抗菌不锈钢的研究进展

综述了抗菌不锈钢材料的抗菌机理、分类,对国内外研究现状进行了讨论,阐述了抗菌不锈钢目前需要解决的关键科学问题是抗菌相表层微观结构、高度弥散的抗菌相与基体组织性能的关系、抗菌相与细菌的吸附关系.提出抗菌不锈钢发挥抗菌性能、抗菌相与细菌活性中心的结构关联是解决问题的必然趋势,指出复合型与单一型抗菌材料的开发是该材料的研究方向.     

抗菌不锈钢的抗菌原理、常规加工与增材制造

各类公共卫生事件频发,催生了各类抗菌产品研发和应用.抗菌材料按原料来源分类包括无机抗菌材料、有机抗菌材料、天然抗菌材料和合成抗菌材料.不锈钢作为运用最广泛的无机金属材料之一,在抗菌材料的应用方面已取得阶段性进展.不锈钢获得抗菌性能的常规加工方法有两种,即表面改性和合金化处理.然而,表面型抗菌不锈钢经磨蚀后极易丧失抗菌效果,合金型抗菌不锈钢中抗菌离子利用率较低,这些都导致不锈钢的抗菌效果不理想.因此,研究者们除研究不同抗菌元素的抗菌机理外,还从提高抗菌不锈钢耐久性和抗菌效率方面进行了不同制备工艺的探索,扩大了抗菌不锈钢的使用范围.近年来,研究者们开发了多种抗菌不锈钢的制备工艺以提高其使用寿命和抗菌性能.通过沉积法、渗透法和喷涂法等方式将抗菌元素被添加到不锈钢表面,可使抗菌层厚度增加,抗菌效果更稳定;适量抗菌金属元素被添加到不锈钢中,经抗菌处理后这些抗菌金属元素能够不断地向介质中释放抗菌金属离子,使不锈钢的抗菌率大幅提高.此外,为了满足抗菌不锈钢在生物医学领域的使用需求,常在其表面引入羟基磷灰石、聚(L-丙交酯-己内酯)等生物相容性良好的物质,或采用先进的制备工艺控制有害金属离子的释放浓度,以实现抗菌性能和生物相容性的有机结合.本文综述了近10年国内外各种抗菌不锈钢的研究现状.介绍了表面改性抗菌不锈钢和合金型抗菌不锈钢的抗菌原理、特点与制造方法.此外,针对常规制造法存在制备周期较长、材料耗损较多、环境污染较严重等问题,本文结合增材制造技术的优势,试图寻找一种新型的抗菌不锈钢制备工艺,以其个性化定制、耗时短、精密加工等优势弥补上述缺点,并且介绍了增材制造抗菌材料在医疗卫生领域中的应用.     

Ag/N离子复合注入刀具不锈钢(AISI420)的表面性能研究

采用MEVVA源和高能气体离子源对刀具不锈钢(AISI420)分别进行N离子、Ag离子和Ag/N离子复合注入,并对注入后的试样进行了硬度、耐磨及抗菌性能的研究。结果表明,N离子的注入能提高不锈钢的硬度和耐磨性能,Ag离子的注入使不锈钢具有优异的抗菌性能,Ag/N离子复合注入使刀具不锈钢的硬度提高了57%,摩擦系数减小了25%,而且具有良好的抗菌性能,对大肠杆菌的杀菌率为95%。     

银离子掺杂有机硅烷薄膜耐蚀和抗菌性能研究

为了制备具有抗菌特性和良好耐腐蚀性的不锈钢,通过溶胶-凝胶方法在乙烯基三甲氧基硅烷偶联剂中加入银离子,得到含银有机硅烷水解溶液,并通过喷涂在不锈钢表面制备了抗菌、耐蚀的不锈钢抗菌膜层,研究了银离子的掺入工艺以及薄膜的抗菌性能和耐蚀性能.结果表明,银离子含量增加到3%以上时,样品的抗菌性能均增加到99.9%以上,不锈钢表面经过预氧化处理的略优于表面未经预氧化处理的薄膜.10?Cl3溶液点蚀试验表明,样品的点蚀率仅为相同条件下不锈钢的1/40.银离子掺杂的乙烯基三甲氧基硅烷薄膜可以明显地提高不锈钢表面的耐腐蚀性能,同时赋予其抗菌性能.     

