the friction pair at all; dark zones). This result originates from the undulation of the AOF surface in Figure 3a, the high hardness of the AOF, and the low normal friction load as well. Thus, the friction and wear did not work on the whole surface, but it did on some contacting protrusions. A similar worn track is also exhibited in Figure 6(c1) for specimen A40V. The difference between those two worn track images is the size of a single worn zone. The size of a single worn zone in Figure 6(b1) is far larger than that in Figure 6(c1). That difference should result from two reasons. The high undulation of the AOF surface is the first reason. The abrasion was concentrated on some specific protruding areas, which were severely worn out and formed a large single worn zone. The other one is the thin AOF on specimen A20V. The thin AOF on peaks of the substrate surface may be wholly worn out or come off of the substrate surface. Therefore, the following friction occurred on the substrate surface. The low hardness of the substrate results in large worn zones. Besides, the undulation of the AOF surface on specimen A40V is far smaller than that on A20V, and the AOF is far thicker. Therefore, the size of worn zones on specimen A40V is small. The main character of the worn track of specimen A20V is wavelike patterns (Figure 6(b2)), but grooves for A40V (Figure 6(c2)). Therefore, the wear mechanism of those two specimens is different. From Figure 6(b3,c3), some big gaps appear in the profile graphs of specimens A20V and A40V. However, those big gaps are the boundaries of the unworn original AOF surface (as can be seen by comparing Figure 6(b2,c2) with the corresponding profile graph). Thus, the Δh of the worn track is just 0.43 μm for A20V and 0.88 μm for A40V extracted, respectively, from Figure 6(b3,c3). Grooves are also the major character of the worn track of specimen A60V (Figure 6(d2)). As stated above, grooves are the typical trace of abrasive wear. Apart from major grooves, some wear debris is also observed. Thus, the wear mechanism of specimen A60V is abrasive wear. The Δh of the worn track in Figure 6(d3) is about 2.67 μm, which is nearly half of the substrate. The shallow worn tracks of all anodized specimens result from the excellent wear resistance and high hardness of the AOF. Results of profile graphs accord with and prove the tendency of the WWR to vary with the applied voltage.

3.4. Corrosion Resistance in the SBF Solution

Potentiodynamic polarization curves and extracted corrosion parameters in the SBF solution of various specimens are shown in Figure 7. The passive region and the corrosion potential of all anodized specimens are higher than the substrate. From the corresponding polarization curves, the corrosion potential (Ecorr) and corrosion current density (icorr) in Figure 7b are extracted using the Tafel extrapolation method. The Ecorr of the substrate is approximately −518.98 ± 45.92 mV. The Ecorr of all anodized specimens is higher than the substrate and increases with the applied voltage. The Ecorr is −466.72 ± 34.95 mV for specimen A20V, −399.39 ± 23.41 mV for A40V, and −365.61 ± 37.45 mV for A60V. Babilas et al. [53] also showed that the Ecorr increases with the applied voltage from 20 to 100 V. The icorr value of the substrate is about 5.9168 ± 0.5342 μA/cm2, which is higher than all anodized specimens. As the applied voltage increases from 20 V to 60 V, the icorr value decreases from 2.3842 ± 0.1532 μA/cm2 to 0.58995 ± 0.1067 μA/cm2. That is, the reduction in icorr value for specimen A60V is up to 90% compared with the substrate. These icorr values are similar to the oxynitride Ti–6Al–4V alloy (0.3~0.5 μA/cm2) [54], anodized Ti–6Al–4V alloy (1.69 μA/cm2 in 3.5 wt.% NaCl and 0.46 in 3.5 wt.% H2SO4) [55], composite anodic film-covered Ti-10V-2Fe-3Al alloy (0.1~3 μA/cm2) [56], and anodized pure Ti (0.79 μA/cm2) [57]; much less than anodized TO2 nanotube-covered Ti-10Mo-0.5Si alloy (21 μA/cm2) [58]; but a little bit higher than nanocomposite-coated TZAV-30 alloy titanium alloy (0.12–0.77 μA/cm2) [59]. The difference between this work and previous values could be caused by alloy composition, coating type, and corrosion conditions, such as corrosive solution [55,60,61]. According to the principle of the potentiodynamic polarization curve test and previous publications [54,62], a higher Ecorr value represents a nobler metal surface; a lower icorr value indicates a better corrosion resistance (or a more protective surface film). Thus, the corrosion resistance in the SBF solution is obviously improved after the TZ30 alloy anodization at applied voltages of 20–60 V. Some publications [63,64] also showed similar results and proved the improving effect of the AOF on the corrosion resistance of Ti alloys.

