石墨烯/银纳米复合材料的制备及抗菌性能研究

采用改进的Hummers法制备氧化石墨(GO),加入一定量的聚乙烯亚胺和硝酸银(PEI-Ag+)配位复合物,通过自组装法组装,利用硼氢化钠的还原性,制备石墨烯/银纳米复合材料。用紫外可见吸收光谱(UV-Vis)、红外吸收光谱(FT-IR)、X射线衍射(XRD)、循环伏安法(CV)、扫描电镜(SEM)、拉曼光谱(Raman)等手段对所制备的石墨烯/银纳米复合材料进行表征。以金黄色葡萄球菌和大肠杆菌为模型对纳米复合材料的抗菌性能进行研究。结果表明:银纳米粒子负载在石墨烯表面形成石墨烯/银纳米复合物材料,石墨烯/银纳米复合材料对金黄色葡萄球菌和大肠杆菌生长具有较好的抑制作用,且抗菌性能稳定。当石墨烯/银纳米复合材料浓度为4和15 mg/m L时,分别对金黄色葡萄球菌和大肠杆菌的抑菌效果好。     

氮离子注入诱导TiO_2涂层在可见光下的抗菌能力（英文）

为了提高钛组件的抗菌能力,通过微弧氧化(MAO)处理和进一步的氮等离子体浸没离子注入(N-PIII)处理,在钛表面制备抗菌涂层。XPS光谱测试结果表明,采用氮离子注入N-PIII法将氮掺入TiO_2涂层,随着注入时间的增加,TiO_2涂层表面氮含量增加。掺氮样品在可见光区域的吸光度显著增加,并且氮注入样品的光吸收峰边缘与微弧氧化样品的光吸收峰相比向红外光区移动。将大肠杆菌和金黄色葡萄球菌接种在样品表面,以评估样品的抗菌能力。细菌实验结果表明,掺氮态TiO_2在可见光下可以有效降低细菌活力。由实验结果可见,微弧氧化和氮离子注入复合工艺制备的抗菌TiO_2涂层在医学和海洋领域具有很大潜力。     

抗菌功能性铝基材料的制备及表征

通过交流电沉积的方法在铝阳极氧化膜的孔内沉积金属铜,制备了铝基抗菌功能性材料;测试了沉积铜的铝阳极氧化膜的抗菌性能.结果表明:电沉积铜的铝阳极氧化膜对大肠杆菌、绿脓杆菌、粪链球菌和金黄色葡萄球菌的抗菌率均大于95%.透射电子显微镜表征了铜在氧化膜孔内的沉积形貌,铜在铝阳极氧化膜孔内呈连续的线状形貌,直径为25 nm.     

纯钛表面两步电化学法制备载银多孔涂层

在医用纯钛表面先采用阳极氧化法制备TiO2纳米管预涂层,然后通过AgNO3溶液浸泡和紫外光照射处理实现银颗粒在预涂层上的固定,再经过微弧氧化处理制备出载银多孔涂层。利用扫描电子显微镜(SEM)、能谱仪(EDS)、X射线光电子能谱(XPS)对涂层表面形貌、载银量、银元素纵向分布及特征进行了表征,并通过金黄色葡萄球菌检验了涂层的抗菌性能。结果表明:两步电化学法可以在纯钛表面制备出含银量较高的多孔涂层,涂层中银元素大部分以纳米颗粒形式存在,涂层表面和最外层Ag元素主要以氧化物的形式存在,而沿涂层法向向内Ag单质与Ag氧化物共存,且涂层具有良好的抗菌性能。     

等离子体电解氧化膜的工艺优化及耐腐蚀性能评价

对镁合金等离子体电解氧化膜的表面制备工艺进行了研究.采用正交设计法优化实验方案,对最佳工艺条件下制备的氧化膜的微观形貌、相组成进行了研究;采用点滴腐蚀、动电位极化曲线、循环阳极极化曲线、电化学阻抗谱及浸泡腐蚀试验对AZ31镁合金及等离子体电解氧化膜的耐腐蚀性能进行了综合评价.结果表明,制备的等离子体电解氧化膜的最佳工艺为KOH 4g/L、硅酸盐20 g/L、氧化电压300 V、氧化时间30 min;氧化膜主要成分为MgSiO3和Mg2SiO4,经过等离子体电解氧化之后其显微硬度、耐点滴腐蚀、耐均匀腐蚀和耐点腐蚀性能较AZ31镁合金均有较大提高.     

