TC4钛合金表面阳极氧化制备TiO_2多孔膜的实验研究

以硫酸为电解液,钛合金(TC4)为阳极,不锈钢片为阴极,采用恒压的氧化方式在钛合金表面获得TiO2多孔膜。通过扫描电镜(SEM)观察了多孔膜的微观形貌并用X射线衍射(XRD)对覆在钛合金基体上的氧化膜进行了物相分析,研究了氧化工艺参数电压、阳极氧化时间和硫酸浓度对TiO2多孔膜相组成的影响。结果表明:TC4钛合金阳极氧化获得的氧化膜为非均一平面的TiO2多孔膜,且膜的孔径分布在90~240nm,XRD分析表明在不同的氧化工艺参数下氧化膜均由锐钛相和金红石相双相晶型组成。在0.5mol/L硫酸溶液中,电压高于100V或氧化时间长于5min即出现锐钛相和金红石相TiO2,随着电压的升高和时间的增长金红石相TiO2的含量逐渐增加;在恒压120V时,硫酸溶液浓度为0.3mol/L即出现锐钛相和金红石相TiO2,随着硫酸浓度的提高金红石相TiO2的含量先增加后减少。     

TiO2纳米管上负载纳米铁的制备及其光电性能研究

采用阳极氧化法在钛金属表面制备出致密有序的TiO2纳米管阵列,分别利用磁控溅射和电子束辐照沉积技术在其上沉积Fe纳米颗粒以提高其光电性能。利用场发射扫描电镜观察两种不同技术制备的TiO2纳米管阵列负载纳米Fe结构的表面形貌。研究比较了不同制备方法得到的样品在紫外光和可见光照射下的光电效应。     

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.     

船用Ti80合金直流阳极氧化研究

在酸性溶液中,采用直流阳极氧化方法、恒电流模式在Ti80合金表面生成氧化膜。研究了氧化过程中电压随时间的变化关系,并对氧化膜的相组成、成分、微观形貌和厚度、绝缘性等性能进行了考核。结果表明,经过阳极氧化后,Ti80合金具有了足够厚且均匀连续的氧化膜,绝缘电阻有了很大的提高。     

Effects of temperature and voltage mode on nanoporous anodic aluminum oxide films by one-step anodization

Many conventional anodic aluminum oxide (AAO) templates were performed using two-step direct current anodization (DCA) at low temperature (0–5 °C) to avoid dissolution effects. This process is relatively complex. Pulse anodization (PA) by switching between high and low voltages has been used to improve wear resistance and corrosion resistance in barrier type anodic oxidation of aluminum or hard anodization for current nanotechnology. However, there are only few investigations of AAO by hybrid pulse anodization (HPA) with normal-positive and small-negative voltages, especially for the one-step anodization, to shorten the running time. In this article, the effects of temperature and voltage modes (DCA vs. HPA) on one-step anodization have been investigated. The porous AAO films were fabricated using one-step anodization in 0.5 M oxalic acid in different voltage modes including the HPA and DCA and the environment temperature were varied at 5–15 °C. The morphology, pore size and oxide thickness of AAO films were characterized by high resolution field emission scanning electron microscope. The pore size distribution and circularity of AAO films can be quantitatively analyzed by image processing of SEM. The pore distribution uniformity and circularity of AAO by HPA is much better than DCA due to its effective cooling at relatively high temperatures. On the other hand, increasing environment temperature can increase the growth rate and enlarge the pore size of AAO films. The results of one-step anodization by hybrid pulse could promote the AAO quality and provide a simple and convenient fabrication compared to DCA.     

不同电解液组成对TiO2纳米管形成的影响

电解液在阳极氧化中发挥着重要作用,对TiO2纳米管的形成与否,形成后管的成分、形貌都有着很大的影响.本实验采用了恒压阳极氧化方式,分别以HF(0.5wt%),(NH4)2SO4 HF(0.5wt%),(NH4)H2PO4 HF(0.5wt%),NaNO3 HF(0.5wt%)为电解液,在钛箔表面获得多孔TiO2膜.用FESEM观察了多孔膜的形貌并用EDX和XPS能谱对膜表面成分和构成进行测试分析.实验结果表明:在单一的HF酸电解液中加入(NH4)2SO4或(NH4)H2PO4后,阳极氧化生成的膜孔径明显减小,并且膜表面形态较差.加入NaNO3后,对膜的形貌影响不是很大.由EDX和XPS能谱分析得出,阴离子中的大部分非金属元素较难进入膜表面,而氮元素却很容易掺杂进入膜的表面形成N-Ti-O结构,从而影响膜的成分构成.这表明本实验利用简单电化学方法实现了N的掺杂.通过XRD测试得出,含不同阴离子的电解液对TiO2膜的晶型转变温度影响不大.     

