抗菌不锈钢材料及其发展现状

综述了各种抗菌不锈钢材料(包括加铜和加银的抗菌不锈钢、表面涂层抗菌不锈钢、抗菌复合不锈钢板)的抗菌机理、特点，应用和开发现状。在普通不锈钢内添加一定量的抗菌金属元素Cu，Ag，Zn等，控制铸造、锻压、轧制以及热处理过程，使抗菌金属元素在不锈钢基体内以一定的大小、形态，均匀弥散地析出，并保证析出相的体积百分比，在不降低普通不锈钢的力学性能和抗腐蚀性能的情况下，赋予其优异的抗菌性能。     

常温制备抗菌不锈钢的研究

抗菌不锈钢是目前材料领域研究的热点.本文以AgNO3、ZnSO4和TiO2为主要原料,制备含有Ag 、Zn2 和TiO2的浸泡液.在常温条件下,将普通不锈钢浸入浸泡液中,制备出表面含有抗菌离子的新型抗菌不锈钢,并对其抗菌性能和持久性进行了表征,结果表明,在经过50次的反复冲洗及NaCl和CH3COOH溶液浸泡,其对金黄色葡萄球菌的平均抑菌率为99.48%,对大肠杆菌的平均抑菌率为99.09%.     

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.     

硬化工艺对双辉渗银不锈钢膜层结构及性能的影响

不锈钢双辉渗银处理获得的渗银层硬度较低且不耐磨,因此设计硬化方案对渗银不锈钢进行硬化,以改善其耐磨性。采用等离子氮碳共渗技术进行渗银层的改性工作,对不同工艺下膜层的微观形貌、成分及物相构成进行了分析,并对比了其硬度及磨损性能。两种硬化工艺下测得的硬度及磨损试验数据如下:渗银处理(×3h)+渗氮碳处理(×10h)工艺制备的试样表面硬度值为283HV0.025,15s,平均摩擦系数为0.4287,磨损失重为12.9mg;渗氮碳处理(×10h)+渗银处理(×3h)工艺制备的硬度值为544HV0.025,15s,平均摩擦系数为0.4266,磨损失重为11.5mg。可以看出渗银处理(×3h)+渗氮碳处理(×10h)工艺未提升渗银不锈钢的表面硬度,渗氮碳处理(×10h)+渗银处理(×3h)工艺将渗银不锈钢的表面硬度提升了近1倍。两种硬化工艺对渗银不锈钢的耐磨性能略有改善。     

Ag/Cu共渗不锈钢表面的微观结构及抗菌性能研究

以银铜合金为靶材,利用辉光等离子体在AISI304不锈钢表面同时渗入银和铜,制备性能优良的抗菌不锈钢。对渗层的形貌、化学组成、耐蚀性能和抗菌性能进行了研究,结果表明,所得渗层在不锈钢表面分布均匀,Ag/Cu元素质量比为4.9∶3;不锈钢表面渗层腐蚀电位由-0.103V提高到0.07V,自腐蚀电流密度从1.66×10-7A/cm2降至5.813×10-9A/cm2,耐腐蚀性能有所提高;渗层对大肠杆菌和金黄色葡萄球菌的杀菌率均达100%。     

含铜奥氏体抗菌不锈钢抗菌性能和机理初步研究

考察了含铜奥氏体抗菌不锈钢的抗菌性能，并对其抗菌机理进行了初步探讨。方法：覆膜法测定杀菌率；透射电镜观察E．coli细胞形态；考马斯亮蓝法测定细胞漏出液中可溶性蛋白含量；琼脂糖凝胶电泳检测菌体基因组DNA考察抗菌不锈钢对DNA的剪切作用。结果：除产气肠杆菌外，奥氏体抗菌不锈钢对其它供试的16种常见微生物均显示较强的抗菌活性，具有广谱抗菌性．在作用9h时可将1×10^7cfu／ml的E．coli全部杀灭，对浓度≤1×10^7cfu／ml的E．coli液在24h内杀灭率达到99．5％。透射电镜结果显示，与奥氏体抗菌不锈钢作用后的E．coli细胞壁和细胞膜破裂，核区不明显；作用后的菌液中可溶性蛋白质含量增加；实验中未检测到有明显的菌体DNA断裂现象．结论：奥氏体抗菌不锈钢具较强的抗菌性能和广谱抗菌性。其作用机理可能为使菌体细胞壁和细胞膜因氧化而破裂，胞内可溶性蛋白漏出，最终导致菌死亡。     

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.     

