Studies to control biofilm formation by coupling ultrasonication of natural waters and anodization of titanium

The main objective of this study was to investigate the combined effect of ultrasonication of natural waters and anodization of titanium on microbial density and biofilm formation tendency on titanium surfaces. Application of 24 kHz, 400 W high power ultrasound through a 14 mm horn type SS (stainless steel) Sonicator with medium amplitude of 60% for 30 min brought about three order decrease in total bacterial density of laboratory tap water, cooling tower water and reservoir water and two order decrease in seawater. Studies on the effect of ultrasonication on dilute pure cultures of Gram-negative and Gram-positive bacteria showed five order and three order decrease for Pseudomonas sp. and Flavobacterium sp. respectively and two order and less than one order decrease for Bacillus sp. and Micrococcus sp. respectively. Ultrasonication increased lag phase and reduced logarithmic population increase and specific growth rate of Gram-negative bacteria whereas for Gram-positive bacteria specific growth rate increased. Studies on the biofilm formation tendency of these ultrasonicated mediums on titanium surface showed one order reduction under all conditions. Detailed biofilm imaging by advanced microscopic techniques like AFM, SEM and epifluorescence microscopy clearly visualized the lysed/damaged cells and membrane perforations due to ultrasonication. Combination of ultrasonication and anodization brought about maximum decrease in bacterial density and biofilm formation with greater than two order decrease in seawater, two order decrease in Bacillus sp. culture and more than four order decrease in Flavobacterium sp. culture establishing the synergistic effect of anodization and ultrasonication in this study.     

Surface treatment of iron by electrochemical oxidation and subsequent annealing for the improvement of anti-corrosive properties

Corrosion resistance of iron oxides on iron foils prepared by anodization, annealing or a combination of both was characterized by electrochemical methods. Even though iron oxide film with a thickness of more than 2 μm could be prepared by single anodization, corrosion resistance deteriorated because the oxide film was in the amorphous phase and contained many defects. Corrosion resistance of iron oxides was also not enhanced by single annealing. Conversely, combination of anodization and subsequent annealing led to a positive shift of the corrosion potential in the Tafel plot, indicating that corrosion resistance was improved. Formation of thicker oxide during anodization was associated with a more positive shift in corrosion potential after annealing. Electrochemical impedance spectroscopy showed that the slowest charge transfer was observed in oxide films grown by a combination of anodization and annealing. We found that the optimum annealing temperature of anodic films in terms of the most positive shift of E_corr was 500 °C.     

TiO2 nanotubes fabricated by electrochemical anodization in molten o-H3PO4-based electrolyte: Properties and applications

Self-organized TiO₂ nanotubes (NTs) can be formed by electrochemical anodization. Anodization is generally performed in aqueous or organic electrolytes containing halogen ions, such as Cl⁻ and F⁻. However, these electrolytes lead to less ordered structures or carbon remnants, thus suppressing the electrical properties and limiting the applications. To overcome these limitations, new anodization approaches were performed in carbon-free electrolyte-based electrolyte. In this review, we summarizes the short history of TiO₂ NTs, general mechanisms of growing NTs, properties, and applications of classic TiO₂ NTs. Then, a new-generation of anodization approach conducted in molten orhto-phosphoric acid is elucidated based on anodization parameters, concluding the optimized condition to form highly ordered TiO₂ NT arrays. Finally, the review addresses further modifications such as heat-treatment, noble metal deposition, thermal dewetting, and double anodization to enhance the optical and electrical properties for use in various applications.     

马来酸在束状TiO2阳极氧化膜上的电催化还原

采用阳极氧化法在0.5 mol·L-1硫酸+1 mol·L-1马来酸的混合溶液中制得了束状TiO2薄膜. X射线衍射(XRD)分析表明样品的晶型结构主要为无定形态; 所制得的样品通过原子力显微镜(AFM)观察, 束状结构TiO2的宽度约2-5 μm, 长度超过20 μm, 束状结构中包含的纳米棒直径约80-150 nm. 将制得的束状TiO2膜电极在上述混合溶液中直接进行原位的循环伏安扫描和恒电流电解实验. 研究结果表明, 马来酸在该电极表面异相电催化还原生成丁二酸; 在恒电流电解过程中采用电极原位活化可明显提高丁二酸的产率和电流效率, 并指出改进电极的原位活化技术是未来研究工作的主要目标.     

甘油基电解液中阴离子对阳极氧化TiO2纳米管生长的影响

在NH4F-甘油-水电解液中, 采用阳极氧化法, 在纯Ti基底上制备了高度取向的TiO2纳米管阵列, 考察了阴离子种类、阳极氧化时间及NaAc浓度对纳米管阵列生长的影响. 结果表明, TiO2纳米管的生长速率和长度强烈依赖于阴离子的种类和浓度. NaNO3和NaCl的加入能增大阳极氧化时的电流密度, 提高TiO2纳米管底部的腐蚀速率, 提高管的生长速率及增加管的长度; 而NaAc的加入更大程度上抑制了已生成的TiO2纳米管顶部的溶解, 提高了纳米管的净生长速率, 得到较长的纳米管阵列.     

