Ag/Zn双元离子注入不锈钢的研制及抗菌性能研究
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摘要
随着人们生活水平和保健意识的提高,抗菌不锈钢作为一种新型材料受到越来越多的关注。本文采用双元金属离子注入的方法制备抗菌不锈钢,得到了一种Ag/Zn双元金属离子注入的马氏体不锈钢。研究了注入参数对马氏体不锈钢的抗菌效果以及耐腐蚀性能的影响,采用X射线光电子能谱(XPS)、原子力显微镜(AFM)和接触角测量仪分析了不锈钢注入层的元素浓度分布、元素的价态、表面粗糙度和表面疏水性。
注入层的XPS测试表明,当Ag注入剂量为2×10~(17)ions/cm~2、Zn为1×10~(17) ions/cm~2,注入加速电压都为47KV时,两种金属离子的注入深度约为70nm,两种金属离子的峰值浓度均在离不锈钢表面以下20nm处,Zn离子为+2价,Ag离子为+1价,因此Zn离子获得注入的能量大,其注入层中相对浓度要高于Ag离子的浓度。Ag/Zn金属离子注入不锈钢表面后,均以离子形式存在于注入层中,Ag以正一价离子形式与氧形成Ag2O,Zn以正二价形式与氧形成ZnO。在注入层内部,Ag与Zn的峰值均没有发生改变。
AFM分析结果表明,随着注入剂量的增大,表征值峰-谷粗糙度明显减小,不锈钢表面粗糙度逐渐减小。接触角测量结果表明,随着离子注入剂量的增加,注入试样表层的疏水性增强。当Ag注入剂量为2×10~(17)ions/cm~2、Zn为2×10~(17) ions/cm~2时,注入试样表面的疏水性达到最大。离子注入试样表面疏水性增强。阳极极化曲线实验表明,离子注入不锈钢后,不锈钢表面的耐腐蚀性能没有下降,甚至有所提高,因此,双元金属离子注入后,不锈钢保持了原有的良好的耐腐蚀性能。
以未经离子注入的不锈钢试样为对照样,单一Ag离子注入和Ag/Zn金属离子注入的不锈钢试样均表现出优良的抗大肠杆菌能力。随着锌离子注入剂量达到4×10~(17) ions/cm~2时,样品抗白色念珠球菌的能力得到显著提升,说明,锌离子的注入有助于抗白色念珠球菌能力的提高。
With the improvement of people’s living and health level, antibacterial stainless steel has attracted much attention due to its structural and functional properties. In this work, martensite stainless steel sample was implanted by Ag/Zn ions at an extracting voltage of 47KV. The structural properties of Ag/Zn implanted stainless steel were studied by Atom Force Microscope (AFM), X ray Photoelectron Spectroscopy (XPS), and surface tensiometer. The corrosion resistance was characterized by electrochemical polarization curve.
Depth profile analysis shows that the Ag/Zn implanted layer is about 70nm in thickness under an implantation dose of 2×10~(17) ions/cm~2 for Ag and Zn ions at an extracting voltage of 47KV. The depth of the peak concentration of Ag and Zn ions is both 20nm. XPS analysis also shows that silver exists in Ag+ and Zn exists in Zn2+, according to the distribution of bingding energy.
The results of AFM show that surface roughness of peak-valley decreases continuously with the increasing of implantation doses. The contact angle analyses imply that surface hydrophobic property of implanted stainless steel are increased with the increasing of implantation doses. The most hydrophobic property is observed with the implantation dose of 2×10~(17) ions/cm~2 Ag ion and 2×10~(17) ions/cm~2 Zn ion. Polarization curve show that the corrosion resistance are also increased with the increasing of implantation dose.
The antibacterial properties of Ag/Zn implanted stainless steel were investigated in vitro using Eschericha coli and Candida albicans. The stainless steel implanted by single Ag ion shows good antibacterial property to Escherichia coli but poor antibacterial property to Candida albicans. The stainless steel implanted by Ag/Zn ions shows good antibacterial property to both Escherichia coli and Candida albicans, with the implantation dose of 2×10~(17) ions/cm~2 Ag ion and 4×10~(17) ions/cm~2 Zn ion.
注入层的XPS测试表明,当Ag注入剂量为2×10~(17)ions/cm~2、Zn为1×10~(17) ions/cm~2,注入加速电压都为47KV时,两种金属离子的注入深度约为70nm,两种金属离子的峰值浓度均在离不锈钢表面以下20nm处,Zn离子为+2价,Ag离子为+1价,因此Zn离子获得注入的能量大,其注入层中相对浓度要高于Ag离子的浓度。Ag/Zn金属离子注入不锈钢表面后,均以离子形式存在于注入层中,Ag以正一价离子形式与氧形成Ag2O,Zn以正二价形式与氧形成ZnO。在注入层内部,Ag与Zn的峰值均没有发生改变。
AFM分析结果表明,随着注入剂量的增大,表征值峰-谷粗糙度明显减小,不锈钢表面粗糙度逐渐减小。接触角测量结果表明,随着离子注入剂量的增加,注入试样表层的疏水性增强。当Ag注入剂量为2×10~(17)ions/cm~2、Zn为2×10~(17) ions/cm~2时,注入试样表面的疏水性达到最大。离子注入试样表面疏水性增强。阳极极化曲线实验表明,离子注入不锈钢后,不锈钢表面的耐腐蚀性能没有下降,甚至有所提高,因此,双元金属离子注入后,不锈钢保持了原有的良好的耐腐蚀性能。
以未经离子注入的不锈钢试样为对照样,单一Ag离子注入和Ag/Zn金属离子注入的不锈钢试样均表现出优良的抗大肠杆菌能力。随着锌离子注入剂量达到4×10~(17) ions/cm~2时,样品抗白色念珠球菌的能力得到显著提升,说明,锌离子的注入有助于抗白色念珠球菌能力的提高。
With the improvement of people’s living and health level, antibacterial stainless steel has attracted much attention due to its structural and functional properties. In this work, martensite stainless steel sample was implanted by Ag/Zn ions at an extracting voltage of 47KV. The structural properties of Ag/Zn implanted stainless steel were studied by Atom Force Microscope (AFM), X ray Photoelectron Spectroscopy (XPS), and surface tensiometer. The corrosion resistance was characterized by electrochemical polarization curve.
Depth profile analysis shows that the Ag/Zn implanted layer is about 70nm in thickness under an implantation dose of 2×10~(17) ions/cm~2 for Ag and Zn ions at an extracting voltage of 47KV. The depth of the peak concentration of Ag and Zn ions is both 20nm. XPS analysis also shows that silver exists in Ag+ and Zn exists in Zn2+, according to the distribution of bingding energy.
The results of AFM show that surface roughness of peak-valley decreases continuously with the increasing of implantation doses. The contact angle analyses imply that surface hydrophobic property of implanted stainless steel are increased with the increasing of implantation doses. The most hydrophobic property is observed with the implantation dose of 2×10~(17) ions/cm~2 Ag ion and 2×10~(17) ions/cm~2 Zn ion. Polarization curve show that the corrosion resistance are also increased with the increasing of implantation dose.
The antibacterial properties of Ag/Zn implanted stainless steel were investigated in vitro using Eschericha coli and Candida albicans. The stainless steel implanted by single Ag ion shows good antibacterial property to Escherichia coli but poor antibacterial property to Candida albicans. The stainless steel implanted by Ag/Zn ions shows good antibacterial property to both Escherichia coli and Candida albicans, with the implantation dose of 2×10~(17) ions/cm~2 Ag ion and 4×10~(17) ions/cm~2 Zn ion.
引文
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