In Vitro Corrosion Resistance of Ta2N Nanocrystalline Coating in Simulated Body Fluids

doi:10.11900/0412.1961.2017.00246

Acta Metall Sin

2018, Vol. 54

Issue (3): 443-456 DOI: 10.11900/0412.1961.2017.00246

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In Vitro Corrosion Resistance of Ta₂N Nanocrystalline Coating in Simulated Body Fluids

Jiang XU¹(

), Xike BAO¹, Shuyun JIANG²

1 College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
2 School of Mechanical Engineering, Southeast University, Nanjing 211102, China

Cite this article:

Jiang XU, Xike BAO, Shuyun JIANG. In Vitro Corrosion Resistance of Ta₂N Nanocrystalline Coating in Simulated Body Fluids. Acta Metall Sin, 2018, 54(3): 443-456.

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Abstract

Due to its combination of outstanding characteristics, such as superior biocompatibility, excellent mechanical properties as well as good corrosion resistance, Ti-6Al-4V alloy has gained much attention as one of the most popular load-bearing biomedical metals in the area of orthopedic and dental. Unfortunately, Ti-6Al-4V alloy suffers from the localized corrosion damage in human body ?uids containing high chloride ion concentrations, which leads to the release of metal ions into the human body. The released ions (e.g., Al and V) are found to not only cause allergic and toxic reactions but also exhibit potential negative effects on osteoblast behavior. To improve the corrosion resistance of Ti-6Al-4V alloy in simulated body ?uids, a 40 μm thick Ta₂N nanocrystalline coating with an average grain size of 12.8 nm was engineered onto a Ti-6Al-4V substrate using a double cathode glow discharge technique. The hardness and elastic modulus of the Ta₂N coating were determined to be (32.1±1.6) GPa and (294.8±4.2) GPa, respectively, and the adhesion strength of the coating deposited on Ti-6Al-4V substrate was found to be 56 N. There is no evidence of crack formation within the coating under loads ranging from 0.49 N to 9.8 N, implying that the Ta₂N nanocrystalline coating has a high contact damage resistance. Moreover, the corrosion resistance of the Ta₂N nanocrystalline coating is significantly greater than that of Ti-6Al-4V alloy when tested in naturally aerated Ringer's solution at 37 ℃. This is due to that the passive film developed on the coating has superior compactness compared with that formed on the uncoated Ti-6Al-4V alloy. XPS analysis indicated that at a low polarized potential, the passive film consisted of TaO_xN_y, which would be converted to Ta₂O₅ at a higher polarized potential. The analysis of Mott-Schottky curves suggested that the passive film formed on the coating exhibits n-type semiconductor properties and, as such, the density and diffusivity of carrier for the coating was considerably lower than that for the uncoated Ti-6Al-4V alloy.

Key words: Ta-N coating Ti-6Al-4V alloy electrochemical corrosion passive film semiconductor property

Received: 21 June 2017

Fund: Supported by National Natural Science Foundation of China (Nos.51374130 and 51675267) and State Key Program of National Natural Science Foundation of China (No.51635004)

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https://www.ams.org.cn/EN/10.11900/0412.1961.2017.00246 OR https://www.ams.org.cn/EN/Y2018/V54/I3/443

Fig.1 XRD spectrum of Ta₂N coating deposited on Ti-6Al-4V substrate

Fig.2 Cross-sectional SEM image (a) and the corresponding EDS elemental maps for Ta (b), N (c) and Ti (d) for the Ta₂N coating

Fig.3 Bright-field plan-view TEM image (a), dark-field plan-view TEM image (b), statistical distribution of the grain sizes (d_ave—average size) (c), SAED pattern (d) and HRTEM image (e)

Fig.4 Cross-sectional TEM image obtained from the intermediate region (a), bright-field TEM image of the square area in Fig.4a (b), bright-field TEM image of the Ta₂N coating/substrate interfacial region (c) and high-magni?cation TEM image of the square area in Fig.4c (d) (Inset in Fig.4b showing HRTEM image)

Fig.5 Load-displacement curves of the Ta₂N coating and Ti-6Al-4V alloy

Fig.6 OM image of Vickers indentation sites in the Ta₂N coating with different applied loads (a), SEM surface image (b) and cross-sectional FIB image (c) of Vickers indentation in the Ta₂N coating under a load of 9.80 N

Fig.7 Acoustic emission signal curve (a) and SEM image of the scratch track (b) of Ta₂N coating (Inset in Fig.7b show the enlarged view of square area)

Fig.8 Potentiondynamic polarization curves for the Ta₂N coating and Ti-6Al-4V alloy in Ringer's solution

Fig.9 Nyquist (a, c) and Bode (b, d) plots of impedance spectra for Ta₂N coating (a, b) and Ti-6Al-4V alloy (c, d) after immersion for different time

Table 1 Electrochemical data derived from potentiodynamic polarization curves of Ta₂N coating and Ti-6Al-4V alloy in Ringer's solution

Fig.10 Equivalent circuit model of Ta₂N coating for 1, 24, 72, 120 h and Ti-6Al-4V alloy for 1 h (a), Ti-6Al-4V alloy equivalent circit model for 24, 72 and 120 h (b) (R_s—solution resistance between the working electrode (WE) and the reference electrode (RE); Q_p—capacitance of constant phase element (CPE); R_p—polariation resisitance; R_op and Q_op—resistance and capacitance of the outer porous layer, respectively; R_ib and C_ib—resistance and capacitance of the inner barrier layer, respectively)

Table 2 Electrochemical parameters derived from impedance fitting for investigated specimens at their respective open circuit potentials in Ringer's solution of Ta₂N coating

Table 3 Electrochemical parameters derived from impedance fitting for investigated specimens at their respective open circuit potentials in Ringer's solution of Ti-6Al-4V alloy

Fig.11 Double logarithmic curves of current density i vs polarization time t for the Ta₂N coating and uncoated Ti-6Al-4V alloy potentiostatically polarized at 0.8 V in Ringer's solution

Fig.12 XPS spectra for the passive films formed on the Ta₂N coating after potentiostatic polarization at 0.2 and 0.8 V for 1 h in Ringer's physiological solution(a) XPS survey spectra(b) high-resolution XPS spectra for Ta4f(c) high-resolution XPS spectra for Ta4p/N1s

Fig.13 Mott-Schottky plots of the passive films of Ta₂N coating (a) and Ti-6Al-4V alloy (b) formed at different potentials in Ringer's physiological solution (C_sc—space charge capacitance, E—electrode potential)

Fig.14 N_d in the passive films formed on Ta₂N coating (a) and Ti-6Al-4V substrate (b) in Ringer's physiological solution as a function of film formation potential E_f

Table 4 Summaries of parameters derived from capacitance measurements for the passive films formed on the Ta₂N coating and Ti-6Al-4V alloy in Ringer's physiological solution

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