Enhancing efficiency of dye-sensitized solar cells by combining use of TiO2 nanotubes and nanoparticles

Titanium dioxide nanotubes (TiNTs) were fabricated from commercial P25 TiO₂ powders via alkali hydrothermal transformation. Dye-sensitized solar cells (DSCs) were constructed by application of TiNTs and P25 nanoparticles with various weight percentages. The influence of the TiNT concentration on the performance of DSCs was investigated systematically. The electrochemical impedance spectroscopy (EIS) technique was employed to quantify the recombination resistance, electron lifetime and time constant in DSCs both under illumination and in the dark. The DSC based on TiNT/P25 hybrids showed a better photovoltaic performance than the cell purely made of TiO₂ nanoparticles. The open-voltage (V_oc), fill factor (FF) and efficiency (η) continuously increased with the TiO₂ nanotube concentration from 0 to 50 wt%, which was correlated with the suppression of the electron recombination as found out from EIS studies. Respectable photovoltaic performance of ca. 7.41% under the light intensity of 100 mW cm⁻² (AM 1.5G) was achieved for DSCs using 90 wt% TiO₂ nanotubes incorporated in TiO₂ electrodes.     

Voltage-dependent fabrication of nanoporous alumina and the applications to nanocapacitors

We investigated the fabrication of anodized aluminum oxide by anodization processes under DC and AC voltage biases. A two-step anodization process was used to fabricate the anodized aluminum oxide dielectrics in order to regulate the ordered nanopore array at the surface. AC samples showed the distorted nanoporous structure instead of a straight nanopore array in DC samples. As increasing the frequency of AC bias the nanovoid or nanocavity structure was formulated with the increased density of nanovoids. Nanoporous alumina was used for the fabrication of Ni-insulator-Al capacitors. The DC sample shows the tunneling process of an increase in leakage current and breakdown. When a negative voltage is applied to the capacitor device, the small current of 2 nA flows at a voltage of 0 V, indicating the existance of residual leakage current. The AC sample had very low leakage currents of the AAO dielectrics and the AAO hexagonal unit cell formed the nanocapacitor with a capacitance of 1-2 aF.     

光催化TiO2薄膜的溅射沉积技术

采用直流反应溅射技术可以制备出具有光催化作用的TiO2薄膜.这种TiO2薄膜经紫外光辐照后,可以分解有机物以及降低水和TiO2薄膜表面之间的接触角.然而,普通的直流反应溅射在制备介质膜时,普遍都存在着工艺不稳定、沉积速率低的问题,所以它不适合于工业化生产.脉冲磁控溅射与直流磁控溅射相比,它在基体表面附近具有较高的等离子体密度以及带电粒子具有较高的能量,这对于TiO2在低温下结晶十分有利.此外,采用双极脉冲模式生长的TiO2薄膜,它的光催化特性要优于单极脉冲模式.这种双极脉冲溅射并结合等离子体发射监控(PEM),使得工艺稳定性得到了改善,沉积速率亦得到了提高.     

Multilayer structure of tantalum anodic oxide films formed in dilute phosphoric acid

An investigation has been made of the multilayer structure of anodic oxide films on pure tantalum, formed up to various voltages with a constant current density of 1.0 mA cm^-2 in 1.0 × 10^-2 N H₃PO₄ at 20°C. For the study, infrared reflectance spectra (IRRS) were recorded and the optical thickness measuring method was successfully applied using the wavelengths of optical interference maxima and a chemical film stripper (concentrated ammonium hydrogen difluoride aqueous solution).The conclusions are that: (1) tantalum anodic oxide films anodized in dilute phosphoric acid consist of three layers, irrespective of the formation voltage; (2) the innermost layer is uniform whatever the anodization voltage; (3) phosphate anions are incorporated in both the outermost and middle layers but not in the innermost layer; (4) all three layers grow from the initial formation stage and the growth rates are nearly equal; (5) for formation voltages below 100 V the middle layer has an unchanging chemical structure, but above 100 V its chemical structure changes with the voltage; (6) the outermost layer appears to vary in chemical structure over all anodization voltages.     