4. Conclusions

The microstructure of anodized TZ30 alloy and its surface performances in the SBF solution are investigated comprehensively. The main conclusions are as follows.
(1)
The main microstructure evolution of the AOF is that compact regions transform gradually into loose regions and then grow into nanotube regions. The thickness of AOF increases from 8.6 ± 4.61 μm to 20.7 ± 2.18 μm as the applied voltage increased to 60 V.
(2)
Surface microhardness increases gradually with the applied voltage. The specimen anodized at 60 V has a surface microhardness of 818.4 ± 19.3 HV, far over the substrate (~364.6 ± 14.4 HV).
(3)
The mean friction coefficient tested in the SBF solution decreases from 0.21 ± 0.022 for the substrate to 0.14 ± 0.011 and 0.16 ± 0.014 for the specimens anodized at 40 V and 60 V, respectively.
(4)
Anodization can obviously improve the corrosion resistance of the TZ30 alloy in the SBF solution. The reduction of corrosion current density is up to 90% for the specimen anodized at 60 V compared to the substrate.

Author Contributions

Methodology, L.Y.; investigation, K.L. and Y.Z.; resources, L.Z. and X.Z.; data curation, G.H.; writing—original draft preparation, K.L.; writing—review and editing, S.L. and X.L.; visualization, Y.S.; project administration, Z.X. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Natural Science Foundation of Hebei Province (grant number. E2021402002, E2021402001), the Department of Education of Hebei Province (grant number ZD2020195, ZD2018213, QN2019040), and the Science and Technology Research and Development Projects of Handan City (grant number 21422111221, 19422111008-20).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Nagels, J.; Stokdijk, M.; Rozing, P.M. Stress shielding and bone resorption in shoulder arthroplasty. J. Shoulder Elb. Surg. 2003, 12, 35–39. [Google Scholar] [CrossRef]
  2. Liang, S. Review of the design of titanium alloys with low elastic modulus as implant materials. Adv. Eng. Mater. 2020, 22, 2000555. [Google Scholar] [CrossRef]
  3. Liang, S.X.; Ma, M.Z.; Jing, R.; Zhang, X.Y.; Liu, R.P. Microstructure and mechanical properties of hot-rolled ZrTiAlV alloys. Mater. Sci. Eng. A 2012, 532, 1–5. [Google Scholar] [CrossRef]
  4. Liang, S.X.; Ma, M.Z.; Jing, R.; Zhou, Y.K.; Jing, Q.; Liu, R.P. Preparation of the ZrTiAlV alloy with ultra-high strength and good ductility. Mater. Sci. Eng. A 2012, 539, 42–47. [Google Scholar] [CrossRef]
  5. Zhang, Y.; Liu, Z.; Zhao, Z.; Ma, M.; Shu, Y.; Hu, W.; Liu, R.; Tian, Y.; Yu, D. Preparation of pure α″-phase titanium alloys with low moduli via high pressure solution treatment. J. Alloys Compd. 2017, 695, 45–51. [Google Scholar] [CrossRef]
  6. Shi, Y.D.; Wang, L.N.; Liang, S.X.; Zhou, Q.; Zheng, B. A high Zr-containing Ti-based alloy with ultralow Young’s modulus and ultrahigh strength and elastic admissible strain. Mater. Sci. Eng. A 2016, 674, 696–700. [Google Scholar] [CrossRef]
  7. Liang, S.X.; Yin, L.X.; Zheng, L.Y.; Xie, H.L.; Yao, J.X.; Ma, M.Z.; Liu, R.P. Tribological behavior and wear mechanism of TZ20 titanium alloy after various treatments. J. Mater. Eng. Perform. 2018, 27, 4645–4654. [Google Scholar] [CrossRef]
  8. Yang, Y.; Xia, C.; Feng, Z.; Jiang, X.; Pan, B.; Zhang, X.; Ma, M.; Liu, R. Corrosion and passivation of annealed Ti–20Zr–6.5Al–4V alloy. Corros. Sci. 2015, 101, 56–65. [Google Scholar] [CrossRef]
