中国腐蚀与防护学报, 2025, 45(4): 1127-1134 DOI: 10.11902/1005.4537.2024.223

研究报告

激光重熔对生物可降解Zn-0.4Mn合金微观结构和性能的影响

岳锐1,2, 刘咏咏1, 杨丽景,2, 朱兴隆2, 陈权昕2, 阿那尔2, 张青科2, 宋振纶2

1 宁波大学材料科学与化学工程学院 宁波 315211

2 中国科学院宁波材料技术与工程研究所海洋关键材料全国重点实验室 宁波 315201

Effect of Laser Surface Remelting on Microstructure and Properties of Biodegradable Zn-0.4Mn Alloy

YUE Rui1,2, LIU Yongyong1, YANG Lijing,2, ZHU Xinglong2, CHEN Quanxin2, A Naer2, ZHANG Qingke2, SONG Zhenlun2

1 School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China

2 State Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China

通讯作者: 杨丽景,E-mail:yanglj@nimte.ac.cn,研究方向为金属材料腐蚀与防护

收稿日期: 2024-07-26   修回日期: 2024-11-07  

基金资助: “尖兵领雁+X”研发攻关计划项目.  2024C03078
宁波市国际科技合作项目.  2023H022
宁波市青年科技创新领军人才项目.  2023QL014

Corresponding authors: YANG Lijing, E-mail:yanglj@nimte.ac.cn

Received: 2024-07-26   Revised: 2024-11-07  

Fund supported: Zhejiang Province Leading Earth Goose + X Program.  2024C03078
Ningbo International R&D Collaboration Project.  2023H022
Ningbo Youth Science and Technology Innovation Leading Talent Project.  2023QL014

作者简介 About authors

岳锐,男,1999年生,硕士生

摘要

锌合金因其较低的腐蚀速率和良好的生物相容性,被认为是潜在的医用可降解金属材料。针对Zn-0.4Mn合金延伸率较好但表面硬度和耐磨性较低以及细胞相容性较差的问题,本研究在合金表面利用激光重熔技术在合金表面进行改性,并对激光重熔后合金的微观结构、显微硬度、耐磨性、耐腐蚀性和细胞相容性进行分析探讨。结果表明,重熔后的Zn-0.4Mn合金表面硬度和耐磨性显著提高;腐蚀电流密度降低以及阻抗的增大,表明了激光重熔提高了Zn-0.4Mn合金的耐腐蚀性;L929细胞毒性实验结果说明锌合金的生物相容性有所提升,这是由于重熔后合金耐蚀性增加,减少了锌离子的溶出。因此,激光重熔是提升锌合金力学性能、降解性能和生物安全性的一种有效手段。

关键词: 锌合金 ; 激光重熔 ; 显微硬度 ; 耐磨性 ; 耐腐蚀性

Abstract

Zn-alloys are regarded as promising biodegradable metallic materials due to their low corrosion rates and favorable cytocompatibility. To address the challenges associated with the Zn-0.4Mn alloy, which exhibits better ductility but lower surface hardness, wear resistance, and cytocompatibility etc., herein, the effect of surface laser remelting on the microstructure, microhardness, wear resistance, corrosion resistance, and cytocompatibility of the Zn-0.4Mn alloy was assessed. The findings revealed that the surface hardness and wear resistance of the remelted Zn-0.4Mn alloy were significantly enhanced. Furthermore, a reduction in corrosion current density and an increase in impedance indicated that laser remelting improved the corrosion resistance of the Zn-0.4Mn alloy. Additionally, L929 cytotoxicity tests demonstrated that the biocompatibility of the Zn-alloy was enhanced due to improved corrosion resistance and reduced leaching of Zn ions. Consequently, laser remelting emerges as an effective method for improving the mechanical properties, degradation characteristics, and biosafety of Zn-alloys.