Hydrothermal synthesis of 1D TiO2 nanostructures for dye sensitized solar cells

Mono-dimensional titanium oxide nanostructures (multi-walled nanotubes and nanorods) were synthesized by the hydrothermal method and applied to the construction of dye sensitized solar cells (DSCs). First, nanotubes (TiNTs) and nanotubes loaded with titanium oxide nanoparticles (TiNT/NPs) were synthesized with specific surface areas of 253 m²/g and 304 m²/g, respectively. After that, thermal treatment of the nanotubes at 500 °C resulted in their transformation into the corresponding anatase nanorods (TiNT-Δ and TiNT/NPs-Δ samples). X-ray diffraction and Raman spectroscopy data indicated that titanium oxide in the pristine TiNT and TiNT/NP samples was converted into anatase phase TiO₂ during the heating. Additionally, specific surface areas and water adsorption capacities decreased after the heat treatment due to the sample agglomeration and the collapse of the inner nanotube channels. DSCs were fabricated with the nanotube TiNT and TiNT/NP samples and with the anatase nanorod TiNT-Δ and TiNT/NPs-Δ samples as well. The highest power conversion efficiency of η = 3.12% was obtained for the TiNT sample, despite its lower specific surface compared with the corresponding nanoparticle-loaded sample (TiNT/NP).     

Fast fabrication of long TiO2 nanotube array with high photoelectrochemical property on flexible stainless steel

Oriented highly ordered long TiO2 nanotube array films with nanopore structure and high photoelectrochemical property were fabricated on flexible stainless steel substrate (50 microm) by anodization treatment of titanium thin films in a short time. The samples were characterized by means of field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and photoelectrochemical methods, respectively. The results showed that Ti films deposited at the condition of 0.7 Pa Ar pressure and 96 W sputtering power at room temperature was uniform and dense with good homogeneity and high crystallinity. The voltage and the anodization time both played significant roles in the formation of TiO2 nanopore-nanotube array film. The optimal voltage was 60 V and the anodization time is less than 30 min by anodizing Ti films in ethylene glycerol containing 0.5% (w) NH4F and 3% (w) H2O. The growth rate of TiO2 nanotube array was as high as 340 nm/min. Moreover, the photocurrent-potential curves, photocurrent response curves and electrochemical impedance spectra results indicated that the TiO2 nanotube array film with the nanoporous structure exhibited a better photo-response ability and photoelectrochemical performance than the ordinary TiO2 nanotube array film. The reason is that the nanoporous structure on the surface of the nanotube array can separate the photo electron-hole pairs more efficiently and completely than the tubular structure.     

Understanding pore rearrangement during mild to hard transition in bilayered porous anodic alumina membranes

We present a systematic study about the influence of the main anodization parameters (i.e., anodization voltage ramp and hard anodization voltage) on the pore rearrangement in nanoporous anodic alumina during mild to hard anodization regime transition. To cover the ranges between mild and hard regimes, the anodization parameters were each set to three levels (i.e., 0.5, 1.0, and 2.0 V s(-1) for the anodization voltage ramp and 80, 110, and 140 V for the hard anodization voltage). To the best of our knowledge, this is the first rigorous study about this phenomenon, which is quantified indirectly by means of a nickel electrodeposition. It is found that pore rearrangement takes place in a relatively random manner. Large areas of pores remain blocked when the anodization regime changes from mild to hard and, under certain anodization conditions, a pore branching takes place based on the self-ordering mechanism at work during anodization. Furthermore, it is statistically demonstrated by means of a design of experiments strategy that the effect of the anodization voltage ramp on the pore rearrangement is practically negligible in contrast to the hard anodization voltage effect. It is expected that this study gives a better understanding of structural changes in nanoporous anodic alumina when anodization is switched from mild to hard regime. Furthermore, the resulting nanostructures could be used to develop a wide range of nanodevices (e.g., waveguides, 1D photonic crystals, Fabry-Pe?rot interferometers, hybrid mosaic arrays of nanowires).     

Structure of nanotubular titanium oxide templates prepared by electrochemical anodization in H2SO4/HF solutions

The electrochemical formation of nanotubular titanium oxide films was investigated in 1 M H₂SO₄ and 0.05-0.4 wt.% HF electrolytes. Depending on anodization condition, i.e. cell voltage, anodization time, HF concentration, TiO₂ porous films having different thickness (from 350 to 500 nm) and pore diameter (from 40 to 150 nm) were obtained. By varying the cell voltage from 10 V to 40 V it was possible to gradually change the crystal structure of titanium oxide from anatase to rutile. The effect of annealing temperature and duration on crystal structure was also considered.     

