Structural characterization of the V2O5/TiO2 system obtained by the sol–gel method

The influence of the vanadium load and calcination temperature on the structural characteristics of the V₂O₅/TiO₂ system was studied by X-ray diffraction and X-ray absorption spectroscopy (XAS) techniques. Samples of the V₂O₅/TiO₂ system were prepared by the sol–gel method under acid conditions and calcined at different temperatures. The rutile phase was found to predominate in pure TiO₂ calcined at 450 °C as a result of the reduction of phase transition temperature promoted by the sol–gel method under acid conditions. The anatase phase became predominant at 450 °C as the amount of vanadium increased from 6 to 9 wt%. A structural change in the TiO₂ phase from predominantly anatase to totally rutile with increased calcination temperature was observed in 6 wt% samples. An analysis of the vanadium X-ray Absorption Near Edge Structure (XANES) spectra showed that the oxidation state of vanadium atoms in the samples containing 6 and 9 wt% of vanadium and calcined at 450 °C was predominantly V⁴⁺. However, the presence of V⁵⁺ atoms cannot be ruled out. A qualitative analysis of extended X-ray absorption fine structure (EXAFS) spectra of the samples containing 6 and 9 wt% of vanadium calcined at 450 °C showed that the local structure around vanadium atoms is comparable to that of VO₂ crystalline phase, in which vanadium atoms are fourfold coordinated in a distorted structure. For the sample after calcination at 600 °C, the EXAFS and XANES results showed that a significant portion of vanadium atoms were incorporated in the rutile lattice with a V_xTi_(1−x)O₂ solid solution formation. The conditions of sample preparation used here to prepare V₂O₅/TiO₂ samples associated with different amounts of vanadium and calcination temperatures proved to be useful to modifying the structure of the V₂O₅/TiO₂ system.     

Preparation of phase pure and well-crystallized Li4Ti5O12 nanoparticles by precision control of starting mixture and calcining at lowest possible temperatures

In an attempt to obtain spinel Li₄Ti₅O₁₂ with smallest possible grain size and highest possible phase purity via a solid state route, we tried to elevate reactivity of the reactant mixture by mechanical activation and appropriate choice of the starting materials. From the stoichiometric mixture comprising Li₂CO₃ and 150 nm anatase, we needed to heat at 950 °C for 1 h to obtain 81–88% phase purity (PhP) of Li₄Ti₅O₁₂ with its average grain size ca 600 nm. After mechanical activation with a multi-ring mill for 30 min, 850 °C was enough to obtain 85–87% pure 500 nm spinel. From a combination of LiNO₃ and 50 nm anatase, 90–91% phase pure product with its grain size 240 nm was obtained at 750 °C due to fusion of the nitrate and shorter diffusion path. By using CH₃COOLi.2H₂O and 50 nm anatase we obtained 130 nm Li₄Ti₅O₁₂ with its PhP ca 90% by milling the mixture preliminarily calcined at 500 °C for 1 h and heating subsequently at 700 for 1 h.     

Facile synthesis of nanostructured CuO for low temperature NO2 sensing

Detection of environmental pollutant and health hazardous, nitrogen dioxide (NO₂) is reported using nanostructured CuO particulates (NPs). Powder X-ray diffraction and field emission scanning electron microscopy were used to probe crystalline phase and morphological details, respectively. Small crystallites of ∼10–12 nm and a strain of 4% were found in the leafy structure of CuO. Raman studies further supported the presence of nanosized CuO phase. This is the first instance of utilizing CuO NPs to detect 5 ppm of NO₂ even at a low operating temperature of 50 °C. The highest sensitivity for NO₂ was observed at 150 °C, for the first time, in CuO NPs. A low activation energy of 0.18 eV was found for sensing process. The CuO NPs sensor responded to NO₂ within a few seconds and recovered totally under a minute. The kinetics of the NO₂ gas adsorption on the CuO film surface was described following the Elovich model.     

Enhanced photocatalytic performance of TiO2 particles via effect of anatase–rutile ratio

In the present work anatase–rutile transformation temperature and its effect on physical/chemical properties as well as photocatalytic activity of TiO₂ particles were investigated. The characterisation of the synthesised and annealed TiO₂ particles were determined by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), dynamic light scattering (DLS) and Brunauer–Emmett–Teller surface area analysis (BET). The refraction in the ultraviolet–visible (UV–vis) range was assessed using a dual-beam spectrophotometer. The photocatalytic performance of the particles was tested on methylene blue solution. The XRD data indicated that the percentage of rutile increased with the annealing temperature and almost 100% of anatase transformed to rutile at 1000 °C. In addition, the phase transformation was a linear function of annealing temperature so phase composition of TiO₂ can be controlled by changing the annealing temperature. The SEM and BET results presented the increase of agglomerate size and the decrease of specific surface area with the increasing annealing temperature. This proved that anatase has smaller particle size and higher surface area than rutile. The photocatalytic activity of the annealed TiO₂ powders reduced with the increase of annealing temperature. The samples annealed at 900 °C and 925 °C with anatase: rutile ratio of 92:8 and 77:23, respectively, showed the best activity. These results suggested that the photocatalytic activity of TiO₂ particles is a function of phase composition. Thus it can be enhanced by changing its phase composition which can be controlled by annealing temperature.     