Keywords: Zn-alloy ; laser surface remelting ; microhardness ; abrasion resistance ; corrosion resistance

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岳锐, 刘咏咏, 杨丽景, 朱兴隆, 陈权昕, 阿那尔, 张青科, 宋振纶. 激光重熔对生物可降解Zn-0.4Mn合金微观结构和性能的影响. 中国腐蚀与防护学报[J], 2025, 45(4): 1127-1134 DOI:10.11902/1005.4537.2024.223

YUE Rui, LIU Yongyong, YANG Lijing, ZHU Xinglong, CHEN Quanxin, A Naer, ZHANG Qingke, SONG Zhenlun. Effect of Laser Surface Remelting on Microstructure and Properties of Biodegradable Zn-0.4Mn Alloy. Journal of Chinese Society for Corrosion and Protection[J], 2025, 45(4): 1127-1134 DOI:10.11902/1005.4537.2024.223

Zn是许多生物体新陈代谢和生长所必需的微量元素,在各种生理过程中发挥重要作用。Zn还是乳酸脱氢酶、乙醇脱氢酶、DNA和RNA等多种酶的重要辅助因子和组成成分[1~3],这使得锌合金成为生物可降解金属材料的优选[4]。目前,对于生物可降解金属的研究主要集中在铁基合金、镁基合金和锌基合金3类。相较于镁基合金和铁基合金,锌合金的降解速率介于二者之间,且不出现气胀等影响组织愈合的现象。因此,锌合金越来越受到关注,成为研究热点[5~9]。理想的生物可降解植入物必须在一段时间内提供临时的机械支持,并在任务完成后完全降解。在不同应用条件下,对锌合金的力学性能和降解速率有不同的要求。然而,纯锌的力学性能较差,无法满足植入物材料的基本要求,因此通常使用合金化来提升锌的力学性能。根据之前的研究,Mn含量小于1% (质量分数)的二元Zn-Mn合金在室温下表现出优异的延展性[10~12],尤其是具有超细晶的Zn-0.4Mn合金,其延伸率可达245.0% ± 9.0%,实现了室温超塑性。相较于纯锌,Zn-Mn合金具有良好的综合力学性能,但其表面硬度仍需进一步提升。尽管合金化可以有效改善锌合金力学性能差的问题,但多数锌合金在体外的细胞相容性差的问题依然存在,其中锌离子浓度过高是影响结果的主要因素。针对锌合金的力学性能和细胞相容性差无法满足医用植入材料要求的问题,表面改性是一种有效的解决手段。常用的表面改性方法包括阳极氧化、碱性浸泡、微弧氧化、氟化物处理、仿生矿化聚合物涂层、磷酸钙涂层、羟基磷灰石(HA)涂层和激光表面重熔(LSR)等[13]。激光表面重熔可以细化表面晶粒,均匀合金元素分布,并提高合金元素的溶解度,同时不会对基底产生明显影响[14]。通过LSR,可以有效提高合金表面的机械强度及粗糙度,提高细胞粘附率,扩大与组织的接触面积;此外,LSR的操作灵活,耗时少,已被用于改善可生物降解镁合金的耐腐蚀性和润湿性[15~18],是调控表面微观结构和性能以满足植入物需求的最合适手段之一。目前,关于在锌合金上使用此技术的研究仍然较少。Wang等[19]的研究表明,由于Zn的蒸气压很高,在LSR过程中Zn通常会蒸发,从而影响最终的效果。另外,熔融锌在氩气中的反应活性较低[20]。因此,本研究采用了较低的热输入和氩气屏蔽,以尽量减少激光对锌合金的损害。

前期研究表明,Zn-0.4Mn合金具有良好的变形能力,同时展现出良好的塑性和优异的延展性[21,22],然而,该合金的强度和硬度较低,并且在加工过程中容易受到热影响导致加工软化,从而降低其强度 [21]。为了在保持Zn-0.4Mn合金良好塑性的同时提升其表面强度,本文采用LSR技术对Zn-0.4Mn合金的表面进行改性处理。本文详细研究了合金的微观结构、力学性能、耐蚀性能和细胞相容性,旨在寻找调控生物可降解锌合金性能的有效方法。

