Initial formation of corrosion products on pure zinc in simulated body fluid

doi:10.1016/j.jmst.2018.05.005

摘要/Abstract

Abstract:

Zinc was recently suggested to be a potential candidate material for degradable coronary artery stent. The corrosion behavior of pure zinc exposed to r-SBF up to 336?h was investigated by electrochemical measurements and immersion tests. The morphology and chemical composites of the corrosion products were investigated by scanning electron microscope, grazing-incidence X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrometer. The results demonstrate that the initial corrosion products on the pure zinc mainly consist of zinc oxide/hydroxide and zinc/calcium phosphate compounds. The pure Zn encounters uniform corrosion with an estimated corrosion rate of 0.02-0.07?mm?y^-1 during the immersion, which suggests the suitability of pure Zn for biomedical applications.

Key words: Zinc, Stent, Corrosion, Simulated body fluid

. [J]. 材料科学与技术, 2018, 34(12): 2271-2282.

Lijun Liu, Yao Meng, Chaofang Dong, YuY an, Alex A. Volinsky, Lu-Ning Wang. Initial formation of corrosion products on pure zinc in simulated body fluid[J]. J. Mater. Sci. Technol., 2018, 34(12): 2271-2282.

图/表 18

Table 1 Comparison of the inorganic ion concentrations and some organic components among human blood plasma, r-SBF, PBS, Ringer’s solution and Hank’s solution.

	Plasma [24]	r-SBF [19]	PBS [20], [21]	Ringer’s solution [22]	Hank’s Solution [23], [25]
Na⁺ (mmol/L)	142.0	142.0	154.05	156.4	141.8
K⁺ (mmol/L)	5.0	5.0	4.14	5.8	5.8
Ca²⁺ (mmol/L)	2.5	2.5	-	2.2	2.5
Mg²⁺ (mmol/L)	1.5	1.5	-	-	0.8
Cl^- (mmol/L)	103.0	103.0	140.6	164.2	147.4
HCO₃^- (mmol/L)	27.0	27.0	-	2.4	4.2
HPO₄^2- (mmol/L)	1.0	1.0	8.06	-	0.3
H₂PO₄^- (mmol/L)	-	-	1.47	-	0.4
SO₄^2- (mmol/L)	0.5	0.5	-	-	0.8
Amino acids (mg/L)	nd	-	-	-
Glucose (g/L)	nd	-	-	-	5.6
Proteins (g/L)	63-80	-	-	-

Fig 1. (a) OCP with respect to time of pure Zn at different immersion periods in r-SBF and (b) OCP of pure Zn as a function of immersion time.

Fig. 2. (a) Potentiodynamic curves of pure Zn at different immersion periods in r-SBF: 0?h, 6?h, 12?h, 24?h, 48?h, 120?h, 168?h, 240?h and 360?h; (b) The current density obtained from PDP curves.

Table 2 The polarization data of the pure Zn at different immersion periods in r-SBF.

Immersion time	E_corr (V vs. SCE)	I_corr (μA?cm^-2)	β_c (V dec)
0?h	-1.12?±?0.09	5.72?±?6.77	0.13?±?0.07
6?h	-1.02?±?0.04	2.55?±?1.03	0.15?±?0.04
12?h	-0.99?±?0.01	4.25?±?1.67	0.15?±?0.21
24?h	-1.03?±?0.0002	6.03?±?2.35	0.17?±?0.05
48?h	-1.01?±?0.01	18.90?±?5.83	0.29?±?0.06
120?h	-1.04?±?0.03	11.30?±?3.52	0.28?±?0.10
168?h	-0.98?±?0.02	5.77?±?3.47	0.13?±?0.04
240?h	-0.99?±?0.02	18.00?±?2.07	0.19?±?0.09
336?h	-1.08?±?0.07	11.90?±?4.29	0.22?±?0.08

Fig. 3. EIS results of pure Zn after immersion in r-SBF: (a) Bode plots of |Z| vs. frequency and phase angle vs. frequency; (b) the equivalent electrical circuit used to fit the EIS data and (c) the total resistance Rt calculated from EIS components. Different immersion periods: 0?h, 6?h, 12?h, 24?h, 48?h, 120?h, 168?h, 240?h and 336?h. Symbols represent experimental data and lines represent simulated spectra.

Table 3 Equivalent electrical circuit parameters of the pure Zn at different immersion periods in r-SBF at 37?°C.