医用不锈钢的研究与发展

不锈钢由于具有优异的力学性能、耐蚀性能和加工性能而被广泛应用于各种医疗器械及手术工具的制造。概述了医用不锈钢的特点和临床应用,以及存在的主要问题,并以高氮无镍奥氏体不锈钢、不锈钢表面改性、抗菌不锈钢为重点,介绍了医用不锈钢近年来在国内外的主要研究进展。表明医用不锈钢的研究与发展,进一步提高或改善了不锈钢的生物安全性、力学性能、耐蚀性能,甚至带来了一些生物功能化,为医用不锈钢的临床应用带来了新的机遇。     

铜对低碳马氏体抗菌不锈钢性能的影响

在低碳马氏体不锈钢中添加适量Cu,经过抗菌热处理,使不锈钢具有优良的抗菌特性。利用X射线衍射仪和恒电位仪分析了抗菌处理后相的分布和耐蚀性,并通过覆膜法测定其抗菌性。结果表明,随着Cu含量的增加,含铜马氏体不锈钢的硬度和抗菌性提高,维钝电流密度、致钝电流密度和致钝电压减小,更易于钝化。     

新型抗菌功能医用金属研究

不锈钢、钛及钛合金等医用金属材料已广泛应用于骨科、齿科及心血管介入等医疗领域,生物可降解镁合金是正在研究发展的新型医用金属材料,具有诱人的临床应用前景。面对目前临床上亟待解决的植入物引发的细菌感染问题,开展医用金属材料的抗菌功能研究意义重大,也是实现金属材料结构/功能一体化发展的新探索。简要介绍了作者近年来在不锈钢、钛合金、可降解镁基金属等医用金属材料的抗菌功能研究方面的主要进展,并展望了抗菌医用金属材料的临床应用前景。     

奥氏体抗菌不锈钢的微观组织及抗菌性能

含Cu奥氏体抗菌不锈钢经特殊的抗菌热处理析出ε—Cu相,采用覆膜法研究其抗菌性能。实验结果表明：奥氏体抗菌不锈钢易于杀灭大肠杆菌和金黄色葡萄球菌;杀灭鼠伤寒杆菌需要一定时间;杀灭白色念株菌需要较长时间。这与细菌的细胞壁组织结构、细胞壁厚度及其属性有关。抗菌不锈钢对细胞壁较薄、肽聚糖含量较低、组织疏松、金属离子易穿透细胞壁的细菌易于杀灭;反之,细菌不易于杀灭。随着抗菌作用时间的延长,溶液中铜离子浓度的提高,抗菌不锈钢的杀菌效力显著提高。奥氏体抗菌不锈钢经表面打磨或磨损仍然具有同样的抗菌性能。     

掺银离子TiO2薄膜的结构及与不锈钢基板的界面反应

采用溶胶-凝胶法在不锈钢表面制备掺银的TiO2薄膜,研究氧化处理对不锈钢表面Ag/TiO2抗菌薄膜组成和性能的影响,利用X-射线衍射谱(XRD)、扫描电子显微镜(SEM)和X-射线光电子能谱(XPS)等对经氧化处理和未经处理的不锈钢表面Ag/TiO2薄膜进行比较,研究薄膜的结构、界面反应特征及机制.发现:未经氧化处理的不锈钢由于其中的铁原子进入薄膜与TiO2反应形成钛酸铁固溶体薄膜;经氧化处理后不锈钢表面形成一层比较致密的氧化铁层,阻止了不锈钢内部的铁原子扩散进入薄膜与TiO2反应,表面同时形成钛酸铁和锐钛矿型的TiO2薄膜;锐钛矿型的TiO2与银离子反应形成钛酸银,既保持了银离子的高杀菌性能(样品的6小时抗菌率达到100%),同时又不至使金属银形成而使材料变色.在未经氧化处理的不锈钢表面,掺银TiO2薄膜中的银离子转化为单质银,抗菌性能低.     