1 实验方法

本研究使用Zn-0.4Mn合金,通过多道次不同轧制比将材料轧制成为4 mm厚度的板材,然后切割成8 mm × 8 mm小块。再经过机械研磨、抛光和乙醇清洗后再进行激光处理。经过LSR处理后,样品表面进一步用抛光布抛光30 s,以去除激光重熔过程中产生的氧化物和杂质。本研究采用波长为1064 nm,最大功率为600 W的脉冲Nd:YAG激光器(JHM-1GY600D)。激光重熔参数如下:起止电流30 A,扫描速率200 mm/min,频率10 Hz,脉宽2 ms,光斑直径0.8 mm,Ar气流量20 L/min。

将上述得到的样品使用稀盐酸(0.1 mol/L)清洗,然后使用抛光布将其表面打磨约15 s去除表面在LSR过程产生的杂质。用400#、800#、1200#和2000#的砂纸依次打磨原始样品和处理过的样品的横截面,使用抛光布抛光至镜面,使用铬酸(200 g/L)腐蚀20 s,用去离子水冲洗并自然干燥。使用配备能量色散光谱仪的场扫描电子显微镜(SEM,FEI Quanta250)分析材料表面和横截面的微观结构。然后使用D8 ADVANCE DAVINCI X射线粉末衍射仪(XRD,BRUKER)对样品进行物相分析,XRD衍射角度范围为10°~90°,扫描速率为4 (°)/min。使用原位纳米压头(G200)测试抛光样品截面的显微硬度,施加5 μN的载荷,下压速率为10 nm/s,峰值保持时间为10 s。每个测试点等距排列,第一个测试点距离样品表面约40 μm,每个测试点之间的间距为50 μm。测试示意图如图1所示。测试点从左到右排列,1为样品重熔区,6为基底。使用Ampadon多功能高温摩擦磨损试验机进行摩擦磨损实验,实验方式为直线高速往复干摩擦,接触力设定为1.5 N,频率设定为1.5 Hz,摩擦时间设定为1800 s。摩擦实验后,使用表面轮廓仪测量试样的摩擦深度。

图1

图1   纳米压痕测试示意图

Fig.1   Schematic diagram of nanoindentation test


使用Auto Lab (PGSTAT 302)电化学工作站对样品进行动电位极化曲线(PDP)和电化学阻抗谱(EIS)测试。采用三电极体系,样品为工作电极,铂片为对电极,饱和甘汞电极为参比电极,测试面积为8 mm × 8 mm,其余面积通过环氧树脂包裹,测试溶液为模拟体液(c-SBF,溶液pH值为7.30~7.40,成分如表1所示),测试温度为室温。工作电极分别为未处理的原始样品和激光重熔后的表面。实验之前,先将样品在SBF中保持30 min,使其达到稳定状态降低误差。

表1   SBF溶液的离子浓度[23]

Table 1  Ion concentration of SBF solution[23]

CompositionConcentration
Na+142 mmol/L
K+5.0 mmol/L
Ca2+2.5 mmol/L
Mg2+1.5 mmol/L
HCO3-4.2 mmol/L
Cl-147 mmol/L
HPO42-1 mmol/L
SO42-0.5 mmol/L
Tris6.069 g/L

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根据ASTMG31-72标准进行腐蚀浸泡实验,每种实验材料至少制备5个平行样品,原始样品打磨抛光至无明显划痕,与激光重熔过的样品一起用无水乙醇超声清洁,使用环氧树脂将样品包裹后按照一定的表面积、腐蚀溶液c-SBF体积比放置在37 ℃恒温箱内,分别浸泡3、7和15 d。试样在不同浸泡时间后取出,使用SEM对腐蚀形貌进行观察和分析。

