不锈钢表面纳米多孔Ti-Cu薄膜的制备及性能研究

发布时间：2018-09-03 19:59

【摘要】：奥氏体不锈钢因具有优异的耐腐蚀性能以及良好的可加工性能,被广泛应用于食品加工、器具器皿、手术器械等领域。在室内外使用环境中,不锈钢制品表面由于被灰尘、油污等沾染而容易滋生细菌、病毒和其他有害微生物。利用表面处理技术制备光催化和抗菌功能的不锈钢具有广阔的应用前景。纳米多孔金属具有独特的多孔结构和性能,在电化学、光化学、催化等领域中得到了广泛的应用。进一步探讨功能型纳米多孔金属材料的制备、改性及性能研究将拓展它们的应用领域。本文利用闭合场非平衡磁控溅射系统在316L不锈钢表面制备Ti-Cu薄膜,然后对Ti-Cu薄膜进行去合金化得到纳米多孔Ti-Cu薄膜。同时,考虑到Ti Ni合金具有独特的形状记忆性能,本文也采用闭合场非平衡磁控溅射技术在不锈钢表面制备了近等原子比Ti Ni薄膜改善不锈钢的耐腐蚀磨损性能。围绕如何使表面改性后的不锈钢赋予光催化、电催化和抗菌性能的同时具有良好的耐腐蚀和磨损性能,优化了制备工艺参数;分别采用X射线衍射(XRD)、扫描电镜(SEM)、辉光放电光谱仪(GDOES)和X射线光电子能谱(XPS)等手段分析了薄膜的组织和结构;研究了薄膜的电催化性能、光催化性能、抗菌性能、磨损性能和腐蚀性能。研究结果如下:1、对薄膜的组织结构和表面形貌进行了分析。经磁控溅射镀膜后不锈钢基体表面均形成了均匀致密的Ti-Cu薄膜,Ti-Cu薄膜主要由Cu_4Ti_3,Cu_(0.81)Ni_(0.19),Ti Ni_(0.8)Cu_(0.2) andγ-Fe相组成;通过去合金法在不锈钢表面形成纳米多孔Ti-Cu薄膜,其中Ti_(31.28)Cu_(64.71)纳米多孔薄膜主要由Cu_4Ti_3和Cu_2Ti_4O相组成。2、利用循环伏安法研究了纳米多孔Ti-Cu薄膜的电催化性能。结果表明,不同酸碱度条件下,纳米多孔Ti-Cu薄膜对乙二醇的电催化氧化表现出明显不同的性能。在碱性条件下,纳米多孔结构材料可以有效地促进乙二醇的氧化反应。3、对不锈钢表面纳米多孔Ti-Cu薄膜的光催化性能进行了研究。结果表明,纳米多孔Ti-Cu薄膜赋予了不锈钢光催化性能,在可见光6小时照射下对亚甲基蓝溶液的降解率是纯二氧化钛薄膜的1.83倍。4、纳米多孔Ti-Cu改性的不锈钢试样均显示出明显的抗菌作用,在24小时内,改性后的不锈钢对大肠杆菌的抗菌作用达到了96.7%,对金黄色葡萄球菌的抗菌作用达到了100%,这主要和Cu掺杂二氧化钛在可见光下的光催化杀菌以及Cu离子杀菌有关。5、通过球-盘磨损试验对Ti-Cu薄膜的腐蚀磨损性能及机理进行了研究。结果表明,在模拟人工体液介质中摩擦副为Si_3N_4时,Ti-Cu薄膜对不锈钢基材具有明显的减摩作用,表面改性处理后的不锈钢表现出更好的抗腐蚀磨损性能。6、用电化学方法研究了Ti-Cu改性前后不锈钢在模拟人工体液中的腐蚀行为,动电位极化曲线测试和电化学阻抗谱分析结果表明,Ti-Cu改性不锈钢表现出比不锈钢基材更良好的耐蚀性能。腐蚀形貌分析表明,不锈钢基材表面可观察到蚀孔,发生点蚀,而Ti-Cu改性层能有效抑制不锈钢表面点蚀坑的形成。7、对不锈钢表面近等原子比Ti Ni薄膜的腐蚀磨损性能进行了研究。结果表明,Ti Ni薄膜有效提高了不锈钢在模拟人工体液中的抗腐蚀磨损性能。这主要和摩擦过程中形成的致密Si O_2和Ti O_2保护薄膜以及Ti Ni薄膜的赝弹性有关。
[Abstract]:Austenitic stainless steel is widely used in food processing, utensils, surgical instruments and other fields because of its excellent corrosion resistance and good machinability. In indoor and outdoor environment, stainless steel products are easy to grow bacteria, viruses and other harmful microorganisms because of being contaminated by dust, oil and other contaminants. Nanoporous metals have been widely used in electrochemistry, photochemistry, catalysis and other fields because of their unique porous structure and properties. Further study on the preparation, modification and properties of functional nanoporous metal materials will expand their applications. In this paper, Ti-Cu thin films were prepared on 316L stainless steel surface by closed-field unbalanced magnetron sputtering system, and then the Ti-Cu thin films were Dealloyed to obtain nanoporous Ti-Cu thin films. Near-isoatomic Ti-Ni thin films were prepared to improve the corrosion and wear resistance of stainless steel. The preparation parameters were optimized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), glow discharge spectroscopy (GDS) and glow discharge spectroscopy. The microstructure and structure of the films were analyzed by means of GDOES and XPS. The electrocatalytic, photocatalytic, antibacterial, wear and