Photocatalysts of Cr Doped TiO2 Film Prepared by Micro Arc Oxidation

通过微弧氧化法在Na3PO4+K2Cr2O7电解液中制备了系列铬掺杂二氧化钛薄膜. X射线和扫描电镜显示薄膜的主要晶相为锐钛矿型二氧化钛,且表面为多孔结构. 在可见光照射下,薄膜对降解亚甲基蓝和分解水有着较好的光催化性能,这主要是由铬的掺杂引起的.由于铬的掺杂,一方面在二氧化钛中形成了Cr3+/Cr4+离子对,另一方面在带隙中形成了氧的空位能级. 前者降低了电子-空穴的复合几率,而后者在二氧化钛的禁带中形成了新的能级. 新能级的形成使得由二氧化钛价带跃迁至氧空位能级所需的光子能量减少. 另外探讨了微弧氧化形成掺杂二氧化钛薄膜的机制.     

Synthesis of narrow band gap (V2O5)x-(TiO2)1−x nano-structured layers via micro arc oxidation

V₂O₅-TiO₂ layers with a sheet-like morphology were synthesized by micro arc oxidation process for the first time. Surface morphology and topography of the layers were investigated by scanning electron microscope (SEM) and atomic force microscope (AFM). Phase structure and chemical composition of the layers were also studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. It was revealed that the composite layers had a sheet-like structure average thickness of which was about 100 nm depending on the applied voltage. The layers consisted of anatase, rutile, and vanadium pentoxide phases fractions of which varied with the applied voltage. The optical properties of the layers were also examined employing a UV-vis spectrophotometer. It was found that the absorption edge of the grown composite layers shifted toward the visible wavelengths when compared to MAO-synthesized pure titania layers. The band gap energy of the composite layers was calculated as 2.58 eV. Furthermore, photo-catalytic performance of the layers was examined by measuring the decomposition rate of methylene blue under ultraviolet and visible irradiations. The results demonstrated that about 90% and 68% of methylene blue solution was decomposed after 120 min ultraviolet and visible irradiations over the composite layers, respectively.     

MAO-synthesized Al2O3-supported V2O5 nano-porous catalysts: Growth, characterization, and photoactivity

V₂O₅-loaded Al₂O₃ layers were successfully grown via micro-arc oxidation (MAO) process for the first time. Surface morphology and topography of the layers were investigated by scanning electron microscope (SEM) and atomic force microscope (AFM). It was found that the composite layers had a porous structure with a rough surface which is suitable for catalytic applications. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDS) techniques were also employed to study phase structure and chemical composition of the composite layers. The layers consisted of γ-alumina, α-alumina, and vanadium pentoxide phases in which their relative contents varied with the applied voltage. Meanwhile, optical properties of the composite layers were investigated using UV-vis spectrophotometry technique, and the band gap energy was calculated as 3.15 eV. Furthermore, photocatalytic performance of the synthesized composite layers was determined by measuring the decomposition rate of methylene blue solution, as a model compound, on the surface of the layers under ultra violet photo-irradiation. It was found that more than 91% of the methylene blue was degraded after 120 min with a rate constant of k = 0.0192 min⁻¹.     

Temperature-induced changes in morphology and structure of TiO2-Al2O3 fibers

Electrospinning of a sol-gel and polymer mixture is used to produce titania-alumina (TiO₂-Al₂O₃) fibers with diameters ranging from 200 to 800 nm. These composite metal-oxide fibers were calcined at various temperatures and their morphology is studied using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The decrease in the average diameter of the fibers with increasing temperature is observed. Powder X-ray diffraction (XRD) reveals that up to 800 °C the composite fibers have anatase titania structure whereas at 900 °C the fibers exhibit mixture of anatase and rutile phases. It is found that specific surface area decreases as a function of temperature in the 700-900 °C range. The change in phase (anatase-to-rutile) and the increase in crystallite size occur simultaneously. The presence of smaller amount of amorphous alumina in the primarily titania-based structure seems to play the role in stabilizing the anatase phase.     

