锌在林格氏液中的体外长期腐蚀降解行为

doi:10.15541/jim20190176

摘要/Abstract

摘要：

锌基可降解生物材料与已被广泛研究的生物可降解材料(镁和铁)相比, 具有更合适的生物降解速率, 因而近年来受到了广泛的研究和关注。然而, 锌在模拟体液中的长期腐蚀降解行为尚不明确。本研究采用电化学腐蚀测试、表面化学成分分析及降解模式演变观察相结合的方法, 系统研究了锌在林格氏液中浸泡56 d的腐蚀演化过程。根据电化学结果显示, 锌的腐蚀速率P_i在浸泡过程中基本保持稳定, 约为0.06~0.10 mm/a; 失重法测定腐蚀速率为0.3 mm/a到0.5 mm/a。浸泡过程中生成的腐蚀产物主要为Zn₅(CO₃)₂(OH)₆和CaCO₃, 为较致密的细条花棒状和块状产物层, 且随着浸泡时间延长逐渐累积。去除腐蚀产物后发现, 样品表面出现较严重的局部腐蚀, 且腐蚀沟槽的尺寸随浸泡时间的延长而增大, 浸泡42 d腐蚀沟槽宽约为10 μm。本研究为锌基可降解生物材料后期表面改性及潜在生物医学应用提供了数据积累和研究基础。

关键词: 可降解锌, 长期腐蚀行为, 电化学测试, 表面化学

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

中图分类号:

TG178
R318

唐帅,张文泰,钱军余,鲜鹏,莫小山,黄楠,万国江. 锌在林格氏液中的体外长期腐蚀降解行为[J]. 无机材料学报, 2020, 35(4): 461-468.

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.

图/表 12

图1 锌浸泡在(37±0.5 )℃林格氏液中7、14、28、42和56 d的PDP曲线

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

图2 根据PDP曲线计算的自腐蚀电位Ecorr和自腐蚀电流密度icorr (a)和根据自腐蚀电流密度计算的腐蚀速率Pi (b)

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

图3 锌浸泡在(37±0.5) ℃下的林格氏液中7、14、28、42和56 d后EIS测试结果

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

图4 锌在浸泡前的EIS数据拟合电路图(a), 浸泡7~56 d后EIS数据拟合电路图(b), 界面电荷转移电阻Rct和腐蚀产物电阻Rp的拟合结果(c), 极化电阻Rpolar的拟合结果(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)

表1 锌在(37±0.5) ℃林格氏液中的EIS拟合结果

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	—

图5 锌浸泡在(37 ± 0.5) ℃的林格氏液中7(a)、14(b)、28(c)、42(d)和56(e) d时的表面形貌

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

图6 锌浸泡在(37±0.5) ℃林格氏液中56 d的截面扫描电镜照片(a)和截面EDS线扫图(b)

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

图7 锌浸泡在(37±0.5) ℃林格氏液中7、14、28、42和56 d的XRD图谱

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

图8 锌浸泡在林格氏液56 d后和浸泡前的XPS图谱

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

图9 锌浸泡在(37±0.5) ℃林格氏液中7(a)、14(b)、28(c)、42(d)和56(e)d后去除腐蚀产物的表面形貌

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

图10 锌浸泡在(37±0.5) ℃林格氏液中56 d去除腐蚀产物后的截面扫描电镜照片

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

图11 失重法测量锌浸泡在(37±0.5) ℃林格氏液中7、14、28、42和56 d的腐蚀速率

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

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