<strong>AZ31</strong>镁合金表面苯丙氨酸、甲硫氨酸和天冬酰胺诱导<strong>Ca-P</strong>涂层耐蚀性能比较

doi:10.11900/0412.1961.2021.00058

金属学报

2021, Vol. 57

Issue (10): 1258-1271 DOI: 10.11900/0412.1961.2021.00058

研究论文

本期目录 | 过刊浏览

AZ31镁合金表面苯丙氨酸、甲硫氨酸和天冬酰胺诱导Ca-P涂层耐蚀性能比较

王雪梅¹, 殷正正¹, 于晓彤¹, 邹玉红², 曾荣昌¹^,³^,⁴(

)

^1.山东科技大学材料科学与工程学院青岛 266590
^2.山东科技大学化学与生物工程学院青岛 266590
^3.郑州大学材料科学与工程学院郑州 450002
^4.武汉理工大学现代汽车零部件技术湖北省重点实验室武汉 430070

Comparison of Corrosion Resistance of Phenylalanine, Methionine, and Asparagine-Induced Ca-P Coatings on AZ31 Magnesium Alloys

WANG Xuemei¹, YIN Zhengzheng¹, YU Xiaotong¹, ZOU Yuhong², ZENG Rongchang¹^,³^,⁴(

)

^1.School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China
^2.School of Chemical and Biological Engineering, Shandong University of Science and Technology, Qingdao 266590, China
^3.School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450002, China
^4.Hubei Key Laboratory of Advanced Technology for Automotive Components, Wuhan University of Technology, Wuhan 430070, China

引用本文:

王雪梅, 殷正正, 于晓彤, 邹玉红, 曾荣昌. AZ31镁合金表面苯丙氨酸、甲硫氨酸和天冬酰胺诱导Ca-P涂层耐蚀性能比较[J]. 金属学报, 2021, 57(10): 1258-1271.
Xuemei WANG, Zhengzheng YIN, Xiaotong YU, Yuhong ZOU, Rongchang ZENG. Comparison of Corrosion Resistance of Phenylalanine, Methionine, and Asparagine-Induced Ca-P Coatings on AZ31 Magnesium Alloys[J]. Acta Metall Sin, 2021, 57(10): 1258-1271.

全文: PDF(5915 KB) HTML

摘要:

为澄清氨基酸基团对成膜的影响，采用苯丙氨酸(Phenylalanine，Phe)、甲硫氨酸(Methionine，Met)和天冬酰胺(Asparagine，Asn) 3种氨基酸调控AZ31镁合金的降解速率，采用恒温水浴法(60℃)在其表面制备了3种氨基酸Ca-P涂层(Ca-P_Phe、Ca-P_Met和Ca-P_Asn)，并使用SEM、EDS 、XRD、FTIR及 XPS对涂层的形貌、成分分布和物相结构进行分析，利用电化学极化和交流阻抗及析氢腐蚀实验对涂层在模拟人体体液(Hank's)中的耐蚀性能进行研究。探讨了氨基酸添加剂在AZ31镁合金表面诱导Ca-P涂层成膜的作用机制。Ca-P、Ca-P_Phe、Ca-P_Met和Ca-P_Asn涂层的厚度分别为(3.47 ± 0.47)、(6.06 ± 0.77)、(7.63 ± 1.70)和(8.23 ± 1.37) μm。涂层主要组成物相为CaHPO₄及Ca₁₀(PO₄)₆(OH)₂(HA)。电化学和析氢实验结果表明，氨基酸提高了Ca-P涂层耐蚀性能。这主要归因于氨基酸分子的缓蚀作用，并在AZ31镁合金表面发生化学吸附。氨基酸中的氨基吸附主要是通过N原子的孤对电子与镁合金表面耦合来实现的；羧基是通过羰基中的O原子与Mg²⁺结合。此外，氨基酸中的杂原子亦能与镁合金的空位分子轨道共享其孤对电子。最后，提出了氨基酸诱导Ca-P涂层的成膜机理。

