Corrosion behavior, antibacterial ability, and osteogenic activity of Zn-incorporated Ni-Ti-O nanopore layers on NiTi alloy

doi:10.1016/j.jmst.2021.04.029

Abstract

Abstract:

Development of bone fixation devices with excellent corrosion resistance, antibacterial ability, and osteogenic activity is critical for promoting fracture healing. In this study, Zn-incorporated nanopore (NP) layers were prepared on the NiTi alloy through anodization and hydrothermal treatment. Results show that Zn can be evenly incorporated into the NP layers in the form of ZnTiO₃. The Zn-incorporated samples exhibit good corrosion resistance and significantly reduce Ni²⁺ release. Meanwhile, the samples can continuously release Zn²⁺, which is responsible for excellent long-term antibacterial ability. Furthermore, the synergetic effect of Zn²⁺ release and nanoporous structure of the NP layers endues the NiTi alloy excellent osteogenic activity, as verified by upregulated alkaline phosphatase activity, secretion of type I collagen, and extracellular matrix mineralization. Therefore, Zn-incorporated Ni-Ti-O NP layers have great potential as biomedical coatings of NiTi-based implant materials.

Key words: Nickel-titanium alloy, Anodization, Corrosion behavior, Antibacterial ability, Osteogenic activity

Yonghua Sun, Yuyu Zhao, He Zhang, Youjie Rong, Runhua Yao, Yi Zhang, Xiaohong Yao, Ruiqiang Hang. Corrosion behavior, antibacterial ability, and osteogenic activity of Zn-incorporated Ni-Ti-O nanopore layers on NiTi alloy[J]. J. Mater. Sci. Technol., 2022, 97: 69-78.

Figures/Tables 9

Fig. 1. (A) SEM morphologies of surface and cross-section. (B) EDS mapping of the cross-sections of Zn-incorporated samples.

Fig. 2. (A) XRD spectra. (B) XPS survey spectra, (C) Ti 2p, (D) Ni 2p, (E) Zn 2p high-resolution spectra of NiTi substrate, NP-5, NP-25, NP-80, NP-5-Zn, NP-25-Zn and NP-80-Zn.

Table 1 Surface chemical composition of different samples.

Sample	Atomic concentrations (at.%)							Ni/Ti ratio
Sample	Ni	Ti	O	C	N	Cl	Zn	Ni/Ti ratio
NiTi	2.62	7.29	22.95	63.15	2.62	-	-	0.36
NP-5	1.33	12.48	36.87	44.21	3.09	2.02	-	0.11
NP-25	1.84	14.27	38.83	41.46	1.69	1.91	-	0.13
NP-80	1.94	14.00	38.83	41.15	2.81	1.26	-	0.14
NP-5-Zn	0.76	10.42	32.33	42.37	3.78	-	10.34	0.07
NP-25-Zn	0.79	13.58	41.55	31.93	-	-	12.16	0.06
NP-80-Zn	0.97	13.3	39.60	32.28	-	-	13.30	0.07

Fig. 3. (A) Polarization curves, EIS spectra in the form of Nyquist plots (B) and Bode plots (C) for NiTi substrate, anodized samples (NP-5, NP-25 and NP-80) and Zn-incorporated samples (NP-5-Zn, NP-25-Zn and NP-80-Zn), full lines represent the fitting results; (D) Equivalent electrical circuit for impedance spectral analysis.

Table 2 Parameters obtained from polarization curves of different samples.

Sample	E_corr (mV vs SCE)	I_corr (nA cm^-2)	β_c (V dec^-1)
NiTi	-373±45.1	166±12.3	0.10±0.010
NP-5	-488±8.5	34.7±4.6	0.09±0.006
NP-25	-497±24.0	24.5±1.6	0.09±0.010
NP-80	-453±12.4	19.4±3.5	0.10±0.011
NP-5-Zn	-510±13.8	11.0±0.7	0.08±0.006
NP-25-Zn	-542±26.7	7.9±0.5	0.08±0.002
NP-80-Zn	-418±13.7	6.9±0.7	0.14±0.020

Table 3 Fitting results of the EIS data.

Sample	R_s (Ω cm²)	R_p (10⁵ Ω cm²)	CPE_P (10^-5Ω^-1 cm^-2 s ^- ⁿ)	n
NiTi	22.04±0.11	5.98±0.12	2.57±0.14	0.95±0.090
NP-5	23.56±2.01	10.61±0.18	3.60±0.05	0.93±0.005
NP-25	25.52±1.03	17.32±4.01	3.31±0.03	0.94±0.001
NP-80	24.76±0.87	32.01±3.87	2.95±0.33	0.95±0.230
NP-5-Zn	18.27±0.04	97.62±0.23	1.66±0.14	0.96±0.002
NP-25-Zn	26.57±1.77	100.02±6.72	1.15±0.02	0.94±0.030
NP-80-Zn	18.69±1.21	138.45±10.32	1.36±0.23	0.95±0.014

Fig. 4. Ni2+ (A) and Zn2+ (B) concentrations released from different samples; (C) Optical images of S. aureus colonies on ager; (D) Antibacterial rates of different samples against S. aureus, **p < 0.01.

Fig. 5. (A) Fluorescence images of the BMSCs at days 1, 4, and 7; (B) Cell proliferation measured by MTT at days 1, 4, and 7. ## p < 0.01; (C) Fluorescent images of the BMSCs grown on different samples for 24 h.

Fig. 6. Qualitative images (A) ALP activity; (B) collagen secretion; (C) ECM mineralization; Quantitative results (D) ALP activity; (E) collagen secretion; (F) ECM mineralization of BMSCs at days 7 and 14. # p < 0.05 and # # p < 0.01.

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