含Cu铁素体抗菌不锈钢的抗菌性能

含Cu铁素体抗菌不锈钢在抗菌热处理过程中析出ε-Cu相,具有抗菌功能.抗菌处理的条件影响析出相的数量和形貌,从而影响其抗菌特性.在时效温度较低时,抗菌析出相基本上呈球形,随着时效温度的升高,析出相逐渐变为长条形并与铁素体基体保持某种取向关系.在抗菌不锈钢抗菌过程的前期,抗菌性能表现为对细菌生长和繁殖的抑制,后期表现为对细菌的杀灭.     

含Cu抗菌不锈钢的工艺与耐蚀性能

与普通0Cr17铁素体不锈钢和0Cr18Ni9奥氏体不锈钢相比，含铜铁素体和奥氏体抗菌不锈钢均具有良好的冷热加工性能和焊接性能．通过提高浇铸温度，抗菌不锈钢能保持良好的铸造性能．奥氏体抗菌不锈钢的抗应力腐蚀性能比0Cr18Ni9不锈钢有很大的提高，而铁素体抗菌不锈钢比0Cr17有明显的下降．与相应的普通不锈钢相比，两种类型抗菌不锈钢的耐点蚀性能均略有下降．     

Effects of Nitrogen Concentration on Microstructure and Antibacterial Property of Copper-Bearing Austenite Stainless Steels

Austenite antibacterial stainless steels have been found to have wide applications in hospitals and food industries. In recent years epsilon copper precipitation in antibacterial stainless steels has obtained much research interest due to its antibacterial action. The objective of this study was to determine the effects of nitrogen concentration on the precipitation of epsilon copper and antibacterial property. Two kinds of austenite antibacterial stainless steels containing copper and different nitrogen concentration （0.02 and 0.08 wt pct, respectively） were prepared and the microstructures were characterized by a combination of electron microscopy and thermodynamic analysis. A mathematical expression was deduced to predict the effect of nitrogen concentration on the activity coefficient of copper, In（fCu/f^0cu）=0.53524＋4.11xN-0.48x^2N. Higher nitrogen was found to increase the free energy difference of copper concentration distribution between precipitation phase and austenite matrix, stimulate the aggregation of copper atoms from austenite, increase the precipitation amount and consequently enhance the antibacterial property of steel.     

Antibacterial property of Ce-bearing stainless steels

Rare earth (RE) elements inhering in low toxicity have been widely used in biomedicine. The RE elements can also improve the hot workability, corrosion resistance and mechanical properties of stainless steels. However, the antibacterial mechanisms of the RE elements are still under discussion and the antibacterial property of RE-bearing stainless steels has not yet been investigated or reported so far. In this paper several Ce-bearing stainless steels were prepared, the microstructure of the steels was examined, and the antibacterial property of Ce-bearing stainless steels was investigated. It was found that Ce-rich zones were precipitated in the Ce-bearing stainless steels and the volume fraction of the Ce-rich zones increased with increasing Ce content. The Ce-bearing stainless steels showed excellent antibacterial property when the amount of Ce added was above a critical value. Compared to the conventional Cu-bearing antibacterial stainless steels, the Ce-bearing stainless steels investigated presently exhibited good antibacterial ability without any thermal aging treatment. The antibacterial mechanism of Ce-bearing stainless steels is also discussed.     