  9. Liang, S.X.; Liu, K.Y.; Yin, L.X.; Huang, G.W.; Shi, Y.D.; Zheng, L.Y.; Xing, Z.G. Review of major technologies improving surface performances of Ti alloys for implant biomaterials. J. Vac. Sci. Technol. A 2022. [Google Scholar] [CrossRef]
  10. Gulati, K.; Martinez, R.D.O.; Czerwiński, M.; Michalska-Domańska, M. Understanding the influence of electrolyte aging in electrochemical anodization of titanium. Adv. Colloid Interface Sci. 2022, 302, 102615. [Google Scholar] [CrossRef]
  11. Pereira, B.L.; Lepienski, C.M.; Seba, V.; Nugent, M.J.D.; Torres, R.; Kuroda, P.A.B.; Grandini, C.R.; Soares, P. Plasma electrolytic oxidation up to four-steps performed on niobium and Nb-Ti alloys. Surf. Coat. Technol. 2022, 438, 128369. [Google Scholar] [CrossRef]
  12. Al Zoubi, W.; Allaf, A.W.; Assfour, B.; Ko, Y.G. Concurrent oxidation–reduction reactions in a single system using a low-plasma phenomenon: Excellent catalytic performance and stability in the hydrogenation reaction. ACS Appl. Mater. Interfaces 2022, 14, 6740–6753. [Google Scholar] [CrossRef]
  13. Saji, V.S. Superhydrophobic surfaces and coatings by electrochemical anodic oxidation and plasma electrolytic oxidation. Adv. Colloid Interface Sci. 2020, 283, 102245. [Google Scholar] [CrossRef]
  14. Matykina, E.; Arrabal, R.; Skeldon, P.; Thompson, G.E. Optimisation of the plasma electrolytic oxidation process efficiency on aluminium. Surf. Interface Anal. 2010, 42, 221–226. [Google Scholar] [CrossRef]
  15. Zhang, X.M.; Tian, X.B.; Yang, S.Q.; Gong, C.Z.; Fu, R.K.Y.; Chu, P.K. Low energy-consumption plasma electrolytic oxidation based on grid cathode. Rev. Sci. Instrum. 2010, 81, 103504. [Google Scholar] [CrossRef]
  16. Macak, J.M.; Tsuchiya, H.; Ghicov, A.; Yasuda, K.; Hahn, R.; Bauer, S.; Schmuki, P. TiO2 nanotubes: Self-organized electrochemical formation, properties and applications. Curr. Opin. Solid State Mater. Sci. 2007, 11, 3–18. [Google Scholar] [CrossRef]
  17. Lee, W.; Park, S.-J. Porous anodic aluminum oxide: Anodization and templated synthesis of functional nanostructures. Chem. Rev. 2014, 114, 7487–7556. [Google Scholar] [CrossRef]
  18. Macak, J.M.; Hildebrand, H.; Marten-Jahns, U.; Schmuki, P. Mechanistic aspects and growth of large diameter self-organized TiO2 nanotubes. J. Electroanal. Chem. 2008, 621, 254–266. [Google Scholar] [CrossRef]
  19. Pérez, D.A.G.; Jorge Junior, A.M.; Asato, G.H.; Lepretre, J.-C.; Roche, V.; Bolfarini, C.; Botta, W.J. Surface anodization of the biphasic Ti13Nb13Zr biocompatible alloy: Influence of phases on the formation of TiO2 nanostructures. J. Alloys Compd. 2019, 796, 93–102. [Google Scholar] [CrossRef]
  20. Ma, Y.; Wu, H.; Zhou, X.; Li, K.; Liao, Y.; Liang, Z.; Liu, L. Corrosion behavior of anodized Al-Cu-Li alloy: The role of intermetallic particle-introduced film defects. Corros. Sci. 2019, 158, 108110. [Google Scholar] [CrossRef]
  21. de Oliveira, L.A.; dos Santos, S.L.; de Oliveira, V.A.; Antunes, R.A. Influence of anodization on the fatigue and corrosion-fatigue behaviors of the AZ31B magnesium alloy. Metals 2021, 11, 1573. [Google Scholar] [CrossRef]