LC4 铝合金表面硬质阳极氧化膜制备及表征

目的在LC4铝合金表面制备硬质阳极氧化膜,讨论工艺参数对膜层厚度和硬度的影响。方法对阳极氧化的时间、温度、电流密度及正负脉冲电流时间比等参数进行优化实验,通过OM,SEM,XRD及显微硬度计等对制备的氧化膜层的厚度、硬度、形貌等进行研究。结果工艺优化后的参数为:温度-2~0℃,正脉冲电流密度4 A/dm2,负脉冲电流密度1 A/dm2,正负脉冲电流时间比6∶1,氧化时间50 min。得到由一系列直径约为50 nm的管状单元结构组成的氧化膜,其厚度为36μm,硬度为420HV。结论制备的阳极氧化膜具有致密的组织结构和高的硬度值。     

铝合金氧化膜阻抗谱图的研究

本实验分别测定了由硫酸氧化法制备的铝合金氧化膜封闭前后在K_2SO_4溶液中的交流阻抗谱(Bode图),由阻抗谱分析获得了有关阻挡层的几何尺寸、阻挡层和多孔层以及封闭产物的电学性质、时效对氧化膜的影响等信息。这些结果与迄今为止的对氧化膜构造的认识是一致的,交流阻抗谱技术在氧化膜结构、封闭机理和质量的研究中,有理论和应用两方面的价值。     

钛合金微弧氧化生物膜制备与性能研究

综合国内外钛合金微弧氧化生物膜制备的方法,主要阐述了电参数与电解液对钛合金微弧氧化生物膜结构以及性能的影响机制.脉冲电源下,电流对膜层的制备具有良好的调整作用,且得到的膜层厚度显著增大.膜层厚度随氧化电压的升高而增加时,膜层表面颜色与腐蚀电位也发生变化.增加脉宽,降低频率时,单脉冲放电能量随之增加,微弧氧化成膜速率显著加快.不同体系电解液制备的膜层表面粗糙度、微孔结构等存在差异.在电解液中引入银、锌、铜离子能有效改善植入物涂层表面细菌黏附引起的异物炎症问题,增强其抗菌作用.基于目前钛合金微弧氧化的研究进展,展望了该研究方向,对钛合金植入物在临床医学应用发展中具有积极的促进作用.     

阳极氧化法制备TiO2多孔膜

通过对TiO2多孔膜阳极氧化制备工艺的研究，提出了其成膜机理。实验以硫酸为电解液，以纯钛(TAl)为阳极，铜片为阴极，采用了恒压和恒流2种阳极氧化方式，在纯钛的表面获得TiO2多孔膜。用FESEM观察其孔径分布在100nm～200nm之间，并且随着阳极氧化电压和电流密度的增加，多孔膜的孔径有增大的趋势。最后，讨论了在硫酸电解液中TiO2多孔膜的形成机制。     

用于环境抗菌的氧稳定W-Ag薄膜（英文）

在溅射沉积的钨薄膜中加入氧以降低薄膜的残余应力，进一步添加含量高达14.3%(摩尔分数)的银以进行抗菌功能化。采用SEM-EDX、XPS和XRD分析薄膜。薄膜仅检测到β-W或W₃O相的X射线衍射峰。氧和银主要以固溶原子的形式存在于薄膜中。银的加入降低了薄膜的硬度(仍然≥10.3 GPa)和弹性模量。动电位极化实验表明WO膜的腐蚀电流密度低于钨膜，而银改变了膜层的腐蚀行为。薄膜表面的贫银氧化钨层抑制了银离子在水中的释放，WOAg膜对大肠杆菌具有良好的抗菌活性。WOAg薄膜将在环境和其他抗菌应用中发挥作用。     

