球磨纳米TiO2的结构转变

采用X射线衍射研究锐钛矿型纳米TiO2在高能球磨过程中及球磨后的纳米TiO2在退火过程中的结构变化。结果表现在室温常压下高能球磨诱发锐钛矿相转变为金红石相和S相。随着退火温度升高，球磨纳米TiO2粉末的晶粒逐渐长大，锐钛矿相逐渐转变为金红石相，而S相并不直接转变为金红石相而是先转变为锐钛矿相，然后由锐钛矿相转变为金红石相。与未球磨的纳米TiO2相比，高能球磨导致的晶粒细化，显微畸变以及晶格缺陷密度的增加而引起的额外储能使球磨后纳米TiO2的锐钛矿相-金红石相转变温度明显降低。     

Properties of TiO2 film prepared from titanium tetrachloride

The properties of TiO₂ film prepared by titanium tetrachloride were investigated with respect to annealing temperatures in terms of phase change, crystallite size, and band gap energy. The TiO₂ film dried at room temperature exhibited an amorphous phase, while films calcined above 281 and at 990°C displayed anatase TiO₂ and a mixture of anatase and rutile, respectively. The TiO₂ film was transformed to an anatase phase through three stages during the annealing processes: (1) removal of water, (2) decomposition of a peroxo group, and (3) amorphous-anatase phase transformation. It was also found that the bandgap energy of TiO₂ film was changed with increasing annealing temperature. This is attributed to the quantum size effect in the range of 475–675°C and to the formation of rutile phase having lower band gap energy than anatase in the range of 675–990°C.     

Mechanical alloying behavior of Nb–Ti–Si-based alloy made from elemental powders by ball milling process

Nb-Ti-Si-based alloy powders were prepared by mechanical alloying(MA) of elemental particles.The evolutions of morphology,size,phase constituents,crystallite size,lattice strain,composition and internal microstructure,etc.,of the alloy powders were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),energy-dispersive spectroscopy(EDS),laser particle size analyzer and transmission electron microscope(TEM) analyses.The alloy particles are gradually refined and their shapes become globular with the increase in milling time.The diffraction peaks of Nb solid solution(Nbss) phase shift toward lower29 angles during ball milling from 2 to 5 h,and after that Nbss diffraction peaks shift toward higher 29 angles with the increase in milling time from 5 to 70 h,which is mainly attributed to the alteration of the lattice parameter of Nbss powders due to the solution of the alloying element atoms into Nb lattice to form Nbss.During ball milling process,the decrease in crystallite size and increase in lattice strain of Nbss powders lead to continuous broadening of their diffraction peaks.A typical lamellar microstructure is formed inside the powder particles after ball milling for 5 h and becomes more refined and homogenized with the increase in milling time.After 40-h-ball milling,the typical lamellar microstructure disappears and a very homogeneous microstructure is formed instead.This homogeneous microstructure is proved to be composed of only supersaturated Nbss phase.     

Effect of annealing temperature on the structure and optical properties of sputtered TiO2 films

TiO₂ thin films were deposited by DC reactive magnetron sputtering. Some TiO₂ thin films samples were annealed for 5 min at different temperatures from 300 to 900 °C. The structure and optical properties of the films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and ultraviolet-visible (UV-vis) spectrophotometry, respectively. The influence of the annealing temperature on the structure and optical properties of the films was investigated. The results show that the as-deposited TiO₂ thin films are mixtures of anatase and rutile phases, and possess the column-like crystallite texture. With the annealing temperature increasing, the refractive index and extinction coefficient increase. When the annealing temperature is lower than 900 °C, the anatase phase is the dominant crystalline phase; the weight fraction of the rutile phase does not increase significantly during annealing process. As the annealing temperature rises to 900 °C, the rutile phase with the large extinction coefficient becomes the dominant crystalline phase, and the columnar structure disappears. The films annealed at 300 °C have the best optical properties for the antireflection coatings, whose refractive index and extinction coefficient are 2.42 and 8 × 10⁻⁴ (at 550 nm), respectively.     

