In Vitro Evaluation of the Feasibility of Commercial Zn Alloys as Biodegradable Metals

doi:10.1016/j.jmst.2016.06.003

摘要/Abstract

Abstract:

In this work, three widely used commercial Zn alloys (ZA4-1, ZA4-3, ZA6-1) were purchased and prepared by hot extrusion at 200?°C. The microstructure, mechanical properties, corrosion behaviors, biocompatibility and hemocompatibility of Zn alloys were studied with pure Zn as control. Commercial Zn alloys demonstrated increased strength and superb elongation compared with pure Zn. Accelerated corrosion rates and uniform corrosion morphologies were observed in terms of commercial Zn alloys due to galvanic effects between Zn matrix and α-Al phases. 100% extracts of ZA4-1 and ZA6-1 alloys showed mild cytotoxicity while 50% extracts of all samples displayed good biocompatibility. Retardant cell cycle and inhibited stress fibers expression were observed induced by high concentration of Zn²⁺ releasing during corrosion. The hemolysis ratios of Zn alloys were lower than 1% while the adhered platelets showed slightly activated morphologies. In general, commercial Zn alloys possess promising mechanical properties, appropriate corrosion rates, significantly improved biocompatibility and good hemocompatibility in comparison to pure Zn. It is feasible to develop biodegradable metals based on commercial Zn alloys.

Key words: Commercial Zn alloys, Biodegradable metals, Mechanical properties, Corrosion behaviors, Cytotoxicity, Hemocompatibility

. [J]. 材料科学与技术, 2016, 32(9): 909-918.

Wang C.,Yang H.T.,Li X.,Zheng Y.F.. In Vitro Evaluation of the Feasibility of Commercial Zn Alloys as Biodegradable Metals[J]. J. Mater. Sci. Technol., 2016, 32(9): 909-918.

图/表 17

Table 1 Chemical compositions (wt%) of commercial Zn alloys

Alloy	Al	Cu	Mg	Zn
ZA4-1	3.5-4.5	0.75-1.25	0.03-0.08	Bal.
ZA4-3	3.5-4.3	2.5-3.2	0.03-0.06	Bal.
ZA6-1	5.6-6.0	1.2-1.6	—	Bal.

Fig. 1. X-ray diffraction patterns of the experimental alloys.

Fig. 2. SEM images of the microstructure of pure Zn and Zn alloys: (a) pure Zn, (b) ZA4-1 alloy, (c) ZA4-3 alloy, (d) ZA6-1 alloy. Matrix and second phases in images are indicated by *.

Table 2 Chemical compositions (at.%) of areas indicated by * in Fig. 2

Area	Zn	Al	Cu	O
A	17.68	77.13		5.19
B	89	3.39	3.15	4.46
C	11.21	84.84		3.94
D	86.23	4.56	3.3	5.92
E	70.8	26.21		2.99
F	89.53	2.89	3.55	4.03

Fig. 3. Mechanical properties of pure Zn and Zn alloys: (a) yield strength, ultimate tensile strength and elongation, (b) compressive yield strength and ultimate compressive strength, (c) tensile stress-stain curves, (d) compressive stress-stain curves, *p?<?0.5, compared with pure Zn.

Fig. 4. Microhardness of pure Zn and Zn alloys, *p?<?0.5, compared with pure Zn.

Fig. 5. Polarization curves of pure Zn and Zn alloys.

Table 3 Electrochemical parameters of pure Zn and Zn alloys in Hank's solution

Material	I_corr (μA cm^-2)	E_corr (V)	Corrosion rate (mm year^-1)
Pure Zn	1.799(0.587)	-0.958(0.074)	0.027(0.009)
ZA4-1	2.986(0.430)	-1.145(0.007)	0.047(0.007)
ZA4-3	7.209(1.451)	-1.196(0.105)	0.374(0.431)
ZA6-1	5.331(1.231)	-1.142(0.007)	0.086(0.020)

Fig. 6. SEM images of pure Zn and Zn alloys after electrochemical tests: (a) pure Zn, (b) ZA4-1 alloy, (c) ZA4-3 alloy, (d) ZA6-1 alloy.

Fig. 7. Chemical compositions of regions in Fig. 6 detected by EDS analysis.

Fig. 8. Elemental (EDS) maps for typical corroded regions in pure Zn and Zn alloys: (a) pure Zn, (b) ZA4-1 alloy, (c) ZA4-3 alloy, (d) ZA6-1 alloy.

Fig. 9. Cell viability after culturing in extraction mediums of pure Zn and Zn alloys for 1, 2 and 4 days: (a) 100% extracts, (b) 50% extracts, *p?<?0.5, compared with pure Zn.

Table 4 Ion concentrations of extraction mediums of pure Zn and Zn alloys

Material	Mg (μg/mL)	Zn (μg/mL)	Al (μg/mL)	Cu (μg/mL)
Pure Zn		12.24
ZA4-1	18.42	9.51	0.050	0.054
ZA4-3	18.65	10.78	0.051	0.058
ZA6-1	18.63	9.52	0.053	0.062
Control	18.05	0.067	0.100	0.041

Fig. 10. Cell cycle analysis of HUVECs cultured in extraction mediums of pure Zn and Zn alloys for 24?h: (a) control group, (b) pure Zn, (c) ZA4-1 alloy, (d) ZA4-3 alloy, (e) ZA6-1 alloy, (f) graphic representations of the cell cycle distributions of HUVECs.

Fig. 11. Fluorescent microscopic images of HUVECs after 24?h culture on the sample surfaces: (a, f) control group, (b, g) pure Zn, (c, h) ZA4-1 alloy, (d, i) ZA4-3 alloy, (e, j) ZA6-1 alloy. Actin and nuclei are in green and blue, respectively.

Fig. 12. Hemolysis percentages of pure Zn and Zn alloys.

Fig. 13. SEM images of adhered platelets on surfaces of pure Zn and Zn alloys: (a) pure Zn, (b) ZA4-1 alloy, (c) ZA4-3 alloy, (d) ZA6-1 alloy.

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