关键词 ： AZ31镁合金, 涂层, 氨基酸, 吸附, 耐蚀性能

Abstract：

Ca-P coating not only enhances the corrosion resistance of biodegradable magnesium alloys but also contributes to the formation of new bones and promotes bone integration around implants. However, the Ca-P coatings may have defects like porosity, low adhesion, and coarse grains, which lead to prefailure in the early stage and then the coatings cannot meet the requirements of long-term clinical service. Amino acids can induce the formation of calcium-bearing phosphates on biodegradable magnesium alloy. To clarify the influence of amino acid groups on film formation, Phenylalanine (Phe), Methionine (Met), and Asparagine (Asn) were used to regulate the degradation rate of magnesium alloy. Three amino acid-induced Ca-P (Ca-P_Phe, Ca-P_Met, and Ca-P_Asn) coatings were prepared on AZ31 magnesium alloy via a constant temperature water bath method at a temperature of 60^oC. Additionally, the morphology of the coatings, composition distributions, and phase structures were observed and analyzed via SEM, EDS, XRD, FTIR, and XPS. The corrosion resistance of the coating in simulated body fluid (Hank's solution) was investigated through electrochemical polarization, AC impedance, and hydrogen evolution tests. The formation mechanisms of amino acid additive-induced Ca-P (Ca-P_Phe, Ca-P_Met, and Ca-P_Asn) coatings on AZ31 magnesium alloy were probed. Results showed that the thicknesses of Ca-P, Ca-P_Phe, Ca-P_Met, and Ca-P_Asn coatings were about (3.47 ± 0.47), (6.06 ± 0.77), (7.63 ± 1.70), and (8.23 ± 1.37) μm, respectively. The main constituents of the amino acid-induced Ca-P coatings were CaHPO₄ and Ca₁₀(PO₄)₆(OH)₂ (HA). The results of electrochemical polarization curves, EIS, and hydrogen evolution tests demonstrated that the addition of amino acids enhanced the corrosion resistance of the Ca-P coatings, which was ascribed to the inhibition and adsorption of amino acid molecules on AZ31 magnesium alloy. The adsorption of the amino group was mainly achieved through the coupling of the lone pair electrons of nitrogen atoms with the surface, whereas the carboxyl group combined with Mg²⁺ via their oxygen atoms. Additionally, heteroatoms in amino acids could share their lone pair electrons with the vacant molecular orbitals of the magnesium alloy. A formation mechanism of amino acid-induced Ca-P coating was proposed.

Key words： AZ31 magnesium alloy coating amino acid adsorption corrosion resistance

收稿日期: 2021-02-01

ZTFLH:

TG174

基金资助:国家自然科学基金项目(52071191);山东省自然科学基金项目(ZR2020ME011);现代汽车零部件技术湖北省重点实验室开放课题项目(XDQCKF2021006)

作者简介: 王雪梅，女，1996年生，硕士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2021.00058 或 https://www.ams.org.cn/CN/Y2021/V57/I10/1258

图1 AZ31镁合金表面Ca-P涂层和3种氨基酸(苯丙氨酸、甲硫氨酸和天冬酰胺)诱导Ca-P涂层(Ca-PPhe、Ca-PMet和Ca-PAsn)制备流程图

图2 AZ31镁合金表面Ca-P涂层和3种氨基酸诱导Ca-P涂层的SEM像

表1 图2中点1~12的EDS分析结果 (atomic fraction / %)

图 3 AZ31镁合金表面Ca-P 涂层和3种氨基酸诱导Ca-P涂层截面形貌的SEM像和元素分布

图4 3种氨基酸诱导Ca-P涂层的XPS谱宽谱和精细谱(b, e, h) C1s (c, f, i) N1s

图5 AZ31镁合金表面Ca-P涂层和3种氨基酸诱导Ca-P涂层的Fourier红外光谱(FTIR)

图6 AZ31镁合金及其Ca-P涂层和3种氨基酸诱导Ca-P涂层的XRD谱

图 7 AZ31镁合金及其Ca-P涂层和3种氨基酸诱导Ca-P涂层的极化曲线

表2 AZ31 镁合金及其Ca-P 涂层和3种氨基酸诱导Ca-P涂层的Tafel极化曲线拟合数据

图8 AZ31 镁合金及其Ca-P涂层和3种氨基酸诱导Ca-P涂层的EIS分析

图9 AZ31镁合金及其Ca-P涂层和3种氨基酸诱导Ca-P涂层EIS的等效电路

Sample	R_s	CPE₁	n₁	R₁	CPE₂	n₂	R_ct	L	R_L
	Ω·cm²	10^-5 Ω^-1·s $n 1$ ·cm^-2		kΩ·cm²	10^-5 Ω^-1·s $n 2$ ·cm^-2		Ω·cm²	H·cm²	Ω·cm²
AZ31	85.88	1.278	0.9056	-	-	-	578.5	439.7	231.5
Ca-P	57.25	0.136	0.6946	-	2.616	0.6438	593.8	3.7	6856.0
Ca-P_Phe	70.00	0.875	0.6515	289.6	1.582	0.7757	7266.0	-	-
Ca-P_Met	84.64	1.859	0.6809	226.3	1.693	0.8297	7465.0	-	-
Ca-P_Asn	80.93	0.742	0.6782	157.8	1.873	0.8144	8552.0	-	-

表3 AZ31镁合金、Ca-P涂层和3种氨基酸诱导Ca-P涂层的EIS拟合数据

图10 AZ31镁合金、Ca-P涂层和3种氨基酸诱导Ca-P涂层的析氢曲线

图11 AZ31镁合金、Ca-P涂层和3种氨基酸诱导Ca-P涂层浸泡160 h后的宏观形貌和SEM像

表4 图11中点1~15的EDS分析结果 (atomic fraction / %)

图12 AZ31镁合金及其Ca-P涂层和3种氨基酸诱导Ca-P涂层浸泡160 h后的FTIR

图13 AZ31镁合金及其Ca-P涂层和3种氨基酸诱导Ca-P涂层浸泡160 h后的XRD谱

图14 Ca-PPhe、Ca-PMet和Ca-PAsn涂层的形成机理示意图

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