Ta2Si short time thermal oxidized layers in N2O and O2 to form high-k gate dielectric on SiC

In this work, we report on two properties of the oxidation of tantalum silicide (Ta₂Si) on SiC substrates making this material of interest as insulator for many wide bandgap or compound semiconductors. The relatively high oxidation rate of tantalum silicide to form high-k insulator layers and its ability for being oxidized in diluted N₂O ambient in a manner similar to the oxidation in O₂ are investigated. Metal-insulator-semiconductor capacitors have been used to establish the actual applicability and constrain of the high-k insulator depending on the oxidation conditions. At 1050 °C, the reduction of the oxidation time from 1 h to 5 min affects primordially the SiO_x interfacial layer formed between the bulk insulator and the substrate. This interfacial layer strongly influences the metal-insulator-semiconductor performances of the oxidized Ta₂Si layer. The bulk insulator basically remains unaffected although some structural differences arise when the oxidation is performed in N₂O.     

Effects of pulse electrodeposition parameters on the properties of Ni-TiO2 nanocomposite coatings

The aim of this study is to investigate the effects of pulse electrodeposition parameters on the properties of nickel-titania composite coatings electrodeposited from a nickel Watts type bath. The effects of average current density, frequency and duty cycle on the surface morphology, crystal size, preferred orientation of the deposits and the amount of embedded nano-TiO₂ particles in the composite coatings were investigated. The results represented the optimum amount of average current density (e.g., 4 A dm⁻²) for obtaining the highest volume percentage of the incorporated titania particles and subsequently the maximum microhardness. Moreover, by increasing the frequency up to 10 Hz while reducing the duty cycle to 10% at constant peak current density, the volume percentage of particles increased to about 7% which is almost twice as much the volume percentage as deposited particles in direct current method. According to the results the composite coating exhibited obviously [1 0 0] + [2 1 1] as preferred orientation at low pulse frequency and the diffraction intensity of the [2 1 1] fiber orientation is increased, probably due to the pH increase adjacent to the electrolyte/cathode interface at higher frequencies. Also, it has been found that by reduction in the duty cycle, more titania particles were incorporated in the composite coatings and this promoted the nickel crystals growth on [1 0 0] planes and consequently the coatings preferred orientation changed from the [2 1 1] to [1 0 0] + [2 1 1] planes.     

Passivation of TiO2 by ultra-thin Al-oxide

The passivation of sol–gel TiO₂ by ultra-thin layers of Al-oxide has been investigated using transient and spectral photovoltage (PV) techniques. The ultra-thin layers of Al-oxide were prepared by the ion-layer gas reaction (ILGAR) technique and modified by thermal treatments in air, vacuum or Ar/H₂S atmosphere. The samples where characterized by elastic recoil detection analysis (ERDA), X-ray photoelectron spectroscopy (XPS), and contact potential difference (CPD) technique. Without an Al-oxide surface layer, electronic states in the forbidden gap of TiO₂ are formed during thermal treatments in vacuum and Ar/H₂S. The trap density is strongly reduced at the TiO₂/Al-oxide interface. The formation of electronic defects is prevented by a closed ultra-thin layer of Al-oxide.     

The comparison of photocatalytic activity of synthesized TiO2 and ZrO2 nanosize onto wool fibers

TiO₂ and ZrO₂ nanocrystals were successfully synthesized and deposited onto wool fibers using the sol-gel technique at low temperature. The photocatalytic activities of TiO₂-coated and ZrO₂-coated wool fibers were measured by studying photodegradation of methylene blue and eosin yellowish dyes. The initial and the treated samples were characterized by several techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS) and X-ray diffraction. The TEM study shows dispersed particles with 10-30 nm in size for TiO₂-coated and 20-40 nm in size for ZrO₂-coated samples on the fiber surface. Comparison of the photocatalytic activity of the coated samples reveals superiority of TiO₂ modified sample with respect to that of ZrO₂ for degradation of both dyes. Our observations indicate that by applying this technique to the fabrics, self-cleaning materials could be designed for practical application.     

In situ formation of Al2O3-SiO2-SnO2 composite ceramic coating by microarc oxidation on Al-20%Sn alloy

In situ formation of Al₂O₃-SiO₂-SnO₂ composite ceramic coating on Al-20%Sn alloy was successfully fabricated in aqueous Na₂SiO₃ electrolyte by microarc oxidation technology. The compositions, structure, mechanical and tribological properties of the composite coating were detailed studied by scanning electron microscope, energy dispersive spectroscopy, X-ray diffraction, hardness tester and ball-on-disc friction tester. It is found that the species originating from the Al-20%Sn alloy substrate and the electrolyte solution both participate in reaction and contribute to the composition of the coating, which results in the generated coating firmly adherent to the substrate. The composite ceramic coating can greatly improve the microhardness and tribological property of Al-20%Sn alloy.     