初始压力对气相爆轰合成纳米二氧化钛纳米颗粒的影响

介绍了利用氢氧混合气体、四氯化钛组成的多元气相系统,爆轰制备纳米二氧化钛粉体的方法。利用XRD分析证明产物为二氧化钛混晶(金红石相和锐钛矿相),晶粒尺度为纳米级。通过XRD、TEM分析可以得出,粒子形状不规则,粒度为20~100nm。研究发现,随着初始压力的增大,金红石相含量增加,纳米颗粒的平均粒度增大,其原因是反应放热的增加和湍流的加强。最后初步探讨了气相爆轰合成纳米二氧化钛粉末的生成机制。     

Microstructural changes of (Ti,W)C solid solution induced by ball milling

The effect of ball milling on microstructural change of (Ti,W)C solid solution was investigated. In addition to the particle size reduction with milling time, detailed studies using the X-ray diffraction line profiles were carried out to evaluate the microstructural parameters, including lattice parameter, crystallite size and microstrain. Nelson–Riley extrapolation and Williamson–Hall method are employed. The results suggest lattice expansion, with the lattice parameter increasing from 4.3212 Ǻ to 4.3241 Ǻ. The defects and surface stress generated during ball milling are deemed to be responsible for the increased d-spacing of (Ti,W)C solid solution with milling time. The crystallite size displays a diminishing trend with increasing milling time, which is consistent with the SEM observation. However, the microstrain developed is tensile in nature and firstly increases with up to 36 h milling, and then the strain reduces for further milling perhaps due to the strain relaxation by the formation of dislocations.     

Low temperature growth of rutile TiO2 films in modified rf magnetron sputtering

Low temperature (≤300°C) growth of rutile TiO₂ films with high refractive index which is equal to bulk TiO₂ crystal was achieved by using a modified sputtering method. Depositions were carried out in rf magnetron sputtering apparatus equipped with an auxiliary permanent magnet just under the grounded electrode. The as-deposited films showed rutile polycrystalline structure and fine surface morphology indicating higher densification. Remarkable changes in composition, total current and energy of incident ions were presented at a Ar–O₂ total pressure of 2.7 Pa. The rutile phase grows in a modified sputtering method in contrast with anatase phase growth in conventional sputtering apparatus.     

Influence of High-Temperature Water Vapor on Titanium Film Surface

This paper describes and analyzes the appearance, phase, and photocurrent of titanium film surfaces after exposure to water vapor at 100–1000 °C. The experimental results show that water vapor at higher than 300 °C can cause measurable oxidation of the titanium surface, and the oxidation product is changed into rutile from anatase in a gradual phase transformation with temperature. In the reaction, the product produced at 500–900 °C is a mixed phase of rutile and anatase. The titanium film surface appearance can change regularly with temperature, and an acicular rutile oxidation product can be produced on the surface at 800 °C. The photocurrent density on titanium surface increases with reaction temperature, and comes to a maximum value at 800 °C. However, with further increase in reaction temperature, the density decreases.     

Synthesis of nano-structured La0.8Ba0.2MnO3 perovskite via a mechano-thermal route

In this study, barium-doped lanthanum manganite, La_0.8Ba_0.2MnO₃, was synthesized via a mechano-thermal route employing high energy ball milling and subsequent heat treatment. The structural evolution, morphology and thermal behaviour of the powders were evaluated using XRD, FESEM, and DTA/TGA, respectively. DTA/TGA results showed that the calcination temperature of the carbonates significantly decreased by increasing the milling time. The results revealed that single phase perovskite was formed at 900 °C in a milled sample for 2 h and this temperature decreased to 600 °C by increasing the milling time to 30 h. The mean crystallite size also decreased from 32 to 20 nm by increasing the milling time from 2 to 30 h. The reaction sequence of La_0.8Ba_0.2MnO₃ formation via the mechano-thermal route is proposed using XRD and DTA/TGA results. FESEM micrographs showed that the mean particle size of the perovskite phase is increased slightly from 30 to 40 nm by increasing the heat treatment temperature from 600 to 900 °C.     

