Ca和Ag的含量对可降解Zn-Li-Ca-Ag合金的组织和性能的影响
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Effect of Ca and Ag Content on Microstructure and Properties of Biodegradable Alloy Zn-Li-Ca-Ag
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通讯作者: 谭丽丽,研究员,lltan@imr.ac.cn,研究方向为生物医用可降解金属材料及器械
责任编辑: 黄青
收稿日期: 2022-11-03 修回日期: 2023-10-12
基金资助: |
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Corresponding authors: TAN Lili, Tel:
Received: 2022-11-03 Revised: 2023-10-12
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作者简介 About authors
闫俊竹,女,1998年生,硕士
制备可降解Zn-Li-Ca-Ag合金,使用光学显微镜(OM)、扫描电镜(SEM)、万能试验机和电化学测试等手段研究了Ca和Ag的含量对这种合金的微观组织、力学性能和耐蚀性能的影响。结果表明:Zn-Li-Ca-Ag合金的微观组织由树枝晶组成,Ca通过第二相强化使锌合金的强度提高,Ag细化枝晶使锌合金的塑性提高。Zn-0.8Li-0.1Ca-0.2Ag合金的抗拉强度达到了186 MPa。Ca和Ag都能提高锌合金的耐蚀性能。
关键词:
Due to the suitable degradation rate and good biocompatibility, Zn-alloys have great potential as biomedical degradable materials. However, the low mechanical properties of pure Zn limit its development as a biomedical material. In this paper, the known degradable Zn-Li-Ca-Ag alloy was further alloyed with different amount of Ca and Ag. The microstructure, mechanical properties and corrosion resistance of the prepared Zn-Li-Ca-Ag alloys were characterized by means of optical microscopy (OM), scanning electron microscopy (SEM), universal testing machine and electrochemical tests. The results showed that the microstructure of the Zn-Li-Ca-Ag alloy was composed of dendrites. The Ca addition can improve the strength of the Zn alloy by second-phase strengthening, and the Ag addition has a positive influence on the plasticity of the Zn alloy by refining the size of the dendrites. Ca has stronger influence on the enhancement of the alloy strength rather than Ag, and amoung others, the Zn-0.8Li-0.1Ca-0.2Ag alloy exhibits the highest tensile strength (186 MPa). The co-addition of Ca and Ag can also improve the corrosion resistance of Zn alloy.
Keywords:
本文引用格式
闫俊竹, 高明, 于晓明, 谭丽丽.
YAN Junzhu, GAO Ming, YU Xiaoming, TAN Lili.
可降解锌合金具有良好的生物相容性,是一种有极大潜力的生物医用可降解材料,其降解速度位于可降解镁基合金和可降解铁基合金之间,降解速度适当且Zn是人体必要的营养元素,参与体内200多种酶的活动与代谢。