The synthesis and characterization of Ti/SnO2-Sb2O3/PbO2 electrodes: The influence of morphology caused by different electrochemical deposition time

For the electrochemical oxidative degradation of wastewater, it is crucial for electrodes to be highly catalytic active, stable in performance and inexpensive in price. This study focuses on the preparation of the Ti/SnO₂-Sb₂O₃/PbO₂ anodes by anodic deposition under galvanostatic conditions and their electrocatalytic activity affected by crystal structure and surface roughness under different electrochemical deposition time, with phenol taken as the model pollutant to evaluate the electrocatalytic activity. The electrode surface morphology is characterized by XRD and SEM-EDX. The treatment effect of phenol is reflected by electrochemical analysis like CV and LSV. An important conclusion from experiment is that electrochemical deposition time has a major impact on electrocatalytic activity with the optimal deposition time observed around 30 min. At both deposition time beyond this optimal time window, electrocatalytic activity of phenol is substantially lowered. Increasing in electrochemical deposition time leads to a more uniform and smooth electrode surface, which enjoys a more compact structure than the “cracked-mud” one but lower specific surface area and catalytic activity. On the contrary, the “cracked-mud” structure means potentially a unique porous structure, which makes morphology at 30 min a perfect one for high electrocatalytic activity.     

The effects of SiO2 and TiO2 on the two-phase burning behavior of aqueous HAN propellant

Silica and titania nanoparticles were included at mass loadings of 1% and 3% in aqueous HAN propellants to evaluate their effects on liquid- and gas-phase decomposition and combustion. Both the liquid-phase and overall burning rates of propellant formulations were indirectly measured in a constant-volume strand burner filled with Argon from pressures of 3–22?MPa using a novel, pressure-based method developed by the authors in recent work. This approach provides overall burn times for propellants such as aqueous HAN which continue to burn beyond the disappearance of the liquid, making it superior to methods based solely on visual observation which only monitor the liquid surface regression. The presence of silica nanoparticles increased the liquid-phase burning rate in the low- and medium-pressure regimes (<10?MPa) and increased the overall burning rate at all pressures evaluated. The maximum amount of burning rate enhancement was realized at the lowest evaluated pressure (3?MPa) which corresponded to 80% and 670% increases in the liquid-phase and overall burning rates, respectively, for a silica loading of 1%, and 160% and 830% increases in the liquid-phase and overall burning rates, respectively, for a silica loading of 3%. The presence of titania did not measurably affect the liquid-phase burning rate, but it did increase the overall burning rate in the low-pressure regime (<5.7?MPa). This low-pressure overall burning rate enhancement was not amplified by further titania loading from 1% to 3% and was maximized at the lowest evaluated pressure (3?MPa) which corresponded to a 500% increase in the overall burning rate. The observed enhancements of the propellant's liquid-phase and overall burning rates were attributed to the presence of catalytic processes which diminish at higher pressures. This work represents the first time nanoparticle additives have been utilized to tailor the combustion of liquid HAN-based monopropellants.     

Favorable recycling photocatalyst TiO2/CFA: Effects of loading percent of TiO2 on the structural property and photocatalytic activity

A series of photocatalysts TiO₂/CFA were prepared using coal fly ash (CFA), waste discharged from coal-fired power plant, as substrate, and then these photocatalysts were characterized by scanning electron microscope, X-ray diffraction analysis, nitrogen adsorption test and ultraviolet-visible absorption analysis. The effects of loading percent of TiO₂ on the photocatalytic activity and re-use property of TiO₂/CFA were evaluated by the photocatalytic decoloration and mineralization of methyl orange solution. The results show that the pore volume and the specific surface area of the TiO₂/CFA both increased with the increase in the loading percent of TiO₂, which improved the photocatalytic activity of TiO₂/CFA. However, when the loading percent of TiO₂ was too high (up to 54.51%), superfluous TiO₂ was easy to break away from CFA in the course of water treatment, which was disadvantaged to the recycling property of TiO₂/CFA. In this study, the optimal loading percent of TiO₂ was 49.97%, and the efficiencies of photocatalytic decoloration and mineralization could be maintained above 99% and 90%, respectively, when the photocatalyst was used repeatedly, without any decline, even at the sixth cycle.     