L-929成纤维细胞用于对样品进行24和72 h的四甲基偶氮唑盐(MTT法)细胞毒性实验。细胞培养基由DMEM (含双抗)和胎牛血清组成。细胞附着到表面后,每24 h更换一次培养基,以监测细胞生长。浸提液的制备遵循ISO 10993-5:2009指南。将样本烘干,用紫外线消毒24 h,然后以2∶3的比例(样本表面积与培养液体积)浸泡在培养液中,在37 ℃的CO2培养箱中浸泡72 h,以达到100%浸泡。细胞培养基和浸泡液混合成25%的浸提液,用于将细胞转移到96孔板中进一步培养。观察细胞附着到表面后,更换浸泡培养液。培养24和72 h后,用4%多聚甲醛固定细胞,并分别用异硫氰酸荧光素(Fluorescein isothiocyanate isomer)和4′,6-二脒基-2-苯基吲哚(4′,6-diamidino-2-phenylindle)对细胞骨架和细胞核进行染色。使用倒置荧光显微镜(Nikon,Ti2-U)监测细胞生长。

2 结果与讨论

2.1 LSRZn-0.4Mn合金表面形貌的影响

经LSR处理的样品的表面形貌和横截面显微组织如图2所示。图2a为经LSR处理后样品的表面。在Ar的保护下,样品的表面损伤降到了最低,获得了高质量的表面。从图2b中LSR处理样品的横截面形态来看,处理后的熔池深度约为120 μm。由于冷却速度过快,重熔区多为树枝状晶粒[24];在基底与重熔区之间形成柱状晶区,原因是固液界面附近的传热特性导致晶粒从基底长到重熔区[25]

图2

图2   LSR处理的Zn-0.4Mn合金的表面和横截面形貌

Fig.2   Surface (a) and cross sectional (b) morphologies of the LSR-treated Zn-0.4Mn alloy


图3显示了原始样品和经LSR处理的Zn-0.4Mn合金的XRD谱。原始样品的XRD谱显示出较强的Zn峰和较弱的MnZn13峰,经LSR处理的Zn-0.4Mn合金显示出衍射强度更均匀的Zn峰,未显示出明显的MnZn13峰,这表明经过LSR处理后大多数的MnZn13相固溶进了Zn基体中。

图3

图3   Zn-0.4Mn合金和LSR处理的Zn-0.4Mn合金的XRD谱

Fig.3   XRD patterns of the Zn-0.4Mn alloy and LSR-treated Zn-0.4Mn alloy


2.2 LSRZn-0.4Mn合金硬度的影响

2.2.1 显微硬度

图4a显示了LSR后试样在截面上的纳米压痕载荷-深度曲线,图4b显示了显微硬度分布。Zn-0.4Mn合金基体的硬度为0.6~0.8 GPa。重熔层的硬度范围为1.5~2.0 GPa,过渡区的硬度约为1.1 GPa。经过LSR处理,在材料的表面减少了MnZn13相的析出,部分MnZn13相固溶进了Zn基体,使得材料表面的微观结构更加均匀,而固溶的Mn原子造成的晶格畸变会增强位错滑移阻力,从而增加了样品的硬度。实验结果表明,LSR处理后重熔层的硬度得到明显提高。

图4

图4   LSR处理的Zn-0.4Mn合金在载荷为5 μN和持续时间为10 s的条件下的载荷-深度曲线和硬度分布曲线

Fig.4   Load-depth curve (a) and brinell hardness distribution curve (b) of LSR-treated Zn-0.4Mn alloy at a load of 5 μN and a duration of 10 s


2.2.2 摩擦磨损

图5a为1800 s内Zn-0.4Mn合金和LSR处理后的Zn-0.4Mn合金摩擦系数的变化曲线,图5bc为样品摩擦后的深度分布曲线,表2显示了1800 s后样品的摩擦系数和磨损深度。从图5a可以看出,经LSR处理后样品摩擦系数减小,在相同应力下的摩擦损失减小。Zn-0.4Mn合金的曲线可分为两个阶段:在Ⅰ阶段,摩擦系数随滑动行程呈波动上升趋势;进入Ⅱ阶段后,摩擦系数波动很小,稳定在平均值0.42附近。而经LSR处理的Zn-0.4Mn合金的摩擦系数稳定在平均值0.30附近。从图5bc中可以看出,在相同的摩擦条件下,激光重熔前后的样品磨损深度差距较大,原始样品的磨损深度为107.99 μm,经LSR处理的Zn-0.4Mn合金磨损深度为10.04 μm,小于重熔层的厚度,所以经LSR处理的Zn-0.4Mn合金的摩擦系数比较稳定。一般而言,金属的硬度越高,其抵抗塑性变形的能力也会越强,耐磨性也越好[26]。实验结果表明,LSR可以降低Zn-0.4Mn合金的摩擦系数,减少摩擦损耗,提高耐磨性。