铝阳极氧化膜的微观结构及沸水封闭处理对膜层显微硬度的影响

通过阳极氧化在铝合金表面获得稳定的阳极氧化膜,并对膜层进行沸水封闭处理,采用扫描电子显微镜(SEM)、电化学阻抗谱(EIS)等分析手段研究了氧化电流密度以及封闭处理对膜层显微硬度的影响。结果表明:随着电流密度的增加,铝合金阳极氧化膜的显微硬度先升高,后降低;沸水封闭会导致铝阳极氧化膜的显微硬度下降;铝阳极氧化膜表面形貌的优劣、多孔层的组织结构和屏蔽性与膜层显微硬度密切相关。     

Anodic oxidation of Al–Ag alloys

The anodic oxidation of solution-treated and quenched Al–Ag alloys containing 0.3, 0.6, 0.9 and 1.2 at.%Ag, is examined in ammonium pentaborate electrolyte, which leads to growth of barrier-type anodic films. Enrichments of silver, 3.1×10¹⁵ Ag atoms cm⁻², are developed in the alloys immediately beneath the amorphous alumina films, with the level of enrichment not depending significantly upon the composition of the bulk alloy. The enrichment is relatively low due to clustering of silver atoms in the bulk alloy, which reduces the concentration of silver that is available to enrich from solid solution. Silver species are incorporated into the anodic film, where they migrate outward faster than Al³⁺ ions.     

Uniformity of passive films formed on ferrite and martensite by different inorganic inhibitors

A comparison of uniformity of passive films formed on ferrite and martensite by three kinds of inorganic inhibitors, chromate, bicarbonate and nitrite, has been made by anodic polarization curve and AC impedance measurements. It was found, by anodic polarization curve analyses, that there was different pitting susceptibility of passive films formed on ferrite and martensite by chromate or bicarbonate. In the solution containing chloride ions, the broken potential of the passive film formed on ferrite by chromate or bicarbonate was more negative than that on martensite. However, the passive films formed on both ferrite and martensite by nitrite had similar pitting susceptibility. Their broken potentials were almost the same. The difference in pitting susceptibility of the passive films was explained by Mott-Schottky analyses. It was found that the passive film formed on ferrite by chromate or bicarbonate had a higher donor concentration than the passive film on martensite. The passive films with higher donor concentrations were more sensitive to chloride ions. However, the passive films formed on both ferrite and martensite by nitrite had the same donor concentration. A uniform passive film can be formed on a martensite mild steel with ferrite bands by nitrite.     

Formation and capacitance properties of Ti-Al composite oxide film on aluminum

Al specimens were covered with TiO2 film by sol-gel dip-coating and then anodized in ammonium adipate solution. The structure, composition and capacitance properties of the anodic oxide film were investigated by transmission electron microscopy (TEM), Auger electron spectroscopy (AES), X-ray diffractometry (XRD) and electrochemical impedance spectroscopy (EIS). It was found that an anodic oxide film with a dual-layer structure formed between TiO2 coating and Al substrate. The film consisted of an inner Al2O3 layer and an outer Ti-Al composite oxide layer. The thickness of layers varied with the number of times of sol-gel dip-coating. The capacitance of anodic oxide films formed on coated specimens was at most 80% higher than that without TiO2. In film formation mechanism, it was claimed that the formation of composite oxide film was mainly affected by the structure of micro-pores network in TiO2 coating which had an influence on Al3+ and O2- ions transport during the anodizing.     

磷酸盐封孔处理对铝合金阳极氧化膜耐蚀性能的影响

为进一步提高铝合金阳极氧化膜的耐蚀性能,采用磷酸盐对其进行封孔处理.利用电化学阻抗谱 (EIS ) 分析该封孔处理对阳极氧化膜耐蚀性能的影响规律,并与常规沸水封孔和铈盐封孔进行比较.实验结果表明,磷酸盐封孔处理后可在阳极氧化膜表面形成约为15 μm厚的致密磷酸盐涂层,与常规沸水和铈盐封孔处理相比,磷酸盐封孔处理的阳极氧化膜具有更好耐蚀性和时效性.该方法可为阳极氧化膜封孔处理提供一种新途径.     