Effect of Ce2(SO4)3 on structure and properties of Ni-Co/Al2O3 composite coating deposited by pulse reverse current method

Composite coating of Ni-Co/Al₂O₃ was deposited in Ce₂(SO₄)₃ containing electrolyte by pulse reverse current (PRC) method. The effect of Ce₂(SO₄)₃ in electrolyte on morphology, microstructure, composition, micro-hardness and residual macrostress of composite coating was investigated. The results indicates that with addition of Ce₂(SO₄)₃ in electrolyte, the composite coating becomes uniform, compact and possesses finer grains, the composite content of Al₂O₃ is enhanced, the micro-hardness of composite coating is improved, while the residual macrostress is decreased.     

Influence of long-term aqueous exposure on surface properties of plasma sprayed oxides Al2O3, TiO2 and their mixture Al2O3-13TiO2

The surface properties of plasma sprayed Al₂O₃- and TiO₂-based coating materials were characterized in order to investigate the influence of surface strain and phase inhomogenity. The materials were water exposed up to 8 months. The bulk crystallographic structure, dissolution behaviour, effective charge (zeta potential, isoelectric point), surface compositions and oxidation states were determined. In addition, the properties of the aging solutions, such as conductivity, supernatant pH (point of zero charge), and redox potential, were monitored during aging.It was shown that the materials were stable under aging conditions, but that considerable surface rearrangements, such as dissolution-reprecipitation and surface site redistributions may occur. However, overall only minor changes in surface properties results from this restructuring process.     

Applying the statistical experimental method to evaluate the process conditions of TiO2 nanotube arrays by anodization method

Vertically oriented TiO₂ nanotube arrays were successfully produced by the anodization technique in NH₄F/H₃PO₄ electrolyte. The structure and morphology were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). It is found that TiO₂ nanotube arrays annealed at 500 °C containing 100% anatase phase and entirely converted into rutile at 800 °C. The response surface methodology (RSM) and Box-Behnken design were applied to find the optimal factor conditions in production of TiO₂ nanotube arrays. Based on the results in preliminary experiments, we selected anodization time, anodization voltage and NH₄F concentration as the key factors to investigate their effects on responses. The regression models were built by fitting the experimental results with a second-order polynomial. By using the regression models, the optimal factor conditions were obtained as follows: anodization time of 300 min; anodization voltage of 15.39 V; NH₄F concentration of 0.50 M. Corresponding to the optimal factor conditions, the predicted average length and diameter of nanotube array were 1429 nm and 33 nm, respectively. Confirmation experiments using the optimized conditions were performed: TiO₂ nanotube arrays were obtained with an average tube length of 1420 nm and average tube diameter of 36 nm. The experimental results are in good agreement with the predicted results.     

Size-dependent microstructure and europium site preference influence fluorescent properties of Eu-doped Ca10(PO4)6(OH)2 nanocrystal

In this study, Eu³⁺-doped nanocrystalline Ca₁₀(PO₄)₆(OH)₂ (Ca_10−xEu_x(PO₄)₆(OH)₂) with different particle sizes have been prepared by the thermal decomposition of precursors. Size-dependent microstructure could be observed in nanocrystalline Ca_10−xEu_x(PO₄)₆(OH)₂. The lattices of Ca_10−xEu_x(PO₄)₆(OH)₂ nanocrystals were more distorted in comparison with the bulk, and the smaller the particle size, the more distorted the lattices. Room temperature photoluminescence showed europium site preference was also size-dependent, with the majority of Eu³⁺ ions occupying Ca(II) sites in the bulk, but more and more Eu³⁺ ions occupying Ca(I) sites in Ca_10−xEu_x(PO₄)₆(OH)₂ with decreasing particle size. Fluorescent properties of Ca_10−xEu_x(PO₄)₆(OH)₂ were considered to be influenced by both microstructure and site preference of Eu³⁺ ions. An abnormal strong intensity of ⁵D₀-⁷F₀ transition was observed in bulk and larger Ca_10−xEu_x(PO₄)₆(OH)₂ nanocrystals, but the relative intensities of ⁵D₀-⁷F₀ transition to ⁵D₀-⁷F_1,2,3,4 transition of Eu³⁺ became weaker as the particle sizes decreased. As the particle sizes became smaller, the ratios of the red emission transition (⁵D₀-⁷F₂) to the orange emission transition (⁵D₀-⁷F₁) (R/O values) first increased by comparing the bulk sample with 96 nm sample, and then decreased by comparing 96 nm sample to 57 nm sample. The quenching concentrations of Ca_10−xEu_x(PO₄)₆(OH)₂ samples increased with decreasing particle size. Possible mechanisms responsible for these phenomena were proposed. Since nanosized Ca_10−xEu_x(PO₄)₆(OH)₂ showed higher fluorescent intensities, higher R/O values and higher quenching concentrations, this material is considered to be a promising phosphor.     

