表面有阳极氧化层的氘化钛热解吸动力学研究

应用反应速率分析方法,测定了氘化钛和表面有阳极氧化层的氘化钛在恒容体系和600～800℃范围内的热解吸反应速率常数,得到氘化钛和阳极氧化的氘化钛热解吸氘的活化能分别为(24.9±1.0)kJ/mol和(38.5±1.2)kJ/mol;氘化钛表面氧化层越厚,表观活化能越大;实验表明氘化钛表面阳极氧化层具有阻氘性能.     

用氧化多孔硅作牺牲层制备悬空微结构

提出一种新的牺牲层工艺。先将阳极氧化生成的多孔硅在300℃的氮气氛下进行退火以稳定其多孔结构，然后将其在700℃下氧化成为具有多孔结构的二氧化硅。用氧化的多孔硅材料作为牺牲层材料，既可以保留多孔硅牺牲层材料释放迅速的优点，又克服了多孔硅在释放时的局限性。实验运用氧化的多孔硅材料作牺牲层成功制备了悬空振膜和悬臂梁结构。     

Preparation of nanoporous titanium oxide films by electrochemical anodic oxidation

We have investigated the conditions of the formation of tubular layers of nanoporous TiO₂ (NPTO) by the anodic oxidation of Ti in a 1% ammonium fluoride solution in ethylene glycol. The results demonstrate that increasing the anode current density and anodization time increases the nanotube diameter. A model has been proposed for the formation of tubular NPTO layers. The model builds on the concept of anisotropic Ti etching. The rate of the formation of the tubular structure of TiO₂ has been shown to be limited by the oxide film growth rate under the conditions of this study.     

Fabrication of novel porous anodic alumina membranes by two-step hard anodization

Porous anodic alumina (PAA) membranes with highly ordered hexagonal cells and a novel pore structure have been fabricated by two-step hard anodization in a H(2)SO(4)-Al(2)(SO(4))(3)-H(2)O system at 40 and 50?V, giving average cell diameters of 77 and 96?nm, respectively. There are several tiny pores embedded in each big shallow pore on the top of the membranes, and there is only one pore in one cell at their bottom. The cells on both sides of the membranes present almost the same periodic arrangement. In order to explore the formation of the novel pore structure, PAA membranes fabricated at different current densities (30-200?mA?cm(-2)) are obtained by maintaining a constant voltage at 40?V. The experimental results show that the interpore distance is not only dependent on the anodization voltage, but is also influenced by the current density, which means that the pore structure of PAA membranes fabricated by hard anodization can be accurately designed and controlled by adjusting the anodization voltage and current density simultaneously.     

高度有序多孔阳极氧化铝膜形成机理的探讨

使用高纯铝片,利用电化学阳极氧化制备了多孔阳极氧化铝(AAO)膜,用原子力显微镜(AFM)对其形貌进行了表征,提出铝阳极氧化过程中纳米孔从无序到有序的自组织模型,探讨了高度有序六角形纳米孔阵列的形成过程,并分析了影响纳米孔有序度的因素及提高有序度的途径.根据自组织模型探讨了长时间阳极氧化和二次氧化条件下形成高度有序六角形纳米孔阵列的机理.     

管状阳极氧化铝模板的表面氧化应力分析及其应用研究

通过对高纯铝片预制铝管分别进行"外表面阳极氧化"(外氧化)和"内表面阳极氧化"(内氧化)制备了管状多孔氧化铝模板(AAO),考察了氧化过程中Al/Al2O3界面的应力影响。实验直观表明,"外氧化"过程中Al/Al2O3界面产生拉伸应力易导致管状模板产生轴向裂纹;而"内氧化"过程中Al/Al2O3界面产生压缩应力使管状模板更加紧密而不易破裂。研究结果表明,Al/Al2O3界面上拉伸应力的有效释放是获得无裂纹管状阳极氧化铝模板的关键。最后,利用管状氧化铝模板制备了放射状Cu纳米线阵列,并对其在膜渗透方面的应用进行了初步尝试。     

Fabrication of highly ordered anodic aluminium oxide templates on silicon substrates

The controlled fabrication of highly ordered anodic aluminium oxide (AAO) templates of unprecedented pore uniformity directly on Si, enabled by new advances on two fronts - direct and timed anodisation of a high-purity Al film of unprecedented thickness (50 mum) on Si, and anodising a thin but pre-textured Al film on Si, has been reported. To deposit high-quality and ultra-thick Al on a non-compliant substrate, a prerequisite for obtaining highly ordered pore arrays on Si by self-organisation while retaining a good adhesion, a specially designed process of e-beam evaporation followed by in situ annealing has been deployed. To obtain an AAO template with the same high degree of ordering and uniformity but from a thin Al film, which is not achievable by the self-organisation alone, pre-patterning of the thin Al surface by reactive ion etching using a freestanding AAO mask that was formed in a separate process was performed. The resultant AAO/Si template provides a good platform for integrated growth of nanotube, nanowire or nanodot arrays on Si. Template-assisted growth of carbon nanotubes (CNTs) directly on Si was demonstrated via a chemical vapour deposition method. By controllably removing the AAO barrier layer at the bottom of the pores and partially etching back the AAO top surface, new CNT/Si structures were obtained with potential applications in field emitters, sensors, oscillators and photodetectors.     