corrosion properties of the films were studied. The results are as follows: 1. The microstructure and surface morphology of the films were analyzed. The surface of the stainless steel substrate after magnetron sputtering were uniform. Ti-Cu thin films consist of Cu_4Ti_3, Cu_ (0.81) Ni_ (0.19), Ti Ni_ (0.8) Cu_ (0.2) and gamma-Fe phases, and Ti_ (31.28) Cu_ (64.71) nanoporous thin films are formed on the surface of stainless steel by dealloying method. The electrocatalytic properties of nanoporous Ti-Cu thin films were investigated. The results showed that the electrocatalytic oxidation of ethylene glycol by nanoporous Ti-Cu thin films exhibited different performances under different pH conditions. The photocatalytic properties of the film were studied. The results showed that the nanoporous Ti-Cu film gave the stainless steel photocatalytic properties. The degradation rate of methylene blue solution was 1.83 times that of pure titanium dioxide film under visible light irradiation for 6 hours. The nanoporous Ti-Cu modified stainless steel samples showed obvious antibacterial effect. Within 24 hours, the degradation rate of methylene blue solution was improved. The antimicrobial activity of the stainless steel was 96.7% against Escherichia coli and 100% against Staphylococcus aureus. This was mainly related to the photocatalytic sterilization of Cu-doped titanium dioxide under visible light and the sterilization of Cu ion. 5. The corrosion and wear properties and mechanism of Ti-Cu films were studied by ball-disk wear test. The results show that Ti-Cu film has obvious antifriction effect on stainless steel substrate when the friction pair is Si_3N_4 in simulated artificial humor medium, and the stainless steel treated by surface modification has better corrosion and wear resistance. 6. The corrosion behavior and electrochemical potential of stainless steel before and after Ti-Cu modification in simulated artificial humor were studied by electrochemical method. Polarization curves and electrochemical impedance spectroscopy analysis showed that Ti-Cu modified stainless steel exhibited better corrosion resistance than stainless steel substrate. Corrosion morphology analysis showed that corrosion holes and pitting could be observed on the surface of stainless steel substrate, while Ti-Cu modified layer could effectively inhibit pitting formation on the surface of stainless steel. The corrosion and wear properties of Ti-Ni thin films with equal atomic ratio were studied. The results show that Ti-Ni thin films can effectively improve the corrosion and wear resistance of stainless steel in simulated artificial body fluids.
【学位授予单位】：太原理工大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TG174.4

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