超声场对钛基PbO2电极电化学氧化Cr3+过程电流效率的影响

本文研究了超声场对Ti／SnO2 Sb2O3／PbO2电极电化学氧化Cr3 过程的影响,探讨了在不同的操作电流密度、反应温度、硫酸浓度及Cr3 浓度下,超声场对硫酸介质中Cr3 电化学氧化生成Cr2O72-过程中的电流效率的影响,并用扫描电镜对有无超声场时不同反应时间下的电极形貌进行了分析。实验结果表明:在相同的反应条件下,有超声场作用时Cr3 电化学氧化过程的电流效率明显高于无超声场时的电流效率。扫描电镜测定发现,有超声场作用时不同反应时间下电极的形貌有明显的变化。     

Fabrication of hydroxyapatite and TiO2 nanorods on microarc-oxidized titanium surface using hydrothermal treatment

AC-type microarc oxidation (MAO) and hydrothermal treatment techniques were used to enhance the bioactivity of commercially pure titanium (CP-Ti). The porous TiO₂ layer fabricated by the MAO treatment had a dominant anatase structure and contained Ca and P ions. The MAO-treated specimens were treated hydrothermally to form HAp crystallites on the titanium oxide layer in an alkaline aqueous solution (OH-solution) or phosphorous-containing alkaline solution (POH-solution). A small number of micro-sized hydroxyapatite (HAp) crystallites and a thin layer composed of nano-sized HAps were formed on the Ti-MAO-OH group treated hydrothermally in an OH-solution, whereas a large number of micro-sized HAp crystallites and dense anatase TiO₂ nanorods were formed on the Ti-MAO-POH group treated hydrothermally in a POH-solution. The layer of bone-like apatite that formed on the surface of the POH-treated sample after soaking in a modified simulated body fluid was thicker than that on the OH-treated samples.     

Influence of processing variables on the formation of La2Zr2O7 in transferred arc plasma torch processing

The transferred arc plasma (TAP) torch process has various noteworthy features such as extremely high temperatures, low environmental impact and short processing time which makes it the most suitable technique for synthesizing ceramic composite materials. Furthermore, it is a direct two-step technique which by its virtue of high temperature and power density paves way for high production rate. Hence in this study, an effort has been made to utilize the TAP torch processing technique for the bulk production of La₂Zr₂O₇ with time effectiveness from the mixture of La₂O₃ and ZrO₂ powders (1:2 mol ratios) which were ball milled for 4 h. For this purpose, transferred arc plasma torch was specially designed in laboratory scale level and the operating parameters were optimized in order to achieve maximum La₂Zr₂O₇ formation efficiency. In this study, the phase and microstructure formation of the processed samples was analyzed via X-ray diffraction (XRD) and scanning electron microscope (SEM) images respectively. Moreover, EDX analysis was incorporated to highlight the superior influence of the longer processing time on the stoichiometric ratio of ZrO₂/La₂O₃ in the processed sample as against input power and the gas flow rate.     

Preparation and characteristics of three-layer YSZ-(YSZ/Al2O3)-YSZ TBCs

Novel three-layer YSZ-(YSZ/Al₂O₃)-YSZ (6 wt.% Y₂O₃ partially stabilized ZrO₂) thermal barrier coatings (TBCs) were successfully prepared on Ni-based superalloy substrate using composite sol-gel and pressure filtration microwave sintering (PFMS) techniques. The coatings were evaluated for the cyclic oxidation resistance, thermal barrier effect and the presences of phases and microstructures. FE-SEM results indicate that the coatings were dense and crack-free. The coatings maintained their structural integrity when they were exposed at 1100 for 100 h. They exhibited superior oxidation resistance, spallation resistance and thermal insulation property compared with single-layer YSZ coatings. Moreover, the detailed mechanisms were discussed in order to understand the improved performance of the three-layer TBCs.