图5

图5   在2 N的载荷和2 Hz的频率下对样品进行1800 s的摩擦和磨损测试的摩擦系数变化曲线和磨损深度曲线

Fig.5   Samples were tested for friction and wear at a force of 2 N and a frequency of 2 Hz for 1800 s: (a) evolution of friction coefficient, (b) wear depth of the Zn-0.4Mn alloy, (c) wear depth of the LSR-treated Zn-0.4Mn alloy


表2   摩擦系数和磨损深度

Table 2  Friction coefficients and wear depth

SampleFriction coefficientDepth of wear / μm
Zn-0.4Mn alloy0.42107.99
LSR-treated Zn-0.4Mn alloy0.3010.04

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2.3 LSRZn-0.4Mn合金腐蚀性能的影响

图6ab显示了原始样品在SBF中浸泡不同时间后的表面腐蚀形态。浸泡3 d后,表面出现了一些腐蚀产物。当浸泡时间延长到7 d时,腐蚀产物继续累积,并出现了明显的腐蚀坑。这是因为Zn-Mn合金中存在第二相MnZn13相,且MnZn13相的电位低于Zn基体,易在腐蚀过程中发生微电偶腐蚀,MnZn13相优先被腐蚀[27,28]图6a3显示,在浸泡15 d后,由于腐蚀产物十分蓬松,所以在腐蚀产物堆积的时候产生剥落,形成了较大的腐蚀坑(图6b3)。图6cd显示了经LSR处理的Zn-0.4Mn合金的表面腐蚀形貌。浸泡3 d后,腐蚀产物开始出现,腐蚀产物的分布与在原始样品上的分布相似(图6c1)。浸泡7 d后,腐蚀产物没有大量的聚集,样品表面的部分区域出现了较浅的腐蚀坑。浸泡15 d后,有更多的腐蚀坑出现,同时腐蚀坑略有加深。与原始样品相比LSR处理的表面腐蚀坑分布得更加均匀,样品趋向均匀腐蚀。

图6

图6   在SBF中浸泡不同天数的试样的腐蚀形貌

Fig.6   Corrosion morphologies of Zn-0.4Mn alloy (a, b) and LSR-treated Zn-0.4Mn alloy (c, d) with (a, c) and without (b, d) corrosion products after immersed in SBF for 3 d (a1-d1), 7 d (a2-d2) and 15 d (a3-d3)


图7所示,在室温下通过PDP和EIS测试评估基体和重熔表面的腐蚀性能。表3为根据Tafel外推法获得的腐蚀电流密度(Icorr)和自腐蚀腐蚀电位(Ecorr)。根据图7a可知,原始合金腐蚀电位和腐蚀电流密度分别为-1.12 V和23.74 μA/cm2,激光重熔过后,Icorr下降,变为16.52 μA/cm2,说明腐蚀速率降低,耐腐蚀性能增强;LSR处理前后的腐蚀速率分别为0.28和0.19 mm/a,LSR处理使腐蚀速率降低。

图7

图7   试样在SBF溶液中浸泡30 min后的极化曲线和EIS

Fig.7   Polarization curves (a), Nyquist (b) and Bode plots (c) of specimens after immersion in SBF solution for 30 min


表3   在SBF溶液的PDP测试结果

Table 3  PDP test results in SBF solutions

SampleIcorr / μA·cm-2Ecorr / VRp / kΩ·cm2CR / mm·a-1
Zn-0.4Mn alloy23.74-1.120.770.28
LSR-treated Zn-0.4Mn alloy16.52-1.120.280.19