外表面不同孔结构的阳极氧化铝模板的自组织制备

经二次阳极氧化制备了外表面不同孔结构的阳极氧化铝模板.用场发射扫描电镜(FE-SEM)对其形貌进行表征,发现在直接阳极氧化的铝箔的外表面自组装形成了规则的六方形的纳米孔,而在去除铝基、扩孔的另一外表面则形成了规则的圆形的纳米孔,外表面纳米孔的平均直径大约为80nm,孔间距大约为110nm,孔密度约为2.5×10n cm-2.在模板的内部形成相互平行且垂直于AAO模板外表面的纳米管的阵列结构,纳米管的平均直径大约为80nm;AAO模板的厚度大约为10/zm.粉末X射线衍射(XRD)表明模板具有非晶态的结构.记录了阳极氧化过程中的电流一时间曲线,探讨了自组织孔洞的形成机理,提出了新型阳极氧化铝模板制备纳/微米结构材料模拟应用.     

Titanium oxide films produced on commercially pure titanium by anodic oxidation with different voltages

Titanium oxide films produced on commercially pure Ti by anodic oxidation with different voltages were analyzed. Anodic oxidation was carried out at room temperature using 1.4 M H₃PO₄ electrolyte and a platinum counter-electrode, in potentiostatic mode under the following conditions: 50 V, 100 V, 150 V, 200 V and 250 V. It was observed that porous titanium layers were formed at all voltage values but morphological differences were observed. Initially, the film was thin but with increasing voltage it broke down locally and porous regions became evident due to the dielectric breakdown. The porosity and the pore size increased with the increasing voltage. The surface morphology in samples formed with 200 V had substantially different porous structures than those formed with other voltage values. The anodic film surface displayed pores and craters formed on the relatively flat ground oxide surface. AFM images showed that higher voltages produced thicker titanium oxide films.     

A comparative study of anodic tantalum pentoxide and high-pressure sputtered titanium oxide

In this work we present a new method to fabricate improved TiO₂ films by using a high-pressure sputtering system. In order to minimize the damage induced in the substrate surface by the ion bombardment, a high chamber pressure of 100 Pa is used, which is very much higher than typical values in conventional systems. We present results obtained by X-ray diffraction and FTIR spectroscopy. Moreover, we will compare the properties of the resulting TiO₂-insulator-metal capacitors with those of anodic Ta₂O₅. Very thin films of TiO₂ have been obtained with a very promising quality for future electron device fabrication.     

Fabrication of ordered Cr nanostructures by self agglomeration on porous anodic alumina membranes

In this paper, we propose an efficient and effective method to fabricate highly ordered Cr nanoarrays with sub-gaps less than 15 nm and particle size less than 50 nm on the top surface of a modified porous anodic alumina membrane (PAA). In addition, the factors that influence the structural parameters of the fabricated nanostructures were studied. With the aid of SEM and AFM images, the amount of sputter-coated Cr was tailored to the given PAA surface morphology. The mechanism of formation of the Cr nanostructures was also discussed.     

Fabrication of mesoporous titanium oxide nanotubes based on layer-by-layer assembly

Titanium oxide (TiO2)/polyacrylic acid (PAA) composite nanotubes were firstly fabricated through the sol-gel process of titanium alkoxide in the inner pores of alumina template followed layer-by-layer assembly with polyacrylic acid (PAA). Mesoporous TiO2 nanotubes could be obtained after the removal of PAA component by calcination and etching of the template with concentrated sodium hydroxide aqueous solution. The surface area of as-prepared porous TiO2 nanotubes was measured as twice larger than that of the conventional TiO2 nanotubes and the pore diameter in the wall of the tubes is several nanometers. Such assembled mesoporous nanotubes can serve as carriers for catalysis release and biomolecules.     

Tailoring defect structure and optical absorption of porous anodic aluminum oxide membranes

Defects influence the optical and electronic properties of nanostructured materials that may be relevant for applications. In self-organized anodic aluminum oxide (AAO) templates we have investigated the effect of annealing, doping and nanoscale metal deposition. Optical absorption spectroscopy has been used as a sensitive probe for the defect density in AAO templates. The electronic spectra are found to be dominated by bands which originate from oxygen-deficient color centers (F⁺, F and F₂). In annealing studies, the integrated absorption of the bands changes non-monotonically with annealing temperature and annealing time. This demonstrates that the concentration of defects can be optimized to tailor the optical properties of the AAO. Metallic Au wires are deposited in the template to establish a plasmonic template or array. The investigations provide an interesting insight into the interplay of reactivity and diffusivity on nanoscales.     