Immersion time	R_s (Ω cm²)	Q_dl (μΩ^-1?s^-1?cm^-2)	n	R_ct (Ω cm²)	C_c (μF?cm^-2)	R_c (Ω?cm²)
0?h	12.17?±?1.99	4.87?±?2.00	0.79?±?0.04	1962.67?±?476.05	2530?±?2880	1144.43?±?297.76
6?h	12.70?±?0.86	2.83?±?0.97	0.81?±?0.01	1765.33?±?462.59	6910?±?5480	977.03?±?293.65
12?h	14.23?±?0.31	2.02?±?0.09	0.84?±?0.01	1181.87?±?338.15	2022?±?1966	398.67?±?108.17
24?h	13.96?±?1.67	1.86?±?0.09	0.83?±?0.03	764.47?±?93.07	1930?±?1030	364.8?±?120.54
48?h	13.08?±?1.25	1.32?±?0.37	0.83?±?0.005	1174.93?±?171.90	4250?±?3690	390.67?±?104.21
120?h	15.03?±?2.07	1.32?±?0.20	0.85?±?0.006	2362.33?±?260.53	1780?±?1610	497.83?±?157.23
168?h	14.00?±?0.86	1.87?±?0.19	0.84?±?0	3442.33?±?1087.38	820?±?330	746.13?±?169.88
240?h	12.79?±?2.04	3.96?±?3.51	0.84?±?0.01	2733.67?±?619.95	1350?±?350	742.17?±?185.11
336?h	13.58?±?1.66	1.90?±?1.14	0.82?±?0.05	1092.17?±?185.01	5240?±?2390	347.17?±?129.61

Fig. 4. Optical images of pure Zn tested in r-SBF for different time: (a) 6?h, (b) 12?h, (c) 24?h, (d) 48?h, (e) 120?h, (f) 168?h, (g) 240?h and (h) 336?h.

Fig. 5. SEM images of pure Zn immersed in r-SBF for (a) 6?h, (b) 12?h, (c) 24?h, (d) 48?h, (e) 120?h, (f) 168?h, (g) 240?h and (h) 336?h. The insets show local high magnification area.

Table 4 EDS data of the surface of Zn samples after immersion in SBF for different time (at.%).

	6?h	12?h	24?h	48?h	120?h	168?h	240?h	336?h
Zn	65.8	64.9	63.4	62.8	46.3	47.8	41.4	17.4
C	23.1	23.9	24.3	23.1	29.3	26.7	31.7	12.5
O	9.6	9.8	10.9	12.2	19.3	21.3	21.8	58.4
P	1.4	0.9	1.1	1.3	3.8	2.8	3.4	8.5
Ca	0.1	0.5	0.4	0.6	1.3	1.4	1.7	3.2
P/Zn	0.021	0.014	0.017	0.021	0.082	0.058	0.082	0.488

Fig. 6. Cross-sectional images and EDS line profile of pure Zn immersed in r-SBF for (a, b) 120?h and (c, d) 240?h.

Fig. 7. FTIR spectra of Zn sample surfaces after immersion in r-SBF for 6?h, 12?h, 24?h, 48?h, 120?h, 168?h, 240?h and 336?h.

Fig. 8. XPS spectra of pure Zn: (a) The overview XPS spectrum, (b) P 2p and (c) Zn 2p3/2 spectra of pure Zn after immersion in r-SBF for 6?h, 12?h, 24?h, 48?h, 120?h, 168?h, 240?h and 336?h; Deconvoluted XPS spectra (d-g) of P 2p after immersion for 6?h, 48?h, 168?h and 336?h, and (h-l) of Zn 2p3/2 after immersion for 0?h, 6?h, 48?h, 168?h and 336?h.

Table 5 Proportion of different component in the corrosion products (%).

Immersion time	Zn₃(PO₄)₂	Ca₃(PO₄)₂	CaHPO₄·2H₂O
6?h	72.2	24.8	3.0
48?h	62.5	32.3	5.2
168?h	58.2	36.2	5.6
336?h	49.0	44.2	6.8

Fig. 9. GIXRD patterns of Zn after immersion in r-SBF solution for 6?h, 12?h, 24?h, 48?h, 120?h, 168?h, 240?h and 336?h. Inset shows the high magnification patterns from 10° to 38° 2θ angle for Zn immersed for 120?h, 168?h, 240?h and 336?h.

Fig. 10. (a) pH vibration in r-SBF, (b) accumulated Zn2+ ion and (c) weight loss vibration of immersed Zn samples as a function of immersion time.

Fig. 11. SEM images of Zn samples after immersed in r-SBF and removal of corrosion product: (a) 48?h and (b) 336?h.

Table 6 Corrosion rates of pure Zn in the r-SBF obtained from the electrochemical measurements (CRi, mm y-1) and immersion tests (CRw, mm y-1).

Immersion time	CR_i (mm?y^-1)	CR_w (mm?y^-1)
0?h	0.08?±?0.10	0
12?h	0.06?±?0.02	0.04?±?0.02
24?h	0.09?±?0.03	0.06?±?0.01
48?h	0.28?±?0.09	0.05?±?0.006
120?h	0.17?±?0.05	0.04?±?0.006
168?h	0.09?±?0.05	0.03?±?0.006
240?h	0.27?±?0.03	0.03?±?0.001
336?h	0.18?±?0.06	0.03?±?0.002

Fig. 12. Schematic illustration of corrosion process of pure Zn immersed in r-SBF solution: (a) the dissolution of Zn and formation of ZnO/Zn(OH)2 at initial stage during immersion; (b) the nucleation of zinc phosphate and calcium phosphates by extending the immersion time; (c) the growth of phosphates and thickening of the corrosion products; (d) partially dissolution of the corrosion product.

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