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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
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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 TaOxNy, 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)

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.

URL: 

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 (dave—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
Sample Ecorr βa -βc icorr ipass
V (vs SCE) mVdecade-1 mVdecade-1 Acm-2 Acm-2
Ta2N coating -0.12±0.01 305.16±13.44 120.63±6.91 (6.76±0.51)×10-9 (4.55±0.31)×10-8
Ti-6Al-4V -0.24±0.01 158.08±9.03 116.48±7.34 (4.20±0.23)×10-7 (9.86±0.34)×10-6
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) (Rs—solution resistance between the working electrode (WE) and the reference electrode (RE); Qp—capacitance of constant phase element (CPE); Rp—polariation resisitance; Rop and Qop—resistance and capacitance of the outer porous layer, respectively; Rib and Cib—resistance and capacitance of the inner barrier layer, respectively)
Immersion time Rs Qp n Cp Rp χ2
h Ωcm2 10-6 Ω-1cm-2sn μFcm-2 Ωcm2
1 34.74±0.35 5.72±0.05 0.941±0.002 3.35±0.13 (4.70±0.31)×106 6.33×10-4
24 28.82±0.61 5.80±0.09 0.922±0.003 2.78±0.09 (7.20±0.36)×106 5.17×10-4
72 65.25±0.71 2.91±0.03 0.932±0.002 1.56±0.05 (8.54±0.39)×106 1.36×10-3
120 47.46±0.64 1.97±0.02 0.936±0.002 1.04±0.03 (1.04±0.10)×107 2.33×10-3
Table 2  Electrochemical parameters derived from impedance fitting for investigated specimens at their respective open circuit potentials in Ringer's solution of Ta2N coating
Immersion time Rs Qop nop Rop Cib Rib
h Ωcm2 10-5 Ω-1cm-2sn 105 Ωcm2 10-5 Fcm-2 Ωcm2
24 24.51±0.18 4.24±0.50 0.815±0.011 1.22±0.06 2.56±0.25 (1.17±0.09)×106
72 27.80±0.22 3.59±0.32 0.844±0.008 1.34±0.04 3.81±0.45 (8.56±0.13)×105
120 30.69±0.20 3.47±0.17 0.845±0.004 1.33±0.03 5.01±0.46 (7.51±0.14)×105
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 (Csc—space charge capacitance, E—electrode potential)
Fig.14  Nd 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 Ef
Sample Potential / V Nd / 1019 cm-3 Efb / V δsc / nm
Ta2N coating 0.4 1.48 -1.50 18.85
0.6 1.10 -1.49 22.93
0.8 0.80 -1.47 28.02
1.0 0.62 -1.48 33.27
Ti-6Al-4V 0.4 11.13 -1.15 9.61
0.6 5.92 -0.90 12.96
0.8 3.42 -0.80 17.61
1.0 2.20 -0.78 23.16
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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