Hydrothermal precipitation of hydroxyapatite on anodic titanium oxide films containing Ca and P

Highly-crystallized hydroxyapatite (HA) can be precipitated during heat treatment in high-pressure steam at 300 °C on an anodic titanium oxide film containing Ca and P (AOFCP), which has been electrochemically formed on a titanium substrate prior to the hydrothermal treatment. Factors affecting the precipitation, such as a percentage of distilled water in the autoclave and additives in the AOFCP, were evaluated by scanning electron microscopy. Ca²⁺ and PO^3– ₄ ions were leached from the AOFCP into a water layer covering the film surface, and nucleate HA heterogeneously on the porous TiO₂ matrix of the AOFCP which was made by the ion leaching. The morphology of the precipitated crystals was significantly affected by the water volume ratio because the concentrations of the Ca²⁺ and PO₄ ^3– ions varied depending on the thickness of the water layer. The amount of the precipitation decreased on the AOFCP which was formed in the solution containing a small amount of Mg²⁺ ions or formed on Ti-6Al-4V alloy instead of titanium.     

Fabrication of lithium-doped zinc oxide film by anodic oxidation and its ferroelectric behavior

A lithium-doped zinc oxide (ZnO) film was obtained by the anodic oxidation of a zinc sheet in a lithium hydroxide (LiOH) solution under an external DC voltage. The formation of the ZnO film on the surface of the Zn sheet is attributed to two simultaneous processes: the electrochemical oxidation of Zn to ZnO, and the chemical dissolution of ZnO. It was also confirmed that Li element was successfully introduced into the lattice of the ZnO film. The curves of the polarization versus applied field were measured to be hysteresis loops, suggesting ferroelectricity of the Li-doped ZnO film. The remanent polarization and the coercive field of the film were measured to be 4.7 × 10⁻³ C m⁻² and 1.2 × 10⁷ V m⁻¹, respectively. This ferroelectricity is believed to be the result of the occupation of off-centered positions in oxygen tetrahedra by the Li⁺ ions.     

TA4电化学抛光和阳极氧化处理表面生物相容性的比较

比较了TA4纯钛材电化学抛光表面和阳极氧化表面的形貌、抗腐蚀性能、微动摩擦磨损性能和生物活性。结果表明,与阳极氧化表面相比,电化学抛光表面具有较多纳米尺度孔穴(孔穴总数较低),较低的表面粗糙度(低约一个数量级),较低的抗腐蚀性能(后者的腐蚀速率比前者的稍大),较低的摩擦系数(0.134vs.0.286),较差的耐磨性能,以及较高的生物活性(模拟体液中Ca-P层的生长速率)。     

Fabrication of hydrogen sensors with transparent titanium oxide nanotube-array thin films as sensing elements

Transparent thin films comprised of highly ordered titania nanotube-arrays were grown from titanium thin films using an anodization technique, from which highly sensitive and selective hydrogen sensors that can operate at room temperature were fabricated. Titanium films sputter deposited on glass at 500 °C were anodized in a fluorine-containing electrolyte to obtain nanotube-array films. Precise monitoring of current during the anodization enabled removal of the samples from the anodization bath at a point where the remaining metal layer became discontinuous, without destroying the nanotube architecture. The samples were then annealed in oxygen at 420 °C to crystallize the nanotube-arrays as well as oxidize any un-anodized metallic regions, yielding transparent films comprised of titanium oxide nanotube-arrays. Herein, we discuss the morphology, structure and optical characterization of these films. When coated with a 10-nm discontinuous palladium layer, the optically transparent nanotube-array films serve as excellent hydrogen sensors, exhibiting a four-order magnitude drop in resistance with exposure to 1000 ppm hydrogen at room temperature.     

非晶型超疏水和超亲水TiO2薄膜的制备与表征

通过溶胶-凝胶法, 以载玻片为基底制得非晶型纳米TiO₂薄膜, 用SEM、 XPS、 XRD和接触角测量仪研究了薄膜的微观形貌、 表面元素、 晶型结构及薄膜的疏水性, 用Wenzel、 Cassie 理论对纳米TiO₂薄膜的润湿性进行了理论分析。结果表明, 经紫外光照射16 h后, 薄膜表面由超疏水性变为超亲水性, 接触角接近0°。薄膜表面合适的粗糙度和低表面能材料表面修饰的协同作用使其表现出良好的超疏水性。