Beneficial effects of nitrogen on austenite antibacterial stainless steels

Nitrogen is a significant alloying element in austenite stainless steels. The aim of this paper is to evaluate the effects of nitrogen on the microstructure and properties of austenite antibacterial stainless steels. Two austenite antibacterial stainless steels containing copper and different nitrogen concentration (0.02 and 0.08 wt%, respectively) were fabricated. The microstructures and composition analysis were carried out using field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and Auger electron spectroscopy (AES). The epsilon copper-rich precipitates are spherical and less than 20 nm in size, with a cube-on-cube orientation relationship with the matrix. They are dispersed on the steel surface with a mean space of about 200 nm. Nitrogen cannot only improve the antibacterial property but enhance significantly the corrosion resistance in chloride media. Nitrogen compensates the harmful effect of epsilon copper precipitates on the corrosion resistance. The nitrogen concentration in the surface of N-2 steel is four times as much as in the surface of N-1 steel. Nitrogen enrichment in the steel surface improves the corrosion resistance. The presence of higher nitrogen increases the strength and decreases the ductility of austenite antibacterial stainless steel, which could be related to the variation of stacking-fault energy associated with nitrogen concentration.     

抗菌材料发展和现状

简要介绍了抗菌材料的分类、抗菌原理及其应用,综述了抗菌不锈钢发展现状及其特点、抗菌原理和应用情况,并对抗菌材料研究进行了展望.     

无镍铬低比重铸造不锈钢的组织和性能的研究

设计并制备出一种新型无镍铬铸造不锈钢材料。利用光学显微和扫描电镜对其组织物征进行了观察，并对其力学性能、耐热耐蚀性进行了测试研究。结果表明：本文所设计的无镍铬不锈钢具有优异的力学性能，良好的高温抗氧化性和耐海水腐蚀性，且达到ＺＧ３０４、ＺＧ３０４不锈钢的性能指标。     

Study of copper precipitation behavior in a Cu-bearing austenitic antibacterial stainless steel

Copper (Cu) precipitation behavior in a type 304 Cu-bearing austenitic antibacterial stainless steel was studied by analyses of variations in micro-hardness, electrical resistivity, electrochemical impedance and lattice constant of the steel, complemented with transmission electron microscopy (TEM) observation, showing more or less changes on these properties of the steel with different aging time. It was found that both micro-hardness and electrical resistivity measurements were relatively sensitive and accurate to reflect the Cu precipitation behavior in the experimental steel, indicating the beginning and finishing points of the precipitation, which are more simple and effective to be used for development of the new type of antibacterial stainless steels.     

Nickel-free austenitic stainless steels for medical applications

Abstract

The adverse effects of nickel ions being released into the human body have prompted the development of high-nitrogen nickel-free austenitic stainless steels for medical applications. Nitrogen not only replaces nickel for austenitic structure stability but also much improves steel properties. Here we review the harmful effects associated with nickel in medical stainless steels, the advantages of nitrogen in stainless steels, and emphatically, the development of high-nitrogen nickel-free stainless steels for medical applications. By combining the benefits of stable austenitic structure, high strength and good plasticity, better corrosion and wear resistances, and superior biocompatibility compared to the currently used 316L stainless steel, the newly developed high-nitrogen nickel-free stainless steel is a reliable substitute for the conventional medical stainless steels.     

Antibacterial Mechanism of Copper-bearing Antibacterial Stainless Steel against E.Coli

A preliminary study was made on the antibacterial mechanism of copper-bearing antibacterial stainless steels against E.coli through experiments of microbiology such as EDTA （ethylenediaminetetraacetic acid） complexing, DNA smearing and AFM （atomic force microscope） observation. It was measured that the antibacterial stainless steels showed excellent antibacterial functions with antibacterial rate to E.coli over 99.99%. The antibacterial rate was weak if the bacteria solution was complexed by EDTA, indicating that the copper ions play a dominant role in the antibacterial effect of the antibacterial stainless steels. The electrophoresis experiment did not show the phenomenon of DNA smearing for E.coli after contacting antibacterial stainless steels, which meant that DNA of E.coli was not obviously damaged. It was observed by AFM that the morphology of E.coli changed a lot after contacting antibacterial stainless steels, such as cell walls being seriously changed and lots of contents in the cells being leaked.