1 实验方法
1.1 Zn-Li-Ca-Ag合金的制备
制备Zn-0.8Li-xCa-0.2Ag (x = 0,0.05,0.1,%,质量分数)和Zn-0.8Li-0.05Ca-xAg (x = 0,0.5,1,%)合金的原料:纯锌(99.99%)、Zn-3Li中间合金、纯钙(99.99%)和纯银(99.99%)。熔炼前,去除原料表面氧化皮、烘干并称重。在200℃将坩埚预热20 min。在熔炼过程中,先将纯锌在450℃的电阻炉中熔化30 min,依次加入中间合金、纯银和纯钙后进行搅拌。将熔体在650℃保温20 min后将温度降至550℃并倒入模具中。使用电感耦合等离子体发射光谱仪(ICP-AES)测量Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金的化学成分,结果列于表1。
表1 Zn-Li-Ca-Ag合金的化学成分
Table 1
Alloy | Li | Ca | Ag | Zn |
---|---|---|---|---|
Zn-0.8Li-0.2Ag | 0.74 | 0 | 0.2 | Bal. |
Zn-0.8Li-0.05Ca-0.2Ag | 0.73 | 0.048 | 0.22 | Bal. |
Zn-0.8Li-0.1Ca-0.2Ag | 0.72 | 0.096 | 0.2 | Bal. |
Zn-0.8Li-0.05Ca | 0.73 | 0.051 | 0 | Bal. |
Zn-0.8Li-0.05Ca-0.5Ag | 0.72 | 0.065 | 0.53 | Bal. |
Zn-0.8Li-0.05Ca-1Ag | 0.74 | 0.044 | 0.98 | Bal. |
1.2 微观结构和性能表征
1.2.1 观测微观结构
将样品用200-2000目碳化硅砂纸研磨并用0.5 mm金刚石抛光膏抛光,用4%硝酸酒精溶液蚀刻后在光学金相显微镜(Zeiss ZM-1)下观察锌基四元合金的微观组织并在特定的放大倍数下拍摄适合每种合金晶粒度水平的图像。用扫描电子显微镜(FEI Inspect F50和FEI Nano SEM Nova 430)表征锌基四元合金样品的显微组织;用能量色散光谱仪(Energy dispersive spectrometer,EDS)分析样品中的相和腐蚀产物的成分。
1.2.2 测试硬度
用硬度计测量Zn-Li-Ca-Ag合金的硬度,载荷为100 g,加载时间为15 s,取每个样品6个压痕测试结果的平均值。
1.2.3 测试力学性能
在室温下使用Zwick Z050万能拉伸机进行拉伸实验,样品上平行段的长度为15 mm宽度为3 mm,厚度为3 mm。每组测试3个平行样品,取其结果的平均值。用扫描电子显微镜(FEI Inspect F50和FEI NanoSEM Nova 430)观察拉伸断口,用以分析Ag和Ca元素对锌合金力学性能的影响。
1.2.4 测试耐蚀性能
进行浸泡实验测试耐蚀性能。用于浸泡实验的锌合金样品的直径为10 mm 长度为5 mm (5组平行样品)。将其称重后浸入37℃的Hank's溶液中,Hank's溶液的成分列于表2。浸泡7、14和21 d后取出样品,用蒸馏水冲洗后在室温下干燥。清洗腐蚀产物前,分析和评价腐蚀产物的表面形貌、元素组成以确定生成的腐蚀产物。按照ASTM G1标准(准备、清洁和评估腐蚀测试样品的标准操作规程)的规定,用200 g/LCrO3去除腐蚀产物。将清洗后的样品称重以确定质量损失。锌合金的腐蚀速率为 (KW)/(ATD),其中系数K = 87600,W为失重(g),A为暴露在Hank's溶液中的样品表面积(cm2),T为暴露时间(h),D为材料的密度(g/cm3)。
表2 Hank's溶液的化学成分
Table 2
Composition | Content / g·L-1 |
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NaCl | 8.00 |
KCl | 0.40 |
MgSO4·7H2O | 0.06 |
CaCl2 | 0.14 |
Na2HPO4·12H2O | 0.06 |
KH2PO4 | 0.06 |
MgCl2 | 0.10 |
NaHCO3 | 0.35 |
1.2.5 测试动电位极化曲线和电化学阻抗谱(EIS)
使用电化学工作站(Gamry Reference 610,USA)进行电化学实验,在37℃的Hank's溶液中使用三电极系统(铂电极为对电极,饱和甘汞电极作为参比电极,样品作为工作电极)。先进行30 min的开路电位测试以确保电化学系统处于稳定状态,然后在100 kHz~10 mHz频率范围内测试电化学阻抗,最后以0.5 mV/s的扫描速率测试动电位极化曲线,其起始电位和终止电位分别为-0.1 V和0.1 V(以开路电位为参照)。使用Gamry Echem Analyst软件拟合动电位极化曲线和电化学阻抗曲线。
