In vitro corrosion resistance and antibacterial performance of novel tin dioxide-doped calcium phosphate coating on degradable Mg-1Li-1Ca alloy

doi:10.1016/j.jmst.2018.09.052

Abstract

Abstract:

A SnO₂-doped calcium phosphate (Ca-P-Sn) coating was constructed on Mg-1Li-1Ca alloy by a hydrothermal process. The fabricated functional coatings were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). A triple-layered structure, which is composed of Ca₃(PO₄)₂, (Ca, Mg)₃(PO₄)₂, SnO₂, and MgHPO₄·3H₂O, is evident and leads to the formation of Ca₁₀(PO₄)₆(OH)₂ in Hank’s solution. Electrochemical measurements, hydrogen evolution tests and plating counts reveal that the corrosion resistance and antibacterial activity were improved through the coating treatment. The embedded SnO₂ nanoparticles enhanced crystallisation of the coating. The formation and degradation mechanisms of the coating were discussed.

Key words: Magnesium alloys, Coatings, Corrosion, Biomedical materials

Lan-Yue Cui, Guang-Bin Wei, Zhuang-Zhuang Han, Rong-Chang Zeng, Lei Wang, Yu-Hong Zou, Shuo-Qi Li, Dao-Kui Xu, Shao-Kang Guan. In vitro corrosion resistance and antibacterial performance of novel tin dioxide-doped calcium phosphate coating on degradable Mg-1Li-1Ca alloy[J]. J. Mater. Sci. Technol., 2019, 35(3): 254-265.

Figures/Tables 17

Table 1 Chemical compositions of as-extruded Mg-Li-Ca alloy, wt. %.

Sample	Mg	Ca	Li	Mn	Si	Fe	Cu	Ni
Mg-Li-Ca alloy	Balanced	1.12	0.88	0.014	0.013	0.0002	0.0002	0.0003

Fig. 1. Illustration of the preparing processes of the Ca-P-Sn coating on the Mg-Li-Ca alloy.

Fig. 2. SEM micrographs: (a) low magnification, (b) high magnification; and (c, d) chemical compositions of Points A and B, respectively, in the Ca-P-Sn coating on the Mg-Li-Ca alloy.

Fig. 3. (a) Hydrogen evolution volume as a function of immersion time, (b) polarization curves, (c) Nyquist plots, (d) Bode plots, equivalent circuits of the (e) Mg-Li-Ca alloy, (f) Ca-P and (g) Ca-P-Sn coatings in Hank’s solution at 37?°C.

Table 2 Electrochemical parameters of the polarization curves of the samples.

Sample	E_corr (V/SCE)	β_a (mV/dec)	-β_c (mV/dec)	i_corr (A/cm²)	P_i (mm/a)
Mg-Li-Ca alloy	-1.55	40.89	238.87	1.01?×?10^-5	0.231
Ca-P coating	-1.49	150.87	156.26	3.57?×?10^-6	0.082
Ca-P-Sn coating	-1.47	121.04	127.44	1.87?×?10^-6	0.043

Table 3 Fitting results of EIS spectra.

Samples	R_s (Ω?cm²)	CPE₁ (Ω^-1?cm^-2?s^-1)	n₁	R_ct (Ω?cm²)	CPE₂ (Ω^-1?cm^-2?s^-1)	n₂	R_f1 (Ω?cm²)	CPE₃ (Ω^-1?cm^-2?s^-1)	n₃	R_f2 (Ω?cm²)	R_L (Ω?cm²)	L (H?cm^-2)	Chi square
Mg-1Li-1Ca alloy	73.48	6.97?×?10^-5	0.65	113.0	2.25?×?10^-6						2.98?×?10³	82.44	8.16?×?10^-4
Ca-P coating	63.85	1.27?×?10^-9	1.00	602.3	7.75?×?10^-7	0.57	4.46?×?10³	6.59?×?10^-5	0.60		2.11?×?10³	1.61?×?10³	9.06?×?10^-4
Ca-P-Sn coating	31.67	3.96?×?10^-8	0.77	744.9	2.35?×?10^-5	0.18	9.99?×?10³	3.80?×?10^-7	1.00	2.68?×?10³	2.99?×?10⁴	1.91?×?10⁵	4.08?×?10^-4

Fig. 4. Numbers of E. coli colonies on the samples: the (a) control, (b) Mg-1Li-1Ca alloy, (c) Ca-P coating, (d) SnO2 nanoparticles and (d) Ca-P-Sn coating.

Fig. 5. (a) Low and (b) high magnification of the coating morphology prepared at room temperature; (c) XRD patterns of the coating prepared at room temperature; (d) the pH values of the bath solution as a function of immersion time at room temperature.

Fig. 6. XRD patterns of the Mg-Li-Ca alloy with and without the Ca-P-Sn coating (A) before and (B) after an immersion in Hank’s solution for 8 days in comparison to the SnO2 nano-particles; (C) the enlarged images of the Ca-P-Sn coating before and after an immersion.

Fig. 7. SEM morphologies of the coatings with the (a) presence of SnO2 at pH 2.9, (b) presence of SnO2 at pH 7.90, (c) absence of SnO2 and (d) presence of Na2SnO3 instead of SnO2 in the solution.

Fig. 8. (a) Cross-sectional SEM image, (b) EDS with line scanning and (c) elemental distributions of the (d) Ca, (e) P, (f) Sn, (g) N, (h) C, (i) O and (j) Mg elements in the Ca-P-Sn coating on the Mg-Li-Ca alloy.

Fig. 9. Schematic illustration of the formation of the Ca-P-Sn coating on the Mg-1Li-1Ca alloy.

Fig. 10. SEM micrographs of the (a) Mg-1Li-1Ca alloy, (b) Ca-P-Sn coating in Hank’s solution at 37?°C after immersion of 8 days.

Table 4 Chemical compositions of spectrums detected by EDS, wt. % (at. %).

Spectra	C	O	Mg	Sn	N	Na	Ca	P	Ca/P
A Substrate	10.40 (15.47)	52.61 (58.71)	29.39 (21.58)	-	-	-	1.08 (0.47)	6.55 (3.77)	- (0.13)
A Coating	19.57 (29.72)	47.06 (53.65)	1.32 (1.00)	3.00 (0.48)	-	0.67 (0.53)	15.57 (7.08)	12.81 (7.54)	- (0.94)
B Coating	25.94 (37.13)	34.13 (36.66)	0.75 (0.53)	-	9.15 (11.22)	0.56 (0.42)	18.36 (7.88)	11.11 (6.16)	- (1.28)

Fig. 11. FTIR spectra of the Ca-P-Sn coating before and after an immersion in Hank’s solution for 8 days.

Fig. 12. Schematic illustration of the corrosion mechanism of the Ca-P-Sn coating on the Mg-1Li-1Ca alloy.

Table 5 Solubility, Ksp [82].

Ca(OH)₂	CaCO₃	MgCO₃	Mg(OH)₂	MgHPO₄·3H₂O	CaHPO₄	Mg₃(PO₄)₂	Ca₃(PO₄)₂	HA
5.5×10^-6	2.9×10^-9	3.5×10^-8	1.8×10^-11	1.5×10^-6	1.0×10^-7	1.0×10^-25	2.0×10^-29	2.35×10^-59

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