  22. Wu, S.; Wang, S.; Liu, W.; Yu, X.; Wang, G.; Chang, Z.; Wen, D. Microstructure and properties of TiO2 nanotube coatings on bone plate surface fabrication by anodic oxidation. Surf. Coat. Technol. 2019, 374, 362–373. [Google Scholar] [CrossRef]
  23. Liu, Z.J.; Zhong, X.; Liu, H.; Tsai, I.L.; Donatus, U.; Thompson, G.E. Characterization of anodic oxide film growth on Ti6Al4V in NaTESi electrolyte with associated adhesive bonding behaviour. Electrochim. Acta 2015, 182, 482–492. [Google Scholar] [CrossRef]
  24. ASTM E1911-19; Standard Test Method for Measuring Surface Frictional Properties Using the Dynamic Friction Tester. ASTM International: West Conshohocken, PA, USA, 2019.
  25. Osório, W.R.; Peixoto, L.C.; Moutinho, D.J.; Gomes, L.G.; Ferreira, I.L.; Garcia, A. Corrosion resistance of directionally solidified Al–6Cu–1Si and Al–8Cu–3Si alloys castings. Mater. Des. 2011, 32, 3832–3837. [Google Scholar] [CrossRef]
  26. Zhang, X.L.; Jiang, Z.H.; Yao, Z.P.; Song, Y.; Wu, Z.D. Effects of scan rate on the potentiodynamic polarization curve obtained to determine the Tafel slopes and corrosion current density. Corros. Sci. 2009, 51, 581–587. [Google Scholar] [CrossRef]
  27. Osório, W.R.; Freitas, E.S.; Garcia, A. EIS and potentiodynamic polarization studies on immiscible monotectic Al–In alloys. Electrochim. Acta 2013, 102, 436–445. [Google Scholar] [CrossRef]
  28. McCafferty, E. Validation of corrosion rates measured by the Tafel extrapolation method. Corros. Sci. 2005, 47, 3202–3215. [Google Scholar] [CrossRef]
  29. Sjöström, T.; Nobbs, A.H.; Su, B. Bactericidal nanospike surfaces via thermal oxidation of Ti alloy substrates. Mater. Lett. 2016, 167, 22–26. [Google Scholar] [CrossRef] [Green Version]
  30. Sikder, P.; Koju, N.; Ren, Y.; Goel, V.K.; Phares, T.; Lin, B.; Bhaduri, S.B. Development of single-phase silver-doped antibacterial CDHA coatings on Ti6Al4V with sustained release. Surf. Coat. Technol. 2018, 342, 105–116. [Google Scholar] [CrossRef]
  31. Cui, W.; Qin, G.; Duan, J.; Wang, H. A graded nano-TiN coating on biomedical Ti alloy: Low friction coefficient, good bonding and biocompatibility. Mater. Sci. Eng. C 2017, 71, 520–528. [Google Scholar] [CrossRef]
  32. Fu, Y.; Mo, A. A Review on the electrochemically self-organized titania nanotube arrays: Synthesis, modifications, and biomedical applications. Nanoscale Res. Lett. 2018, 13, 187. [Google Scholar] [CrossRef] [PubMed]
  33. Deen, K.M.; Farooq, A.; Raza, M.A.; Haider, W. Effect of electrolyte composition on TiO2 nanotubular structure formation and its electrochemical evaluation. Electrochim. Acta 2014, 117, 329–335. [Google Scholar] [CrossRef]
  34. Qin, J.; Cao, Z.; Li, H.; Su, Z. Formation of anodic TiO2 nanotube arrays with ultra-small pore size. Surf. Coat. Technol. 2021, 405, 126661. [Google Scholar] [CrossRef]
  35. Gong, Z.; Hu, Y.; Gao, F.; Quan, L.; Liu, T.; Gong, T.; Pan, C. Effects of diameters and crystals of titanium dioxide nanotube arrays on blood compatibility and endothelial cell behaviors. Colloids Surf. B Biointerfaces 2019, 184, 110521. [Google Scholar] [CrossRef]
  36. Fraoucene, H.; Sugiawati, V.A.; Hatem, D.; Belkaid, M.S.; Vacandio, F.; Eyraud, M.; Pasquinelli, M.; Djenizian, T. Optical and electrochemical properties of self-organized TiO2 nanotube arrays from anodized Ti−6Al−4V alloy. Front. Chem. 2019, 7, 66. [Google Scholar] [CrossRef] [Green Version]