壳聚糖/单宁酸复合胶体粒子的制备及功能涂层研究

以壳聚糖(Chitosan,CS)和单宁酸(Tannic acid,TA)为组装基元,在水溶液中通过pH诱导组装制备壳聚糖/单宁酸(CS/TA)复合胶体粒子,用透射电子显微镜(TEM)对复合胶体粒子的尺寸及形貌进行了表征。再将复合胶体粒子水分散液为电泳沉积液,通过电泳沉积技术诱导复合胶体粒子在316L不锈钢表面二次组装制备纳米功能涂层;利用接触角测试对涂层表面的亲疏水性进行了研究;并通过体外细胞实验探究了涂层的细胞相容性,抗菌实验测试了涂层对金黄色葡萄球菌和大肠杆菌的抗菌活性。研究结果表明,通过电诱导胶体粒子可以在316L不锈钢表面形成了致密的纳米涂层材料,涂层具有良好的细胞相容性和抗菌作用,在生物涂层领域有着潜在应用前景。     

静电纺制备耐水抗菌性姜黄素纳米纤维膜及其性能研究

姜黄素(Cur)在医药上有着很广泛的应用，可用于抗癌、抗菌、抗病毒、抗炎等。制备了一种聚乙烯醇/聚丙烯酸(PVA/PAA)载姜黄素纳米纤维材料，可用于伤口敷料，能有效抗菌，可促进伤口愈合。首先采用二甲亚砜将姜黄素溶解，再将含有姜黄素的溶液与PVA/PAA水溶液共混，利用静电纺丝技术制备出纳米纤维膜后对其进行高温热交联处理使其提高耐水性。对纳米纤维膜的表面形貌、化学结构、抗菌性能、溶胀性能以及透湿性能进行表征与分析。结果表明：PVA/PAA载姜黄素纳米纤维膜具有一定的抗菌效果，并且透湿性以及吸液性能良好。     

载银羟基磷灰石抗菌织物的研究

通过硝酸钙和磷酸钠水溶液反应合成了磷灰石纳米浆料，并进一步制备出载银羟基磷灰石粉料。用透射电镜、红外光谱仪和转靶X射线衍射仪对载银羟基磷灰石进行了形貌和物相等分析，用原子吸收光谱仪测定了载银羟基磷灰石粉料Ag^ 含量，并利用后整理法加工出载银羟基磷灰石抗菌织物，对载银羟基磷灰石粉料和织物均进行了抗菌效果的测试。结果表明，载银羟基磷灰石粉料和织物均有很强的抑菌效果，市场应用前景十分广阔。     

Ag-doped 45S5 Bioglass?-based bone scaffolds by molten salt ion exchange: processing and characterisation

There is increasing interest in developing scaffolds with therapeutic and antibacterial potential for bone tissue engineering. Silver is a proven antibacterial agent which bacteria such as MRSA have little or no defense against. Using an ion exchange method, silver ions have been introduced into 45S5 Bioglass(?) based scaffolds that were fabricated using the foam replication technique. This technique allows the introduction of Ag(+) ions onto the surface of the scaffold without compromising the scaffold bioactivity and other physical properties such as porosity. Controlling the amount of Ag(+) ions introduced onto the surface of the scaffold was achieved by tailoring the ion exchange parameters to fabricate samples with repeatable and predictable Ag(+) ion release behavior. In vitro studies in simulated body fluid were carried out to ensure that the scaffolds maintained their bioactivity after the introduction of Ag(+) ions. It was also shown that the addition of low concentrations (2000:1 w/w) of silver ions supported the attachment and viability of human periodontal ligament stromal cells on the 3D scaffolds. This work has thus confirmed ion exchange as an effective technique to introduce Ag(+) ions into 45S5 Bioglass(?) scaffolds without compromising the basic properties of 45S5 Bioglass(?) which are required for applications in bone tissue engineering.     

The effect of substrate material on silver nanoparticle antimicrobial efficacy

With the advent of nanotechnology, silver nanoparticles increasingly are being used in coatings, especially in medical device applications, to capitalize on their antimicrobial properties. The attractiveness of nanoparticulate silver systems is the expected increased antimicrobial efficacy relative to their bulk counterparts, which may be attributed to an increased silver ion (Ag+) solubility, and hence availability, that arises from capillarity effects in small, nanometer-sized particles. However, a change of the material upon which the antimicrobial nanoparticulate silver is deposited (herein called "substrate") may affect the availability of Ag+ ions and the intended efficacy of the device. We utilize both theory and experiment to determine the effect of substrate on ion release from silver particles in electrochemical environments and find that substrate surface charge, chemical reactivity or affinity of the surface for Ag+ ions, and wettability of the surface all affect availability of Ag+ ions, and hence antimicrobial efficacy. It is also observed that with time of exposure to deionized water, Ag+ ion release increases to a maximum value at 5 min before decreasing to undetectable levels, which is attributed to coarsening of the nanoparticles, and which subsequently reduces the solubility and availability of Ag+ ions. This coarsening phenomenon is also predicted by the theoretical considerations and has been confirmed experimentally by transmission electron microscopy.     