2 实验结果
2.1 铸态Zn-Li-Ca-Ag系合金的微观组织
图1和图2分别给出了铸态Zn-Li-Ca-Ag系合金微观组织的OM图和SEM照片。可以看出,铸态Zn-0.8Li-0.2Ag合金的显微组织由粗大的初始树枝晶构成,添加0.05%Ca后显微组织中出现暗色棱角分明的析出物(图2b),且随着Ca含量的提高析出物的尺寸增大。表3为图2中标记位置的EDS能谱分析,可以看出这种析出物主要含有Ca和Zn,可能是CaZn13相。Zn-0.8Li-0.05Ca-xAg合金的微观组织也由大量的树枝晶构成,随着Ag含量的提高枝晶的尺寸减小。在四种不同成分的Zn-Li-Ca-Ag系合金中都没有观察到含Ag的第二相,因为合金中Ag的含量远低于Ag在Zn中的固溶度(5%,原子分数),Ag全部固溶到了锌基体中而不能生成含Ag的第二相[18]。
图1
图1
铸态Zn-0.8Li-xCa-0.2Ag合金和Zn-0.8Li-0.05Ca-xAg合金的微观组织
Fig.1
Microstructure of cast Zn-0.8Li-xCa-0.2Ag and Zn-0.8Li-0.05Ca-xAg alloys (a) 0, (b) 0.05, (c) 0.1, (d) 0, (e) 0.5, (f) 1
图2
图2
铸态Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金中第二相的分布
Fig.2
Second phase distribution of as-cast Zn-0.8Li-xCa-0.2Ag and Zn-0.8Li-0.05Ca-xAg alloys (a) 0, (b) 0.05, (c) 0.1, (d) 0,(e) 0.5, (f) 1
表3 图2中标记位置的能谱结果
Table 3
Point | Element / mass fraction, % | ||
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Zn | Ca | Ag | |
1 | 98.71 | 0 | 1.29 |
2 | 95.09 | 4.91 | 0 |
2.2 铸态Zn-Li-Ca-Ag系合金的力学性能
图3给出了铸态Zn-Li-Ca-Ag系合金的显微硬度。可以看出,随着Ca含量的提高合金的维氏硬度随之提高。铸态Zn-0.8Li-0.2Ag合金的维氏硬度为58.484HV,添加0.05%和0.1%的Ca使其维氏硬度分别提高至66.282HV和70.054HV。而Ag的加入对合金硬度的影响不大,Zn-0.8Li-0.05Ca-xAg合金的显微硬度均约为60HV。
图3
图3
铸态Zn-0.8Li-xCa-0.2Ag合金和Zn-0.8Li-0.05Ca-xAg合金的显微硬度
Fig.3
Microhardness of as cast Zn-0.8Li-xCa-0.2Ag alloy and Zn-0.8Li-0.05Ca-xAg alloy
图4给出了铸态Zn-Li-Ca-Ag系合金的应力应变曲线和力学性能。可以看出,随着Ca和Ag含量的提高铸态合金的抗拉强度明显提高。Zn-0.8Li-0.2Ag合金的抗拉强度为136 MPa,Ca含量为0.05%的合金其抗拉强度提高到151 MPa,Ca含量为0.1%的合金其抗拉强度最高186 MPa。Zn-0.8Li-xCa-0.2Ag合金的抗拉强度高于Zn-0.8Li-0.05Ca-xAg,铸态Zn-0.8Li-0.05Ca的抗拉强度为99 MPa,添加0.5%和1%Ag的合金其强度分别提高到112 MPa和124 MPa。虽然铸态Zn-Li-Ca-Ag系合金的强度均有所提高但是其延伸率较低,图4中的应力-应变曲线表明所有铸态合金都没有出现屈服而直接断裂。图5给出了铸态Zn-Li-Ca-Ag系合金拉伸后微观断口的形貌。可以看出,所有成分的合金其断口均呈现出典型的解理断裂的特征,表明属于脆性断裂。随着Ca含量的提高Zn-Li-Ca-Ag系合金的断裂延伸率降低,而随着Ag含量的提高合金的延伸率和抗拉强度呈现出同步提高的趋势。
图4
图4
铸态Zn-0.8Li-xCa-0.2Ag合金(x = 0, 0.05, 0.1%) 和Zn-0.8Li-0.05Ca-xAg合金(x = 0, 0.05, 0.1%)的应力应变曲线和室温拉伸力学性能
Fig.4