  37. Ivanova, A.A.; Surmeneva, M.A.; Tyurin, A.I.; Pirozhkova, T.S.; Shuvarin, I.A.; Prymak, O.; Epple, M.; Chaikina, M.V.; Surmenev, R.A. Fabrication and physico-mechanical properties of thin magnetron sputter deposited silver-containing hydroxyapatite films. Appl. Surf. Sci. 2016, 360, 929–935. [Google Scholar] [CrossRef]
  38. Gui, L.; Peng, J.; Li, P.; Peng, R.; Yu, P.; Luo, Y. Electrochemical degradation of dye on TiO2 nanotube array constructed anode. Chemosphere 2019, 235, 1189–1196. [Google Scholar] [CrossRef]
  39. Niu, D.; Zhou, Q.; Zhu, X.; Feng, X.; Chen, S.; Wang, A.; Song, Y. Formation of TiO2 nanopetal architectures originated from anodic titanium oxide nanotubes. Chem. Phys. Lett. 2020, 759, 137950. [Google Scholar] [CrossRef]
  40. Jiang, Z.; Dai, X.; Middleton, H. Investigation on passivity of titanium under steady-state conditions in acidic solutions. Mater. Chem. Phys. 2011, 126, 859–865. [Google Scholar] [CrossRef]
  41. Jiang, Z.; Dai, X.; Norby, T.; Middleton, H. Investigation of pitting resistance of titanium based on a modified point defect model. Corros. Sci. 2011, 53, 815–821. [Google Scholar] [CrossRef]
  42. Aladjem, A. Anodic oxidation of titanium and its alloys. J. Mater. Sci. 1973, 8, 688–704. [Google Scholar] [CrossRef]
  43. Zhang, L.; Duan, Y.; Gao, R.; Yang, J.; Wei, K.; Tang, D.; Fu, T. The effect of potential on surface characteristic and corrosion resistance of anodic oxide film formed on commercial pure titanium at the potentiodynamic-aging mode. Materials 2019, 12, 370. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  44. Liang, S.X.; Yin, L.X.; Li, J.X.; Ma, M.Z.; Liu, R.P. Isothermal oxidation behavior of the TZAV-20 alloy. Mater. Des. 2015, 86, 458–463. [Google Scholar] [CrossRef]
  45. Qiao, X.; Liang, S.; Yin, L.; Li, D. Microstructural evolution and mechanical properties response of the ZT40 alloy with hot rolling. World J. Eng. 2015, 12, 431–436. [Google Scholar] [CrossRef]
  46. Aniołek, K. Structure and properties of titanium and the Ti-6Al-7Nb alloy after isothermal oxidation. Surf. Eng. 2020, 36, 847–858. [Google Scholar] [CrossRef]
  47. Guleryuz, H.; Cimenoglu, H. Surface modification of a Ti–6Al–4V alloy by thermal oxidation. Surf. Coat. Technol. 2005, 192, 164–170. [Google Scholar] [CrossRef]
  48. Liu, M.; Wang, Z.; Shi, C.; Wang, L.; Xue, X. Corrosion and wear behavior of Ti-30Zr alloy for dental implants. Mater. Res. Express 2019, 6, 0865c8. [Google Scholar] [CrossRef]
  49. Singh, R.; Dureja, J.S.; Dogra, M.; Gupta, M.K.; Mia, M.; Song, Q. Wear behavior of textured tools under graphene-assisted minimum quantity lubrication system in machining Ti-6Al-4V alloy. Tribol. Int. 2020, 145, 106183. [Google Scholar] [CrossRef]
  50. Wang, Y.; Zou, B.; Huang, C. Tool wear mechanisms and micro-channels quality in micro-machining of Ti-6Al-4V alloy using the Ti(C7N3)-based cermet micro-mills. Tribol. Int. 2019, 134, 60–76. [Google Scholar] [CrossRef]
  51. Wu, H.; Baker, I.; Liu, Y.; Wu, X.; Munroe, P.R.; Zhang, J. Tribological studies of a Zr-based bulk metallic glass. Intermetallics 2013, 35, 25–32. [Google Scholar] [CrossRef]
  52. Bin, F.; Luo, Z.J. Finite element simulation of the friction mechanism in plastic-working technology. Wear 1988, 121, 41–51. [Google Scholar] [CrossRef]