简单两步法制备载银TiO_2纳米管

简单两步法制备载Ag的TiO2纳米管。采用溶胶-凝胶结合水热法制备TiO2纳米管(TiNT),利用传统的"银镜反应",得到表面载Ag的TiO2纳米管(Ag-TiNT)。利用X射线衍射(XRD)、高分辨率透射电镜(TEM)、电子衍射能谱(EDS)对产物进行了表征。结果表明,Ag粒子均匀地分散在纳米管的外表面。从UV-Vis吸收光谱上可以观察到,载银的TiO2纳米管在可见光区域的吸收有了明显提高。     

5A06铝合金阳极氧化和微弧氧化膜绝缘性能研究

采用阳极氧化和微弧氧化方法对5A06铝合金进行表面绝缘化处理,并对试样膜层的形貌、物相、绝缘电阻、漏电流、击穿电压和抗液氮冲击等性能进行了研究.结果表明,5A06阳极氧化膜为非晶相,而微弧氧化膜主要为晶相γ-Al2O3.无论是阳极氧化膜还是微弧氧化膜,干燥条件下的交流和直流击穿电压均较潮湿条件下的高;相同电流模式下,氧...     

Unexpected adsorption of oxygen on TiO2 nanotube arrays: influence of crystal structure

We present kinetics data of O2, n/iso-butane, CO2, and CO adsorbed at ultrahigh vacuum conditions on TiO2 nanotube (TiNTs) arrays produced by electrochemical anodization; amorphous and polycrystalline (anatase and mixed anatase/rutile) TiNTs have been studied addressing structure-activity relationships. Oxygen distinctly interacts with the TiNTs, whereas this process is not observed on fully oxidized TiO2 single crystals. Both molecularly and atomically bonded oxygen have been observed. Variations in the binding energies of alkanes were also detected.     

直流反应溅射TiO2薄膜的制备及其性能研究

采用直流反应磁控溅射的方法,溅射高纯钛靶在ITO石英衬底上制备了TiO2薄膜.用XRD、Raman光谱、AFM和紫外-可见光分光光度计分别测试了TiO2薄膜的结构、表面形貌和紫外-可见光透射谱,研究了工艺因素中溅射气压、氧氩比和退火温度对薄膜结构的影响.采用C(胶)/TiO2/ITO三层结构研究了锐钛矿TiO2薄膜的紫外光响应.实验结果表明较低的溅射气压、合适的氧氩比和较高的退火温度有利于锐钛矿TiO2薄膜的结晶.在2 V的偏压下,锐钛矿TiO2薄膜的紫外光响应上升迟豫时间约为3 s,稳定光电流可达到2.1 mA,对紫外光的灵敏性和稳定的光响应表明TiO2薄膜有可能成为一种新的紫外光探测器材料.     

铜表面电化学制备黑陶质感转化膜的研究

对铜在无硒电化学发黑液中的行为进行了研究.首先通过试验选择NaOH-H3BO3作为缓冲溶液体系,研究了铜在含0.1 mol/L Na2S的缓冲溶液中的循环伏安行为.根据循环伏安曲线上氧化峰的位置,确定铜电化学发黑的适宜电势.然后在不同电势下通过恒电势氧化或循环氧化-还原等方法制备了发黑膜.采用目视和电化学阻抗谱测量等方法,对发黑膜的色度、均一性、致密性和腐蚀防护性能进行了比较.结果表明,循环氧化-还原不能形成性能优良的发黑膜.在-0.8 V和-0.6 V (vs SCE)下形成的发黑膜颜色不均匀,色泽不佳,而在-0.05 V(vs SCE)条件下进行恒电势氧化则可在铜金属表面形成均匀致密、具有黑陶质感的发黑膜.     

Electrical and optical properties of vitreous chalcogenide semiconductor films

Nitrogen-doped tantalum films were deposited by d.c. sputtering in a semicontinuous d.c. diode system. Their electrical properties varied with nitrogen in a similar manner to that generally reported; e.g. the resistivity first decreased from 200 μω cm to a minimum value of 140 μω cm and then increased monotonically. The film density also decreased with increasing nitrogen flow. The films were oxidized both by anodization and by the thermal oxidation in an oxygen atmosphere at 550°C. For a given anodization voltage, the capacitance decreased by approximately 50% when the nitrogen content in the sputtered film reached an estimated 30 at.%. The thermal oxides acted as waveguides for He-Ne light and their refractive indices were strongly dependent on nitrogen concentration. For Ta₂O₅, the indices for TE and TM modes were 2.21 but both decreased by different amounts as the nitrogen concentration increased. For the highest nitrogen concentration, the values for the TE and TM modes were 1.91 and 1.82 respectively. The birefringence must be due to local asymmetry around the Ta atom which is caused by the presence of nitrogen but the mechanism responsible for the ordering in amorphous or randomly oriented micropolycrystalline films is not clear.