铂微电极位点上氧化铝纳米孔的制备

金属微电极表面的纳米级处理可以大大提高电极的性能。本文基于微加工及电化学技术在铂微电极位点上制备了一致性良好的氧化铝纳米结构。通过对基片铂层表面等离子体处理,使铝膜与铂层之间粘附力明显增强。利用二次阳极氧化法,在铂微电极位点上制备出纳米孔。结果表明,30V是该条件下比较理想的氧化电压。同时,通过对氧化过程中电流的监测,发现当铝膜完全氧化后电流大幅上升,可将此现象作为终止阳极氧化的标志。这种微电极位点处的氧化铝模板可进一步用于不同材料纳米微电极的制备。     

还原剂对多孔阳极氧化铝纳米孔道结构的影响

多孔阳极氧化铝(PAA)和多孔阳极氧化钛纳米管(PATNT)的结构调控近年来倍受关注. 在形成机理尚不清楚的情况下, 对PAA和PATNT的结构调控很难避免盲目性. 为验证“氧气气泡模具”可以形成纳米孔道这个新观点, 本文采用化学方法对PAA的结构进行调控, 成功地引入了一种还原剂来吸收纳米孔道中的氧气气泡. 在添加还原剂的草酸溶液中得到了一种特殊的阳极氧化铝膜. 研究了还原剂的含量对磷酸溶液中形成PAA孔道结构的影响, 结果表明随着还原剂含量的增加, PAA的孔道直径逐渐减小, 有序性降低. 对比了添加还原剂前后阳极氧化过程的电压-时间曲线的差异, 结果表明, 在含有还原剂溶液中制备的阳极氧化铝膜的导电性明显提高. 在密封的条件下, 还原剂能吸收掉孔道中的氧气, 使气泡模具效应消失, 得到完全的致密型氧化膜. 这些实验事实充分证明PAA中有序孔道的形成是氧气气泡模具效应的结果.     

Oscillatory regime of titanium anodization under voltage control

Regular current oscillations during anodization of titanium in potentiostatic conditions were postulated in the literature but never documented experimentally. We here report emergence of such oscillatory anodization on Ti submitted previously to the activation procedure. Activation consisted in remaining the specimen under open circuit conditions in the electrolyte containing fluoride ions. The sign of the activation end point was fast drop of the electrode potential to negative values, well below the potential of the cathodic hydrogen evolution. At the active state titanium exposed to the electrolyte its surface free of oxides and subsequent anodization occurred on the bare metal and not on the metal covered with native oxide.Oscillations were observed in 1 M H₂SO₄ in the voltage range from 6 to 30 V in both voltage scan and step experiments. Their amplitude, shape and spectral character changed with anodization voltage. Electrolyte mixing had no influence on oscillations suggesting no role played by the transport in the electrolyte bulk. At elevated temperature oscillations were more regular and similar was the influence of mixture of H₂SO_4aq with ethylene glycol. The latter introduced however strong ohmic voltage drop in the electrolyte this causing the change of the shape and periods of oscillations.     

Thick porous tungsten trioxide films by anodization of tungsten in fluoride containing phosphoric acid electrolyte

In the present work, we report on the formation of mesoporous thick tungsten trioxide films grown on tungsten foil by anodization in fluoride containing concentrated phosphoric acid (85%) electrolyte. Under optimized experimental conditions, mesoporous WO₃ films with a thickness up to approximately 2 μm are formed. SEM shows the films to consist of a connected network with a typical pore and feature diameter of ca 50 nm. These films as formed are amorphous and can be annealed to orthorhombic WO₃ structure. These thick porous films can show significant enhanced electrochromic and improved photocatalytic properties.     

Synthesis and growth mechanism of zirconia nanotubes by anodization in electrolyte containing Cl−

The formation and growth of a self-organized zirconia porous layer can be achieved directly by anodization of Zr in chloride containing electrolytes. The morphology of the porous layers is affected by electrochemical conditions such as Cl⁻ concentration. Zirconia nanotubes with diameters ranging from 250 to 300 nm and a length of 33 μm were formed under proper conditions. The nanotubes have smooth and straight walls. The composition of the nanotubes was characterized by using an energy dispersive spectrometer. Selected area electron diffraction investigation reveals that the as-anodized zirconia nanotubes have an amorphous structure. Crystal phase transition and structural stability of the ZrO₂ nanotubes after heat treatment were characterized. A possible growth mechanism is presented.