Stress-strain curves (a, b) and room temperature tensile mechanical properties (c) of as cast Zn-0.8LixCa-0.2Ag alloys (x = 0, 0.05, 0.1, mass fraction, %) (a) and Zn-0.8Li-0.05Ca-xAg alloys (x = 0, 0.05, 0.1, mass fraction, %) (b)
图5
图5
铸态Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金的断口形貌
Fig.5
Fracture morphology of as cast Zn-0.8Li-xCa-0.2Ag and Zn-0.8Li-0.05Ca-xAg alloys (a) 0, (b) 0.05, (c) 0.1, (d) 0, (e)0.5, (f) 1
2.3 铸态Zn-Li-Ca-Ag系合金的体外腐蚀性能
2.3.1 在模拟体液中浸泡发生的氧化还原反应和腐蚀产物的形貌
图6a,b给出了Zn-Li-Ca-Ag系合金浸泡在模拟体液中pH值与浸泡时间的关系。可以看出,浸泡在Hank's溶液中的六种锌合金,其pH值与浸泡时间的关系均呈现先降低后升高最后趋于稳定的趋势。在前7 d内pH值迅速下降,主要原因是锌合金溶液中发生氧化还原反应产生了H+。随着浸泡时间的延长,Hank's溶液中的Cl-与Zn(OH)2发生反应
生成Zn2+和OH-使溶液的pH值提高,浸泡15 d后pH值趋于稳定。
图6
图6
铸态Zn-0.8Li-xCa-0.2Ag合金(x = 0, 0.05, 0.1, mass fraction / %)和Zn-0.8Li-0.05Ca-xAg合金(x = 0, 0.05, 0.1, mass fraction / %)在Hank's溶液中浸泡21 d的pH值的变化曲线和腐蚀速率
Fig.6
Variation of pH value (a, b) and corrosion rate (c) of as cast Zn-0.8Li-xCa-0.2Ag alloy (x = 0, 0.05, 0.1%) (a) and Zn-0.8Li-0.05Ca-xAg alloy (x = 0, 0.05, 0.1%) (b) after immersion in Hank's solution for 21 d
图7给出了铸态Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金在Hank's溶液中浸泡7 d后腐蚀产物的形貌。可以看出,Zn-0.8Li-xCa-0.2Ag合金的腐蚀产物呈“针状”和“雪花状”,而Zn-0.8Li-0.05Ca-xAg合金的腐蚀产物呈“球状”。表4列出了图7中标记位置的能谱,可见Zn-0.8Li-xCa-0.2Ag合金中的腐蚀产物中锌氧原子比接近1∶1,Zn-0.8Li-0.05Ca-xAg合金中腐蚀产物的锌氧原子比接近1∶3。根据典型的腐蚀产物形貌和能谱推测,雪花状和针状腐蚀产物可能是ZnO,而球状腐蚀产物可能是ZnCO3。图8给出了铸态Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金在Hank's溶液中浸泡7 d后腐蚀产物的XRD谱,印证了这个推测。Zn-0.8Li-xCa-0.2Ag合金的腐蚀产物主要是ZnO,而Zn-0.8Li-0.05Ca-xAg的腐蚀产物主要是ZnCO3。除了ZnO和ZnCO3,腐蚀产物中还有ZnCl2和CaCO3。
图7
图7
铸态Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金在Hank's溶液中浸泡7 d后腐蚀产物的形貌
Fig.7
Corrosion products morphology of as cast Zn-0.8Li-xCa-0.2Ag and Zn-0.8Li-0.05Ca-xAg alloys after 7 d of immersion in Hank's solution (a) 0, (b) 0.05, (c) 0.1, (d) 0, (e) 0.5, (f) 1
表4 图7中标记位置的能谱结果
Table 4
Element | Point | |
---|---|---|
1 | 2 | |
C | 0% | 0.82% |
O | 36.00% | 60.03% |
Na | 7.94% | 7.76% |
P | 12.63% | 5.10% |
K | 0.42% | 0. 17% |
Ca | 4.55% | 0.70% |
Zn | 38.47% | 25.42% |
Total | 100.00% | 100% |
图8
图8
铸态Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金在Hank's溶液中浸泡7 d后腐蚀产物的XRD谱
Fig.8