退火工艺对二氧化钛薄膜光催化性能的影响

利用磁控溅射法制备得到二氧化钛薄膜,将薄膜在高温管式炉中分别进行退火,利用XRD、AFM和紫外-可见光谱仪研究了不同温度下退火前后薄膜的晶相结构、光学性能和光催化性能。结果表明,随着退火温度的升高二氧化钛的晶相由锐钛矿向金红石转变,600℃时为两相共存,表面颗粒大小也会有相应变化,锐钛矿相表现出了更好的光催化性能。     

Kinetics of mechanically induced anatase-to-rutile phase transformations under inelastic impact conditions

This work investigates the kinetics of the anatase-to-rutile phase transformation of TiO₂ powders during ball milling. Two elementary stages are observed, namely the transformation of anatase to the TiO₂ II phase and of this latter to rutile. Such consecutive reactions were studied under inelastic impact regimes. Based on a suitable modeling of transformation kinetics, the fraction of powder processed on average at each collision was estimated. The mass of powder involved in phase transformation and microstructural refinement processes at each collision was then worked out by a systematic variation of the powder charge inside the reactor.     

Effect of Nb doping on the phase transition and optical properties of sol-gel TiO2 thin films

Various content Nb-doped TiO₂ thin films were prepared by sol-gel process. XRD analysis shows that the existence of crystalline TiO₂ in anatase and rutile form depends on the Nb content in the examined samples. It is observed that Nb promotes the anatase to rutile phase transition but has a depression effect on the anatase grain growth. It is found that incorporation of about 4 at.% of Nb completely transforms anatase TiO₂ to the rutile form at a calcination temperature as high as 900 °C. The mechanism is proposed. Optical analyses show that the films have an average of 60% transmission in visible region. The energy gap values using Tauc's formula have also been estimated. The band gap of rutile Ti_1−xNb_xO₂ solid solutions increases with increasing x.     

Phase formation of nano-TiO<Subscript>2</Subscript> particles during flame spraying with liquid feedstock

The nanostructured TiO₂ photocatalytic coatings were synthesized through flame spraying with liquid feedstock under different conditions. The nanostructured TiO₂ deposit of substantial anatase phase was annealed at different temperatures. X-ray diffraction analysis showed that significant transformation from anatase to rutile occurred at a temperature above 600 °C. However, thermal analysis suggested that the phase transformation from anatase to rutile started at a temperature from 400 to 500°C. It was found that the grain size of rutile phase was larger than that of anatase. The deposits annealed at temperatures lower than 450°C were photocatalytically active. However, the deposit annealed at 500°C, which contained 95% anatase crystalline, became photocatalytically inactive. Based on the experimental findings, a model is proposed to explain the phase transformation of the nano-TiO₂ particles and the phase formation in flame-spraying of nanostructured TiO₂ deposit with liquid feedstock. The original version of this paper was published as part of the DVS Proceedings: “Thermal Spray Solutions: Advances in Technology and Application,” International Thermal Spray Conference, Osaka, Japan, 10–12 May 2004, CD-Rom, DVS-Verlag GmbH, Düsseldorf, Germany.     

High pressure electrical resistivity studies on Ni-doped TiO2 nanoparticles

Electrical resistivity measurement of Ni-doped TiO₂ nanoparticles were performed under high pressure using a Bridgman opposed anvil setup. It is observed that, anatase phase nanoparticles shows a sudden increase in resistivity below the pressure limit of 4 GPa and is attributed to the transition from anatase to rutile phase. In addition, the transition limit is shifted towards lower pressure region with increase in dopant concentration. But, Ni-doped TiO₂ nanoparticles with rutile phase shows a rapid decrease in resistivity up to 5 GPa and thereafter it becomes constant. Samples with constant resistivity behavior are mainly ascribed to the semiconductor-metallic transformation.     

Thermal stability and magnetic saturation of annealed nickel-tungsten and tungsten milled powders

Crystal structures, microstructures and magnetic saturation of annealed pure W powder along with W-40 wt.% Ni powder mixtures processed by high-energy ball milling were investigated using XRD, DTA, SEM and saturation magnetization techniques. Thermally induced transformations occurred at low temperature annealing. Supersaturated metastable Ni(W) solid solution formed during mechanical milling decomposed during annealing treatment into FCC Ni-rich, FCC W-rich phases and an eta-type phase which was constituted of BCC lattice of W enveloped by two FCC lattices of Ni and W. The structures of the major annealing products were close to Ni₁₀W and W₃Ni₂. The magnetic saturation of the milled W powder and W-Ni mixtures decreased with the increase in annealing temperature. Milling time was more influential on the magnetic properties of the annealed pure W powders.     