Formation of silver nanoparticles in poly(perfluorosulfonic) acid membrane

The formation of silver nanoparticles by chemical reduction of Ag+-loaded Nafion-117 membrane with NaBH4 was studied using radioactivity tagged ions. The counterion-exchange method (Ag(m)+ <--> Na(s)+) was used to obtain a membrane sample with a varying proportion of Ag+ ions. The X-ray elemental mapping across the thickness of the membrane by energy-dispersive X-ray spectrometer attached to the environmental scanning electron microscope (ESEM/EDAX) indicated that Na+ and Ag+ were uniformly distributed in the membrane samples before reduction. The average size of nanoparticles formed after reduction was found to be 15 +/- 3 nm, irrespective of the concentration of silver ions present in the membrane before reduction. Energy-dispersive X-ray fluorescence (EDXRF) analyses of the membrane samples, carried out before and after reduction, indicated that the Ag concentration on the membrane surface was considerably increased after reduction. EDXRF measurements of the membrane samples, obtained from reduction carried out in a dead end cell, indicated that Ag nanoparticles were formed only on the membrane surface exposed to NaBH4 solution. Reduction carried out with NaBH4 tagged with 22Na showed that the formation of Ag nanoparticles involved exchange of Ag+ ions from ion-exchange sites in the interior of the membrane with Na+ ions, followed by reduction of Ag+ ions with BH4- ions at the surface of membrane. The study of self-diffusion of water, Na+, and Cs+ ions in the membrane loaded with Ag nanoparticles indicated that formation of Ag nanoparticles did not affect the diffusional transport properties of the membrane. The ion-exchange capacity and water uptake capacity were also not affected by the formation of Ag nanoparticles in the membrane. The spatial distribution of Ag nanoparticles across the thickness of the membrane obtained by ESEM/EDAX showed that Ag nanoparticles were confined to a few-micrometer surface layer of the membrane. Based on these observations, an attempt has been made to explain the mechanism of the formation of Ag nanoparticles in the membrane.     

Nano-Ag-loaded hydroxyapatite coatings on titanium surfaces by electrochemical deposition

Hydroxyapatite (HA) coatings on titanium (Ti) substrates have attracted much attention owing to the combination of good mechanical properties of Ti and superior biocompatibility of HA. Incorporating silver (Ag) into HA coatings is an effective method to impart the coatings with antibacterial properties. However, the uniform distribution of Ag is still a challenge and Ag particles in the coatings are easy to agglomerate, which in turn affects the applications of the coatings. In this study, we employed pulsed electrochemical deposition to co-deposit HA and Ag simultaneously, which realized the uniform distribution of Ag particles in the coatings. This method was based on the use of a well-designed electrolyte containing Ag ions, calcium ions and l-cysteine, in which cysteine acted as the coordination agent to stabilize Ag ions. The antibacterial and cell culture tests were used to evaluate the antibacterial properties and biocompatibility of HA/Ag composite coatings, respectively. The results indicated the as-prepared coatings had good antibacterial properties and biocompatibility. However, an appropriate silver content should be chosen to balance the biocompatibility and antibacterial properties. Heat treatments promoted the adhesive strength and enhanced the biocompatibility without sacrificing the antibacterial properties of the HA/Ag coatings. In summary, this study provided an alternative method to prepare bioactive surfaces with bactericidal ability for biomedical devices.     

