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Acta Metall Sin  2019, Vol. 55 Issue (8): 1008-1018    DOI: 10.11900/0412.1961.2018.00469
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Fabrication and Properties of Anodic Oxide Nanotubular Arrays on Zr-17Nb Alloy
Ling LI1,Shenglian YAO1,Xiaoli ZHAO2,3,Jiajia YANG1,Yexi WANG1,Luning WANG1,4()
1. Beijing Innovation Center for Materials Genome Engineering, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
2. Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), Northeastern University, Shenyang 110819, China
3. Institute of Ceramics and Powder Metallurgy, School of Materials Science and Engineering, Northeastern University, Shenyang 110819, China
4. State Key Laboratory of Advanced Metallic Materials, University of Science and Technology Beijing, Beijing 100083, China
Cite this article: 

Ling LI,Shenglian YAO,Xiaoli ZHAO,Jiajia YANG,Yexi WANG,Luning WANG. Fabrication and Properties of Anodic Oxide Nanotubular Arrays on Zr-17Nb Alloy. Acta Metall Sin, 2019, 55(8): 1008-1018.

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Abstract  

Zr-17Nb alloy has been introduced as a candidate for spinal ?xation rods because of its excellent mechanical properties and biocompatibility, low magnetic susceptibility, appropriate initial Young's modulus, remarkable deformation-induced variation of the Young's modulus, good ductility and relatively small springback. It has been recognized that nanotubular surface modification via anodic oxidation on metals is an efficient approach to highly improve biocompatibility of metallic implant. It is thus necessary to understand the formation of nanotubular arrays on Zr-17Nb alloy and carry out the evaluation on the nanotubular arrays. Electrochemical anodization was applied to modify the Zr-17Nb alloy surface to promote the bonding of alloy to human bone. Nanotubular arrays were formed on the surface of Zr-17Nb alloy by applying a 70 V constant potential in a glycerol electrolyte containing 0.35 mol/L NH4F and 5%H2O (volume fraction). XRD, SEM, HRTEM, EDS and XPS were used for the structural, morphological and compositional analyses of the nanotubular arrays. Results showed that during anodic oxidation process, the oxidation and dissolution rate of Zr were almost consistent with those of Nb. By extending the anodization duration from 10 min to 120 min, the diameter of nanotubes increased from about 20 nm to about 67 nm, and the length of nanotubes increased from about 2.4 μm to about 6.8 μm. After annealing at 450 ℃ for 60 min, the nanotube films were converted from amorphous to crystalline, mainly composed of orthogonal phase zirconia (ZrO2) and orthogonal phase zirconium niobium oxide (Nb2Zr6O17). The elastic modulus of the nanotube films decreased and the hardness increased. At the same time, the contact angle was reduced and the hydrophilicity was improved after annealing. Results demonstrate that highly ordered nanotubular arrays could be fabricate on the Zr-17Nb alloy. It is promising that nanotubular surface modification could be an efficient approach for enhancement of the biocompatibility of the alloy.

Key words:  Zr-17Nb alloy      anodic oxidation      nanotube array      phase analysis      mechanical property     
Received:  11 October 2018     
ZTFLH:  TB383  
Fund: Supported by National Natural Science Foundation of China(Nos.51501008 and U1560103)

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2018.00469     OR     https://www.ams.org.cn/EN/Y2019/V55/I8/1008

Fig.1  Variation of current density with anodic oxidation duration (Inset shows current density transition during the first 2 min of anodization: I—the portion where current density rapidly decreases; II—the portion where current density slowly increases; III—the portion where current density slowly decreases)
Fig.2  Top view (a1~d1) and cross-sectional (a2~d2) SEM images of nanotubular arrays on Zr-17Nb alloy prepared with anodic oxidation time of 10 min (a1, a2), 30 min (b1, b2), 60 min (c1, c2) and 120 min (d1, d2) (Insets in Figs.2a2~d2 show the enlarged views of square areas)
Fig.3  Variation of nanotubes diameter (a) and nanotubular arrays thickness (b) with anodic oxidation time
Fig.4  Cross-sectional SEM image (a) and element distributions of Zr (b), Nb (c), O (d) and F (e) of nanotubular arrays prepared by anodizing for 120 minColor online
PointMass fraction of ZrMass fraction of NbNb/(Zr+Nb)
%%%
162.212.116.3
259.013.018.1
357.212.317.7
456.612.117.6
555.713.219.2
653.811.818.0
754.111.117.0
Table 1  Analyses of cross-sectional elements of nanotubular array prepared by anodizing for 120 min in Fig.4a
Fig.5  XRD spectra of Zr-17Nb alloy and nanotubular arrays prepared by different anodization time (a) and GAXRD spectra of nanotubular arrays prepared by anodizing for 120 min before and after annealing at 450 ℃ (b)
Fig.6  HRTEM and EDS analyses of nanotube prepared by anodizing for 120 minColor online(a) TEM image of single nanotube(b1~b4) element distributions of Zr, Nb, O and F, respectively, on a single nanotube(c) HRTEM image of the region I in Fig.6a on a single nanotube, with the fast Fourier transformation (FFT) of the HRTEM image inserted(d) HRTEM image of the region II in Fig.6a on a single nanotube, with the FFT of the HRTEM image inserted
PointMass fraction of ZrMass fraction of NbNb/(Zr+Nb)
%%%
159.712.717.5
257.014.219.9
354.714.621.1
Table 2  Analyses of cross-sectional elements of a single nanotube prepared by anodizing for 120 min and annealing at 450 ℃ in Fig.6a
Fig.7  XPS survey spectra of three groups of samples (Zr-17Nb, nanotubular array prepared by anodizing for 120 min, nanotubular array prepared by anodizing for 120 min and annealing at 450 ℃) (a) and high resolution spectra of Zr3d (b), Nb3d (c), O1s (d) and F1s (e) on nanotubular array anodized for 120 min before and after annealing treatment at 450 ℃
SpecimenYoung's modulusHardness
GPaGPa
Zr-17Nb alloy73.4±9.63.4±0.6
Anodic oxidation 2 h42.5±9.60.5±0.3
Annealing 2 h13.0±8.30.6±0.2
Table 3  Mechanical properties of Zr-17Nb alloy, nanotubular arrays prepared by anodic oxidation for 2 h before and after annealing at 450 ℃
Fig.8  Surface contact angles of Zr-17Nb alloy (a), nanotubular arrays prepared by anodic oxidation for 2 h before (b) and after (c) annealing at 450 ℃
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