Nanocrystalline τ2 phase obtained by mechanical alloying of Al60Fe15Si15Ti10 powder mixture followed by consolidation

In the present work an elemental powder mixture of Al60Fe15Si15Ti10 (at.%) was mechanically alloyed in a high-energy ball mill. A part of the milling product was examined in a calorimeter, while another portion was subjected to consolidation by hot-pressing at 1000 °C for 180 s under a pressure of 7.7 GPa. The results obtained show that a nanocrystalline cubic phase with the lattice parameter a₀ = 11.645 Å, isomorphous with the τ₂ (Al₂FeTi) phase, is formed during mechanical alloying process. Heating of the milling product in the calorimeter up to 720 °C causes limited growth of grains, however the τ₂ phase remains nanocrystalline with the mean crystallite size of 28 nm. Grain growth takes place during consolidation of the milling product as well, although the τ₂ phase remains nanocrystalline with the mean crystallite size of 34 nm. The microhardness of the bulk nanocrystalline sample is 1013 HV0.2 and its open porosity is 0.3%. The results obtained show that the quality of compaction with preserving nanometric grain size of the τ₂ phase is satisfactory and its microhardness is relatively high.     

废弃SCR脱硝催化剂与废NaCl盐焙烧回收催化剂中的钛、钒、钨（英文）

通过废弃选择性催化还原(SCR)脱硝催化剂与废NaCl盐焙烧,可以将催化剂中的钨和钒与钛分离。在最佳浸出条件下(焙烧温度900℃,焙烧时间3 h,废盐与废催化剂的质量比为0.5,浸出温度80℃,反应时间60 min),钨和钒的浸出率分别达到84.63%和66.42%,同时钛的损失率仅为1.3%。废NaCl盐和焙烧温度可以促进锐钛矿型TiO₂转化为金红石型TiO₂,反应后得到了金红石型TiO₂。金红石型TiO₂中的钛的价态为四价,晶格氧和化学吸附氧分别占57.26%和42.74%。该方法可以同时解决2种废弃物的处置问题。     

Crystal structure analysis and thermoelectric properties of p-type pseudo-binary (Al2Te3)x–(Bi0.5Sb1.5Te3)1−x (x = 0 0.2) alloys prepared by spark plasma sintering

Sm³⁺-doped TiO₂ nanocrystalline has been successfully prepared by low temperature combustion synthesis (LCS). Results showed that the samarium doping was found to be able to significantly inhibit the anatase–rutile phase transformation. Photocatalytic degradation experiments indicated that doping samarium ions in TiO₂ could enhance photocatalytic activity in photocatalytic degradation of methylene blue. The increase in photocatalytic activity is probably due to prevention of electron–hole recombination and the existence of a synergistic effect between anatase and rutile. The highest enhancement in photoreactivity was obtained at 0.5 mol% samarium ions doping, which may be in favor of the most efficient separation of the charge carriers. It has been found that the photocatalytic activity is drastically increased under the presence of a small amount of anatase phase (only 5.9% anatase) compared to pure rutile, and the sample calcined at 600 °C with 51.61% rutile shows the highest photocatalytic activity, which suggests the existence of a synergistic effect between anatase and rutile powders in the Sm³⁺-doped TiO₂, which is similar to that of undoped TiO₂.     

Synthesis and characteristics of W-Ni-Fe nano-composite powders prepared by mechanical alloying

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Synthesis of nano-crystalline RuAl by mechanical alloying

Nano-crystalline RuAl was synthesised by mechanical alloying. The evolution of the nano-crystalline RuAl phase during the mechanical alloying process using ruthenium and aluminium powders was studied. During the milling process, the peaks corresponding to reflections from the aluminium planes disappeared. The variation of crystallite size and microstrain with milling time was evaluated using X-ray diffraction (XRD) patterns. though the XRD results showed the formation of a RuAl phase after 7h of milling, scanning electron microscopy studies revealed that the RuAl phase was formed after 2h of milling. The analysis revealed that average crystallite sizes of 17 and 120 nm were obtained for RuAl and Ru phases, respectively, during the milling process. Density value of 97 % of the theoretical value was obtained for the milled powder mixture after cold compaction and sintering.