XRD patterns of corrosion products of cast Zn-0.8Li-xCa-0.2Ag and Zn-0.8Li-0.05Ca-xAg alloys after 7 d of immersion in Hank's solution
图9
图9
铸态Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金在Hank's溶液中浸泡21 d去除腐蚀产物后的形貌
Fig.9
Corrosion morphologies of as cast Zn-0.8Li-xCa-0.2Ag and Zn-0.8Li-0.05Ca-xAg alloys immersed in Hank's solution for 21 d after removing corrosion products (a) 0, (b) 0.05, (c) 0.1, (d) 0, (e) 0.5, (f) 1
图6b给出了六种样品在37℃模拟体液中浸泡7、14和21 d后的腐蚀速率。可以看出,这六种不同样品腐蚀速率的变化趋势相似。随着浸泡时间的延长试样表面腐蚀产物的增加,保护了合金而使腐蚀速率降低并趋于一个稳定值。在浸泡初期,六种成分合金的腐蚀速率较高,Zn-0.8Li-0.2Ag合金浸泡第7 d的腐蚀速率最高(0.134 mm·a-1)。由于腐蚀产物的保护,浸泡21 d后合金的腐蚀速率明显降低,Zn-0.8Li-0.05Ca-0.2Ag合金的腐蚀速率最低(0.01375 mm·a-1)。虽然不同成分的锌合金其腐蚀速率随浸泡时间变化的趋势相同,但是不同合金的耐蚀性能不同。添加合金元素钙使合金的腐蚀速率降低,随着钙含量的提高锌合金的腐蚀速率先降低后提高。添加合金元素银使合金的腐蚀速率提高,随着银含量的提高腐蚀速率先提高后降低。
2.3.2 动电位极化曲线和EIS曲线
图10给出了Zn-Li-Ca-Ag合金在Hank's溶液中的动电位极化曲线和EIS曲线。可以看出,这些合金的动电位极化曲线的特征相似。在极化曲线的阳极分支上均出现了明显的钝化区,表明在样品表面生成的致密钝化膜可提高合金的耐蚀性。合金的腐蚀电位越高,腐蚀电流密度越小,合金耐蚀性能越好;腐蚀电位越低,腐蚀电流密度越大,合金耐蚀性越差。表5列出了动电位极化曲线的拟合结果。可以看出,Zn-0.8Li-0.05Ca-0.2Ag合金的腐蚀电流密度最小(3.130 μA/cm2),Zn-0.8Li-0.05Ca-0.5Ag合金的腐蚀电流密度最大(12.20 μA/cm2)。动电位极化曲线的拟合结果表明,六种不同成分锌合金其耐蚀性能高低的排序为:Zn-0.8Li-0.05Ca-0.2Ag > Zn-0.8Li-0.1Ca-0.2Ag > Zn-0.8Li-0.05Ca > Zn-0.8Li-0.2Ag > Zn-0.8Li-0.05Ca-1Ag > Zn-0.8Li-0.05Ca-0.5Ag。
图10
图10
Zn-0.8Li-xCa-0.2Ag合金和Zn-0.8Li-0.05Ca-xAg合金的动电位极化曲线,Nyquist曲线和等效拟合电路
Fig.10
Potential polarization curves (a, b), Nyquist curves and equivalent fitting circuit of Zn-0.8Li-xCa-0.2Ag (x = 0, 0.05, 0.1, masss fraction, %) alloy (c) and Zn-0.8Li-0.05Ca-xAg alloy (x = 0, 0.5, 1, masss fraction, %) (d)
表5 极化曲线的拟合结果
Table 5
Alloys | Corrosion potential (Ecorr) / V vs. SCE | Corrosion current density (Icorr) / μA·cm-2 | Corrosion rate (Vcorr) / mm·a-1 |
---|---|---|---|
Zn-0.8Li-0.2Ag | -1.240 | 6.330 | 2.820 |
Zn-0.8Li-0.05Ca-0.2Ag | -1.250 | 3.130 | 1.396 |
Zn-0.8Li-0.1Ca-0.2Ag | -1.270 | 5.250 | 2.341 |
Zn-0.8Li-0.05Ca | -1.190 | 5.420 | 3.480 |
Zn-0.8Li-0.05Ca-0.5Ag | -1.290 | 12.20 | 7.838 |
Zn-0.8Li-0.05Ca-1Ag | -1.220 | 7.580 | 4.866 |
