Long-term in Vitro Corrosion Behavior of Zinc in Ringer’s Solution

doi:10.15541/jim20190176

Abstract

Abstract:

In recent years, zinc-based biodegradable materials have gained significant attention due to their desirable biodegradation rate compared with other extensively explored biodegradable metals, such as magnesium and iron. However, the long-term corrosion behavior of zinc in simulated body fluid remain unclear. In this study, we performed a 56 d immersion test to reveal the long-term evolution of corrosion behavior of zinc in Ringer’s solution using electrochemical methods and surface analysis. The results showed that the corrosion rate of Zn calculated from current density ranged from 0.06 to 0.1 mm/a during the immersion. Its corrosion rate, determined by weight loss method, was from 0.3 mm/a to 0.5 mm/a. The corrosion products were mainly composed of Zn₅(CO₃)₂(OH)₆ and CaCO₃. These products were firm, rod- and block-like formed on Zn surface, and gradually accumulated with increase of immersion time. Its surface morphology after removing corrosion products exhibited increasing sizes of corrosion pits and grooves with increase of immersion time. And width of the corrosion pits and grooves was about 10 μm after 42 d immersion. This study provides a guideline for the further surface modification and biomedical applications of Zn-based materials in terms of biodegradation profile.

Key words: biodegradable zinc, long-term corrosion behavior, electrochemical test, surface chemistry

CLC Number:

TG178
R318

TANG Shuai,ZHANG Wentai,QIAN Junyu,XIAN Peng,MO Xiaoshan,HUANG Nan,WAN Guojiang. Long-term in Vitro Corrosion Behavior of Zinc in Ringer’s Solution[J]. Journal of Inorganic Materials, 2020, 35(4): 461-468.

Figures/Tables 12

Fig. 1 Potentiodynamic polarization curves of Zn immersed in Ringer’s solution at (37±0.5) ℃ for 7, 14, 28, 42 and 56 d

Fig. 2 Parameters of corrosion potential and corrosion current density obtained from PDP curves (a), and corrosion rate Pi obtained from current density (b)

Fig. 3 Nyquist plots measured by Electrochemical Impedance Spectroscopy (EIS) (a), bode plots of |Z| vs. frequency (b) and bode plots of phase angle vs. frequency (c) of Zn immersed in Ringer’s solution at (37±0.5) ℃ for 7, 14, 28, 42 and 56 d

Fig. 4 EIS data fitted with Equivalent electrical circuit (EEC) for 0 d (a) and EEC for 7 to 56 d (b), interfacial charge transfer resistance Rct and the corrosion products resistance Rp obtained from fitted results of the EIS spectra (c), and polarization resistance Rpolar calculated from EIS components as a function of time (d)

Table 1 The evolution of fitted results of electrochemical impedance spectroscopy of Zn in Ringer’s solution at (37±0.5) ℃

Samples	R_s/ (Ω∙cm²)	Q_p1/(×10^-6, sⁿ^*∙Ω^-1∙cm^-2)	n₁	R_p1/ (Ω∙cm²)	Q_p2/(×10^-6, sⁿ^*∙Ω^-1∙cm^-2)	n₂	R_p2/ (Ω∙cm²)	Q_dl/(×10^-6, sⁿ^*∙Ω^-1∙cm^-2)	n₃	R_ct/(×10³, Ω∙cm²)	Z_w/(×10^-3, s^1/2∙Ω^-1∙cm^-2)
0 d	21.09	35.00	0.76	105	—	—	—	2376	0.80	0.45	3.81
7 d	22.48	5.05	0.71	576	315.0	0.49	3458	155	0.61	6.28	—
14 d	16.21	1.24	0.65	175	13.7	0.74	2266	798	0.56	4.26	—
28 d	21.28	16.80	0.72	260	344.0	0.22	2893	322	0.81	10.42	—
42 d	22.91	0.95	0.74	430	232.0	0.49	2200	243	0.82	9.22	—
56 d	23.56	2.71	0.70	511	121.0	0.50	3342	290	0.57	12.88	—

Fig. 5 Surface morphology of Zn immersed in Ringer’s solution at (37±0.5)℃ for 7 (a), 14 (b), 28 (c), 42 (d), and 56 (e) d

Fig. 6 Cross-sectional images (a) and EDS line profile (b) of Zn immersed in Ringer’s solution at (37±0.5) ℃ for 56 d

Fig. 7 XRD spectra of Zn immersed in Ringer’s solution at (37±0.5) ℃ for 7, 14, 28, 42, and 56 d

Fig. 8 XPS spectra (a) and high-resolution O 1s (b) and (c) Ca 2p spectra of bare Zn and Zn after being immersed in Ringer’s solution for 56 d

Fig. 9 Surface morphology of Zn immersed in Ringer’s solution at (37±0.5) ℃ for 7 (a), 14 (b), 28, (c) 42 (d), and 56 d (e) after removal of corrosion products

Fig. 10 Cross-sectional SEM images of Zn immersed in Ringer’s solution at (37±0.5) ℃ for 56 d after removal of corrosion products

Fig. 11 Corrosion rate Pw calculated from weight loss of Zn after immersion in Ringer’s solution at (37±0.5) ℃ for 7, 14, 28, 42 and 56 d