  53. Babilas, D.; Urbańczyk, E.; Sowa, M.; Maciej, A.; Korotin, D.M.; Zhidkov, I.S.; Basiaga, M.; Krok-Borkowicz, M.; Szyk-Warszyńska, L.; Pamuła, E.; et al. On the electropolishing and anodic oxidation of Ti-15Mo alloy. Electrochim. Acta 2016, 205, 256–265. [Google Scholar] [CrossRef]
  54. Pohrelyuk, I.; Tkachuk, O.; Proskurnyak, R.; Guspiel, J.; Beltowska-Lehman, E.; Morgiel, J. Influence of regulated modification of nitride layer by oxygen on the electrochemical behavior of Ti–6Al–4V alloy in the Ringer’s solution. Mater. Corros. 2019, 70, 2320–2325. [Google Scholar] [CrossRef]
  55. Jáquez-Muñoz, J.M.; Gaona-Tiburcio, C.; Chacón-Nava, J.; Cabral-Miramontes, J.; Nieves-Mendoza, D.; Maldonado-Bandala, E.; Delgado, A.D.; Flores-De los Rios, J.P.; Bocchetta, P.; Almeraya-Calderón, F. Electrochemical corrosion of titanium and titanium alloys anodized in H2SO4 and H3PO4 solutions. Coatings 2022, 12, 325. [Google Scholar] [CrossRef]
  56. Wu, Y.; Wu, H.; Wu, L.; Xie, Z.-H.; Liu, L.; Dai, X.; Zhang, G.; Yao, W.; Li, Y.; Pan, F. Influence of electrolyte temperature on morphology and properties of composite anodic film on titanium alloy Ti-10V-2Fe-3Al. Coatings 2020, 10, 1109. [Google Scholar] [CrossRef]
  57. Sasireka, A.; Rajendran, R.; Raj, V. In Vitro corrosion resistance and cytocompatibility of minerals substituted apatite/biopolymers duplex coatings on anodized Ti for orthopedic implant applications. Arab. J. Chem. 2020, 13, 6312–6326. [Google Scholar] [CrossRef]
  58. Nascimento, D.S.; Matos, G.R.L.; Moreira, F.K.V.; Macedo, M.C.S.S.; Souza, S.A. Anodizing-induced evolution of nanostructural surface morphologies in Ti-10Mo-xSi alloys for enhanced corrosion resistance. Surf. Coat. Technol. 2019, 377, 124924. [Google Scholar] [CrossRef]
  59. Liu, K.Y.; Liang, S.X.; Zhou, Y.X.; Liu, X.Y.; Shi, Y.D.; Huang, G.W.; Su, H.J.; Zheng, L.Y.; Xing, Z.G. Nanocomposite coatings and electrochemical corrosion behavior of TZAV-30 titanium alloy in simulated body fluid solution. J. Mater. Eng. Perform. 2022. [Google Scholar] [CrossRef]
  60. Bodunrin, M.O.; Chown, L.H.; Merwe, J.W.v.d.; Alaneme, K.K.; Oganbule, C.; Klenam, D.E.P.; Mphasha, N.P. Corrosion behavior of titanium alloys in acidic and saline media: Role of alloy design, passivation integrity, and electrolyte modification. Corros. Rev. 2020, 38, 25–47. [Google Scholar] [CrossRef]
  61. Dias Corpa Tardelli, J.; Bolfarini, C.; Cândido dos Reis, A. Comparative analysis of corrosion resistance between beta titanium and Ti-6Al-4V alloys: A systematic review. J. Trace Elem. Med. Biol. 2020, 62, 126618. [Google Scholar] [CrossRef]
  62. Jones, D.A. Principals and Prevention of Corrosion, 2nd ed.; Prentice-Hall: Hoboken, NJ, USA, 1996. [Google Scholar]
  63. Fattah-alhosseini, A.; Molaei, M.; Babaei, K. The effects of nano- and micro-particles on properties of plasma electrolytic oxidation (PEO) coatings applied on titanium substrates: A review. Surf. Interfaces 2020, 21, 100659. [Google Scholar] [CrossRef]
  64. Yao, J.; Wang, Y.; Wu, G.; Sun, M.; Wang, M.; Zhang, Q. Growth characteristics and properties of micro-arc oxidation coating on SLM-produced TC4 alloy for biomedical applications. Appl. Surf. Sci. 2019, 479, 727–737. [Google Scholar] [CrossRef]
Figure 1. XRD patterns of various anodized specimens.