根据容抗弧的半径可判断合金的降解性能。容抗弧的半径越大,表明表合金的耐蚀性能越好,降解速率低。由图10可见,合金降解速率由低到高的排序为:Zn-0.8Li-0.05Ca-0.2Ag < Zn-0.8Li-0.1Ca-0.2Ag < Zn-0.8Li-0.05Ca < Zn-0.8Li-0.2Ag < Zn-0.8Li-0.05Ca-1Ag < Zn-0.8Li-0.05Ca-0.5Ag。
六种合金都只有一个容抗弧,表明合金在Hank's溶液中只有一个时间常数,对应合金和溶液界面上的反应电阻和双电层电容。半圆形的容抗弧,表征了电化学电荷传递过程。加入少量Ca使电极反应过程中容抗弧的半径增大,阻力增加,腐蚀电流减小。加入少量的Ag使合金容抗弧半径减小,阻力减小,腐蚀电流密度增大。Zn-0.8Li-0.05Ca合金的腐蚀电流密度为5.42 μA/cm2。银含量为0.5%和1%的合金,其腐蚀电流密度分别增大到12.2 μA/cm2和7.58 μA/cm2。由图10还可见,Zn-0.8Li-0.05Ca-0.2Ag合金在高频区的容抗弧直径比其它两种合金的大,表明Zn-0.8Li-0.05Ca-0.2Ag合金比其它三种合金的电荷转移电阻大。Zn-0.8Li-0.2Ag和Zn-0.8Li-0.1Ca-0.2Ag合金的电极容抗弧直径小,表明其具有较小的电荷转移电阻和较强的活性。
3 讨论
3.1 合金元素对Zn-Li-Ca-Ag系合金力学性能的影响
与钙对锌合金力学性能的影响不同,随着银含量的提高锌合金的强度和塑性均有所提高。Ag在Zn中的最大固溶度原子分数为5.0%,添加量为0.5%和1%不会生成第二相而是完全固溶到基体中。同时,Ag的添加使合金的晶粒细化[18],根据Hall-Patch关系使合金的抗拉强度提高。固溶强化作用,使Zn-Li-Ca-Ag系合金的强度随着银含量的提高而提高。同时细化晶粒后,更多的晶粒可参与协调变形,也使合金的塑性变形能力提高。因此,随着Ag含量的提高合金的延伸率随之提高。
3.2 合金元素对Zn-Li-Ca-Ag系合金耐蚀性能的影响
Ca的加入在锌合金中生成CaZn13相,与Zn基体之间的电位差使二者构成原电池而发生电偶腐蚀。CaZn13相作为电化学腐蚀的阳极先腐蚀,对基体Zn有较好的保护作用。因此,在合金中添加钙元素使其耐蚀性能提高。但是Ca含量达到0.1%时CaZn13相的偏聚较为明显,活性阳极面积的增大产生严重的局部腐蚀,使合金的耐腐蚀性能降低[20]。Ca含量为0.05%的合金中第二相较少,CaZn13相作为阳极优先腐蚀,对基体的保护作用较好,避免了严重的局部腐蚀,此时合金的耐蚀性最好。Ag的固溶使合金的电位降低(表5)和整体的耐蚀性能变差。因此,添加Ag的合金其腐蚀速率与Zn-0.8Li-0.05Ca相比有所提高。但是,Ag的加入使锌合金的枝晶细化[18],均匀了合金的组织。因此,继续提高Ag含量使合金的耐蚀性能随之提高。
表4中给出了腐蚀产物的EDS结果。可以看出,添加Ca的合金其腐蚀产物主要是氧化锌,而添加Ag的合金其腐蚀产物主要是碳酸锌。图11给出了两类合金在Hank's溶液中的腐蚀机制。在Hank's溶液中,氯离子的存在可能破坏氢氧化锌溶解与生成的更易溶的氯化物盐之间的平衡,促进合金的进一步溶解[22]。同时,Zn(OH)2保护层并不致密。腐蚀介质穿过腐蚀层与内部的基体发生化学反应而产生局部的腐蚀孔洞。在孔洞内合金与腐蚀介质形成一个自催化腐蚀电池而导致更严重的局部腐蚀,使质量损失进一步加快。与ZnO相比,腐蚀产物ZnCO3在试样表面形成一层致密的腐蚀产物层,将溶液中的氯离子与基体隔离开,从而减缓了合金的腐蚀[23]。因此,在同一浸泡周期,加入Ca的合金其腐蚀速率高于添加不同含量Ag的合金。
图11
图11
Zn-0.8Li-xCa-0.2Ag和Zn-0.8Li-0.05Ca-xAg合金在Hank's中的腐蚀机制示意图
Fig.11
Schematic illustration of the corrosion mechanism of Zn-0.8Li-xCa-0.2Ag (a) and Zn-0.8Li-0.05Ca-xAg (b) alloys in Hank's solution
4 结论
(1) 可降解Zn-Li-Ca-Ag系合金的微观组织由初生Zn枝晶和层片状共晶组织构成,加入Ca元素使微观组织中出现棱角分明且形状规则的CaZn13相。随着Ca含量的提高CaZn13相含量增多。Ag主要以固溶的形式存在于基体中,随着Ag元素的提高合金显微组织中粗大树枝晶的尺寸减小。
(2) 因CaZn13相的作用,随着Ca含量的提高可降解Zn-Li-Ca-Ag系合金的强度和硬度提高,延伸率降低。因固溶强化和枝晶细化,随着Ag添加量的提高合金的强度和延伸率显著提高。
(3) 随着Ca含量的提高可降解Zn-Li-Ca-Ag系合金的耐腐蚀性能先提高后降低。
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