铝上阳极氧化膜在铬酸盐/重铬酸盐溶液中的溶解

铝上的阻挡型阳极氧化膜浸泡在不同 pH 的铬酸盐/重铬酸盐溶液中时,膜的电容会不断增大,通常都把这一现象归因于阳极氧化膜的单纯的均匀减薄。然而,本研究表明,在经过这样浸泡的膜的截面超薄切片的透射电镜照片上,膜厚度的减小比由电容数据算出的结果小得多。由这两种方法获得的膜厚数据的明显差异,用膜的简单溶解是无法解释的。它很可能跟铬酸根离子在阳极氧化膜中较复杂的渗透过程有关,渗透了的膜到最终才变得松散而溶解。这一结论得到了俄歇电子能谱分析的佐证,因为在浸泡过的膜的外层发现有铬的存在。     

铝阳极氧化膜形成过程中离子迁移的规律及对膜形态的影响

用透射电镜、标记原子及等离子体发射光谱定量分析等技术,研究了铝阳极氧化膜生长过程中离子迁移分数及其对膜形态的影响。实验发现,在膜形成过程中,铝和含氧离子沿相反方向漂移穿过膜。在同一电解质溶液中,铝离子的真实迁移分数基本恒定。当电流密度超过某一临界值时,部份铝离子在膜与溶液界面处形成新膜物质,膜的形态为壁垒型。而当电流密度小于临界电流密度时,全部铝离子均进入溶液。这时膜完全由含氧离子在膜与基体界面处形成,由于溶液对膜外表面的侵蚀,形成的膜为多孔型。推导了膜生长效率的理论表达式;表观迁移分数的关系式.用溶解—沉积理论解释了铝离子在膜与溶液界面处形成新膜物质的机理。     

The effects of sealing on cracking tendency of anodic films on 2024 aluminum alloy after heating up to 300 °C

The influence of sealing methods on cracking tendency of anodic films on 2024 alloys after heating was studied. The anodic films were sealed by the methods of ambient water, boiling water, nickel fluoride and potassium dichromate, respectively. The results showed that the sealing mechanisms had important effects on initiation of cracks in anodic films during sealing process. The condensation of sealing products resulted in cracking of anodic films during sealing in boiling water, nickel fluoride solution and ambient water. On heating, the thermal stress was released mainly by widening and deepening of the originally initiated cracks during sealing. The cracks may penetrate through the anodic films and have detrimental effect on corrosion resistance of the films. The dichromate sealed anodic film showed an obviously decreased cracking tendency, which was attributed to the lower hydration extent and the opening pores during sealing process. Even after heating, there was no crack observed in the film. The result suggests that an “opening sealing” mode is beneficial to decrease the cracking tendency of anodic films during sealing and heating processes.     

阳极氧化二氧化钛薄膜的光电化学防腐蚀特性

利用阳极氧化法制备TiO2薄膜，并研究了薄膜的光电化学防腐作用．XRD和SEM分析表明TiO2薄膜由非晶和锐钛矿组成．其表面形貌较为粗糙．在紫外光的照射下，测试了薄膜在模拟海水中的电极电位、极化曲线、电化学阻抗谱以及与碳钢的耦合电流．结果表明TiO2薄膜对碳钢在模拟海水中的腐蚀具有较好的光阴极保护作用．     

Electroless deposition of W-doped Ag films onto p-Si（100） from diluted HF solution

Tungsten-doped silver films were prepared by immersing hydrogen-terminated silicon wafers into the solution of 2.5 mmol/L [Ag₂WO₄]+0.1 mol/L HF at 50 °C. Their growth and composition were characterized with atomic force microscopy and X-ray photoelectron spectroscopy, respectively. The effect of tungstate ions on the deposition of silver was investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) by comparing W-doped Ag film with Ag film. It is found that the molar fraction of tungsten in the deposits is about 2.3% and the O to W molar ratio was about 4.0 and W-doped Ag films have good anti-corrosion in air at 350 °C. The doping of tungsten cannot change the deposition of silver.