Figure 1. XRD patterns of various anodized specimens.
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Figure 2. SEM and EDS images of the AOF on specimens (ai) A20V, (bi) A40V, and (ci) A60V; (a1,b1,c1) the corresponding SEM images; (a2,a3,b2,b3,c2,c3) are the corresponding enlarged SEM images; (a4,b4,c4) are the corresponding EDS images.
Figure 2. SEM and EDS images of the AOF on specimens (ai) A20V, (bi) A40V, and (ci) A60V; (a1,b1,c1) the corresponding SEM images; (a2,a3,b2,b3,c2,c3) are the corresponding enlarged SEM images; (a4,b4,c4) are the corresponding EDS images.
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Figure 3. Thickness of the AOF on specimens (a) A20V, (b) A40V, and (c) A60V, and (d) H_mean.
Figure 3. Thickness of the AOF on specimens (a) A20V, (b) A40V, and (c) A60V, and (d) H_mean.
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Figure 4. Mean surface microhardness of various specimens.
Figure 4. Mean surface microhardness of various specimens.
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Figure 5. Tribological results: (a) friction coefficient vs. distance curves, and (b) FC_mean and WWR.
Figure 5. Tribological results: (a) friction coefficient vs. distance curves, and (b) FC_mean and WWR.
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Figure 6. Wear trace and profile graphs of specimens: (ai) substrate, (bi) A20V, (ci) A40V, and (di) A60V; x1 (x = a, b, c, d) is the worn trace, x2 (x = a, b, c, d) is the enlarged worn trace image, x3 (x = a, b, c, d) is the profile graph of the corresponding specimen.
Figure 6. Wear trace and profile graphs of specimens: (ai) substrate, (bi) A20V, (ci) A40V, and (di) A60V; x1 (x = a, b, c, d) is the worn trace, x2 (x = a, b, c, d) is the enlarged worn trace image, x3 (x = a, b, c, d) is the profile graph of the corresponding specimen.
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Figure 7. Potentiodynamic polarization curves (a) and corrosion parameters (Ecorr and icorr) (b) of various specimens.
Figure 7. Potentiodynamic polarization curves (a) and corrosion parameters (Ecorr and icorr) (b) of various specimens.
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Liu, K.; Zhou, Y.; Yin, L.; Shi, Y.; Huang, G.; Liu, X.; Zheng, L.; Xing, Z.; Zhang, X.; Liang, S. Surface Microstructure and Performance of Anodized TZ30 Alloy in SBF Solution. Metals 2022, 12, 719. https://doi.org/10.3390/met12050719

AMA Style

Liu K, Zhou Y, Yin L, Shi Y, Huang G, Liu X, Zheng L, Xing Z, Zhang X, Liang S. Surface Microstructure and Performance of Anodized TZ30 Alloy in SBF Solution. Metals. 2022; 12(5):719. https://doi.org/10.3390/met12050719

Chicago/Turabian Style

Liu, Kaiyang, Yixin Zhou, Lixia Yin, Yindong Shi, Guangwei Huang, Xiaoyan Liu, Liyun Zheng, Zhenguo Xing, Xiliang Zhang, and Shunxing Liang. 2022. "Surface Microstructure and Performance of Anodized TZ30 Alloy in SBF Solution" Metals 12, no. 5: 719. https://doi.org/10.3390/met12050719

APA Style

Liu, K., Zhou, Y., Yin, L., Shi, Y., Huang, G., Liu, X., Zheng, L., Xing, Z., Zhang, X., & Liang, S. (2022). Surface Microstructure and Performance of Anodized TZ30 Alloy in SBF Solution. Metals, 12(5), 719. https://doi.org/10.3390/met12050719

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