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图7bc显示了原始样品和LSR处理样品的Nyquist图和Bode图。Nyquist图显示LSR前后样品均表现为两个容抗弧,高频容抗弧代表着电子转移过程,低频容抗弧代表着金属溶解过程中的物质转移过程,并且经过LSR处理的样品具有更大的容抗弧半径,说明经过LSR处理的样品的耐腐蚀性更好。Bode图中存在两个峰,这与Nyquist图和双时间常数的等效电路相匹配,在这个等效电路中,Rs是溶液电阻,Rcpf是腐蚀产物层电阻,Rct是样品与溶液之间的电荷转移电阻,QcpfQdl相当于双电层电容。表4显示了EIS等效电路的拟合结果,经过LSR处理的样品的Rct (767 Ω·cm2)小于原始样品的Rct (1109 Ω·cm2),但经过LSR处理的样品的Rcpf (607.8 Ω·cm2)大于原始样品的Rcpf (202.9 Ω·cm2),而更高的Rcpf + Rct值表明具有更好的耐腐蚀性。实验结果表明,LSR可以提高Zn-0.4Mn合金的耐腐蚀性,这是由于经过LSR处理导致部分表面的MnZn13相固溶进了Zn基体中,使得与表面基体Zn相发生微电偶腐蚀的MnZn13相数量减少,从而提升了合金的耐蚀性。

表4   在SBF溶液中的EIS拟合结果

Table 4  Results of EIS fitting in SBF solution

SampleRs / Ω·cm2Qcpf-Yo / Ω·cm-2·S-nQcpf-nRcpf / Ω·cm2Qct-Yo / Ω·cm-2·S-nQdl-nRct / Ω·cm2
Zn-0.4Mn alloy16.33.49 × 10-60.93202.91.60 × 10-60.991109
LSR-treated Zn-0.4Mn alloy13.42.10 × 10-40.56607.82.58 × 10-30.66767

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2.4 LSRZn-0.4Mn合金细胞相容性的影响

图8显示了Zn-0.4Mn合金和LSR处理过的Zn-0.4Mn合金25%浸提液中培养24和72 h后经由荧光染色得到的L-929细胞形态。表5列出了体积液和培养液中的元素含量。培养24 h后,各浸提液中细胞的生长情况与对照组无明显区别;培养72 h后,经过LSR处理的样品组的细胞生长情况明显优于Zn-0.4Mn合金组,这是由于LSR处理后,部分表面的MnZn13相固溶进了Zn基体中,从而减少了Zn-0.4Mn中的第二相MnZn13的析出,局部的Zn和MnZn13形成的电位差相较与未经处理的原始样品的电位差低[29],减少了锌离子的释放,促进了细胞生长,LSR对Zn-0.4Mn合金的细胞相容性有一定的提升。

图8

图8   L-929细胞在25%浓度提取物的不同试样中培养24和72 h后的生长形态

Fig.8   Growth morphologies of L-929 cells cultured for various times in Zn-0.4Mn alloy (a), LSR-treated Zn-0.4Mn alloy (b) and comparison group (c) with 25% concentration of extracts


表5   ICP-OES对浸提液中元素的测定结果

Table 5  Results of ICP-OES determination of the elements in the sample extract

SampleZn / mg·L-1Mn / mg·L-1Ca / mg·L-1P / mg·L-1
Culture medium0.02< 0.0133.8861.97
Zn-0.4Mn alloy5.810.0133.3964.79
LSR-treated Zn-0.4Mn alloy8.390.0336.9663.67

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3 结论

(1) LSR能有效提高Zn-0.4Mn合金的表面硬度和耐磨性,这归因于LSR促进了Mn原子固溶,而固溶的Mn原子造成的晶格畸变会增加位错滑移的阻力。

(2) LSR能有效提高Zn-0.4Mn合金的表面耐腐蚀性,归因于LSR使得会与基体Zn相发生微电偶腐蚀的MnZn13相数量减少。

(3) LSR处理的Zn-0.4Mn合金可改善其细胞相容性,归因于LSR处理的Zn-0.4Mn合金减少了Zn-0.4Mn中的第二相MnZn13的析出,降低了局部的Zn和MnZn13形成的电位差,减少了Zn的析出,从而提高细胞活性,降低对细胞的毒性。

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