壳聚糖修饰银纳米颗粒的制备及抗菌性能研究

采用液相化学还原法,以壳聚糖为修饰剂,硼氢化钠为还原剂,制备了壳聚糖修饰银纳米颗粒(chitosan-Ag NPs)。通过X射线粉末衍射仪、透射电子显微镜、傅立叶变换红外光谱仪等对所制备样品的结构和形貌进行了表征。结果表明,所制备纳米颗粒具有面心立方Ag的晶型结构,壳聚糖通过氨基和羟基中的N、O原子与Ag+的化学键合作用修饰在纳米颗粒表面,起到了限制颗粒粒径长大和防止其团聚的作用。采用肉汤连续稀释法检测了样品对大肠杆菌和金黄色葡萄球菌的抑菌杀菌性能,结果表明chitosan-Ag NPs具有优异的抗菌性,抗菌性能受到粒径大小的影响。     

Tungsten film as a hard and compatible carrier for antibacterial agent of silver

Silver-containing tungsten (W–Ag) films for antibacterial applications were deposited on glass, silicon, and 316L stainless-steel substrates by magnetron sputtering with the silver target current of 0–2.0 A. The addition of silver improves adhesion of the films on glass substrate due to the reduced residual stress in the films. SEM and EDX analyses reveal Ag-rich tiny dots (~?20 nm) at the surface of W–Ag films with high silver contents. In XRD patterns, silver peaks are present for the samples deposited at 1.5 and 2.0 A, and tungsten grain size is decreased from?~?23 to 10 nm by silver addition. XPS analysis shows that tungsten is slightly oxidized (WO₃) at the top surface of the film, and silver presents mainly in metallic state. The low Ag/W ratios and the small surface roughness (<?8 nm) indicate that silver segregation at the film surface is not obvious. Microhardness of the samples with ≤?6.7 at.% silver is nearly seven times that of the stainless steel (~?250 HV). The coated samples are hydrophobic tested by contact angle measurement. The potentiodynamic polarization and the soaking test simulating the inflammatory state show that even corrosion occurs and silver addition decreases corrosion resistance of the films. The antibacterial ratio of the coated samples increases with silver content, being 91% at 4.2 at.% silver content tested by agar plate counting method. In agar disk diffusion assay, no inhibition zone is observed for all samples. The antibacterial property of the W–Ag films is localized, long-lasting, and reusable, which would be beneficial for their potential biomedical and environmental applications.     

Synthesis of titanium oxide thin films containing antibacterial silver nanoparticles by a reactive magnetron co-sputtering system for application in biomedical implants

Titanium oxide thin films containing silver (Ag) nanoparticles were synthesized on commercially pure titanium (cp-Ti) substrates using a reactive magnetron co-sputtering method. The goal was to maximize bactericidal activity along with sustained biocompatibility. Furthermore, this study examined the correlation between Ag nanoparticle dispersion in the films and the antibacterial efficacy of the Ag ions released from the films. The results showed that there might be two factors affecting the inhibition of bacterial attachment to the surface of the specimens: surface morphology and Ag ion release. MTT assay results demonstrated that there was no cytotoxicity on fibroblast cells in any group. Overall, the magnetron sputtered Ag nanoparticle-containing titanium oxide coatings in this study can be used as an efficient antibacterial layer with sustained biocompatibility.     

TiO2/Ag型抗菌活性碳纤维的制备和性能表征

采用涂覆和焙烧的简便方法,将载银二氧化钛(TiO2/Ag)均匀地沉积在活性碳纤维表面.利用扫描电镜、氮气吸脱附等对活性碳纤维结构进行表征,研究发现活性碳纤维的微孔结构、活性碳纤维的高吸附性能基本保持不变.利用改良抑菌圈法研究了这类TiO2/Ag活性碳纤维对大肠杆菌、金黄色葡萄球菌、枯草杆菌和链球菌的杀灭效果.结果表明,因Ag和TiO2相互协同作用,TiO2/Ag活性碳纤维的抗菌性大大提高,当Ag含量为0.5%时,在37°C培养4小时后,TiO2/Ag活性碳纤维对大肠杆菌、金黄色葡萄球菌就有很强的抗菌能力.由于TiO2特殊的光催化特性,使TiO2/Ag活性碳纤维不仅适用于水的净化抗菌处理,更适用于空气的净化抗菌处理.     

沉积扩散法制备含银抗菌不锈钢工艺研究

采用沉积扩散法制备含银抗菌不锈钢层,通过抗菌试验、盐干湿循环腐蚀试验、SEM、XPS等检测手段,研究了沉积扩散工艺制备含银抗菌不锈钢的抗菌性能、耐蚀性能及银在不锈钢基体中的分布状态和价态.结果表明,基材表面化学镀银后经离子轰击抗菌处理(工艺参数:电压1.25 kV,电流3 A,气流量20～60 mL/min,时间4 h),所得含银抗菌不锈钢的杀菌率达到99%以上,耐蚀性能没有降低,银在基体中呈弥散状态分布,其价态为零价态.