References 23

[1]	BOWEN PATRICK K, DRELICH JAROSLAW, GOLDMAN JEREMY . Zinc exhibits ideal physiological corrosion behavior for bioabsorbable stents. Advanced Materials, 2013,25(18):2577-2582.
[2]	BOWEN PATRICK K, SHEARIER EMILY R, ZHAO SHAN , et al. Biodegradable metals for cardiovascular stents: from clinical concerns to recent Zn-Alloys. Advanced Healthcare Materials, 2016,5(10):1121-1140.
[3]	MOSTAED EHSAN, SIKORA-JASINSKA MALGORZATA, DRELICH JAROSLAW W , et al. Zinc-based alloys for degradable vascular stent applications. Acta Biomaterialia, 2018,71:1-23.
[4]	BIN BUM-HO, BHIN JINHYUK, TAKAISHI MIKIRO , et al. Requirement of zinc transporter ZIP10 for epidermal development: implication of the ZIP10-p63 axis in epithelial homeostasis. Proceedings of the National Academy of Sciences, 2017,114(46):12243-12248.
[5]	ZHU DONG-HUI, SU YING-CHAO, YOUNG MARCUS L , et al. Biological responses and mechanisms of human bone marrow mesenchymal stem cells to Zn and Mg biomaterials. ACS Applied materials & Interfaces, 2017,9(33):27453-27461.
[6]	HAASE HAJO, RINK LOTHAR . Multiple impacts of zinc on immune function. Metallomics, 2014,6(7):1175-1180.
[7]	LIN SONG, WANG QI-LONG, YAN XIN-HAO , et al. Mechanical properties, degradation behaviors and biocompatibility evaluation of a biodegradable Zn-Mg-Cu alloy for cardiovascular implants. Materials Letters, 2019,234:294-297.
[8]	KAFRI ALON, OVADIA SHIRA, GOLDMAN JEREMY , et al. The suitability of Zn-1.3% Fe alloy as a biodegradable implant material. Metals, 2018,8(3):153.
[9]	SHI ZHANG-ZHI, YU JING, LIU XUE-FENG , et al. Effects of Ag, Cu or Ca addition on microstructure and comprehensive properties of biodegradable Zn-0.8 Mn alloy. Materials Science and Engineering: C, 2019,99:969-978.
[10]	ZHENG YU-FENG, WU YUAN-HAO . Revolutionizing metallic biomaterials. Acta Metallurgica Sinica, 2017,53(3):257-297.
[11]	CHEN YING-QI, ZHANG WEN-TAI, MAITZ MANFRED F , et al. Comparative corrosion behavior of Zn with Fe and Mg in the course of immersion degradation in phosphate buffered saline. Corrosion Science, 2016,111:541-555.
[12]	TÖRNE KARIN, LARSSON MARIANN, NORLIN ANNA , et al. Degradation of zinc in saline solutions, plasma, and whole blood. Journal of Biomedical Materials Research Part B: Applied Biomaterials, 2016,104(6):1141-1151.
[13]	ZHAO LI-CHEN, ZHANG ZHE, SONG YU-TING , et al. Mechanical properties and in vitro biodegradation of newly developed porous Zn scaffolds for biomedical applications. Materials & Design, 2016,108:136-144.
[14]	LIU LI-JUN, MENG YAO, DONG CHAO-FANG , et al. Initial formation of corrosion products on pure zinc in simulated body fluid. Journal of Materials Science & Technology, 2018,34(12):2271-2282.
[15]	LIU XIAO, YANG HONG-TAO, LIU YANG , et al. Comparative studies on degradation behavior of pure zinc in various simulated body fluids. JOM, 2019,71(4):1414-1425.
[16]	STANDARD ASTM . G102-89, Standard Practice for Calculation of Corrosion Rates and Related Information from Electrochemical Measurements. Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA, 2015.
[17]	STANDARD ASTM . G31-72. Standard practice for laboratory immersion corrosion testing of metals. Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA, 2004.
[18]	SHI ZHI-MING, LIU MING, ATRENS ANDREJ . Measurement of the corrosion rate of magnesium alloys using Tafel extrapolation. Corrosion Science, 2010,52(2):579-588.
[19]	HUANG JUN . Diffusion impedance of electroactive materials, electrolytic solutions and porous electrodes: Warburg impedance and beyond. Electrochimica Acta, 2018,281:170-188.
[20]	WU J, ZHANG SD, SUN WH , et al. Influence of oxidation related structural defects on localized corrosion in HVAF-sprayed Fe-based metallic coatings. Surface and Coatings Technology, 2018,335:205-218.
[21]	SHI ZHI-MING, CAO FU-YONG, SONG GUANG-LING , et al. Low apparent valence of Mg during corrosion. Corrosion Science, 2014,88:434-443.
[22]	SIMõES AM, BASTOS AC, FERREIRA MG , et al. Use of SVET and SECM to study the galvanic corrosion of an iron-zinc cell. Corrosion Science, 2007,49(2):726-739.
[23]	BLANDA GIUSEPPE, BRUCATO VALERIO, PAVIA FRANCESCO CARFì , et al. Galvanic deposition and characterization of brushite/ hydroxyapatite coatings on 316L stainless steel. Materials Science and Engineering: C, 2016,64:93-101.