Comparative PEEM and AES study of surface morphology and composition of Cu films on Si and 3C–SiC substrates

We have conducted photoemission electron microscope (PEEM) and Auger electron spectroscopy (AES) studies on the Cu(30 nm)/3C–SiC(1 0 0) and Cu(30 nm)/Si(1 0 0) samples annealed successively up to 850 °C. With PEEM, lateral diffusion of Cu atoms on the 3C–SiC substrate was observed at 400 °C while no lateral diffusion was seen for the Cu/Si(1 0 0) samples up to 850 °C. The 30 nm Cu thin film on 3C–SiC began to agglomerate at 550 °C, similar to the case for the Cu/Si(1 0 0) system. No further spread of the lateral diffusion region was found in subsequent annealing up to 850 °C for Cu/3C–SiC while separated regular-sized dot structures were found at 850 °C for Cu/Si(1 0 0). AES studies of Cu/Si(1 0 0) system showed partial interface reaction during Cu deposition onto the Si(1 0 0) substrate and oxidation of the resultant Cu₃Si to form SiO₂ on the specimen surface at room temperature in air. Surface segregation of Si and C was observed after annealing at 300 °C for Cu/Si(1 0 0) and at 850 °C for the Cu/3C–SiC system. We have successfully elucidated the observed phenomena by combining PEEM and AES considering diffusion of the constituent elements and/or reaction at interfaces.     

Densification and microstructure of lead zirconate titanate ceramics fabricated from a triol sol–gel powder

Lead zirconate titanate (PZT) nano-powder was prepared by a triol sol–gel process. X-ray diffraction and transmission electron microscopy results showed that as-synthesized amorphous powder started to crystallize at the calcination temperature above 500 °C. The crystalline powder was formed into pellets and sintered at temperatures between 900 and 1300 °C. Co-existence of tetragonal and rhombohedral phase was observed in all ceramics. Microstructural investigation of PZT ceramics showed that uniform grain size distribution with average grain size of ∼0.8–2.5 μm were received with sintering temperature up to 1200 °C. Further increasing the temperature caused abnormal grain growth with the grain as large as 13.5 μm. An attempt to optimize densification with uniform grain size distribution was also performed by varying heating rate and holding time during sintering. It was found that dense (∼97%) sol–gel derived PZT ceramic with uniform microstructure was achieved at 1100 °C with a heating rate of 5 °C min⁻¹ and 6 h dwell time.     

Ultrasound with low intensity assisted the synthesis of nanocrystalline TiO2 without calcination

A novel method has been developed for the preparation of nano-sized TiO₂ with anatase phase. Nanoparticles with diameter about 6 nm were prepared at a relatively low temperature (75 °C) and short time. The synthesis was carried out by the hydrolysis of titanium tetra-isopropoxide (TTIP) in the presence of water, ethanol, and dispersant under ultrasonic irradiation (500 kHz) at low intensity. The results show that variables such as water/ethanol ratio, irradiation time, and temperature have a great influence on the particle size and crystalline phases of TiO₂ nanoparticles. Characterization of the product was carried out by different techniques such as powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and UV–vis spectroscopy.     

Anatase TiO2 nanocrystals prepared by mechanochemical synthesis and their photochemical activity studied by EPR spectroscopy

Anatase TiO₂ has been prepared by mechanochemical synthesis using TiOSO₄·xH₂O and Na₂CO₃ as starting reactants. The reaction was performed in high-energy ball mill using steel and corundum jars, respectively. The final products were obtained by annealing the milled powder in the temperature range of 300–700 °C and subsequently by washing out the water-soluble byproduct Na₂SO₄·xH₂O. When steel jars were used, the annealing in the range of 300–600 °C led to anatase. For products milled in corundum, the stability of anatase increased up to 700 °C. Transition electron microscopy (TEM) showed that crystallites with a size in the range of 20–50 nm with equiaxed morphology were obtained after milling in corundum and annealing at 600 and 700 °C. The process of photoinduced reactive hydroxyl radical generation in aerated aqueous titania suspensions was studied by EPR spectroscopy using spin trapping technique. The presence of iron impurities in the samples milled in steel substantially decreases the radical formation. The rate of radical formation is substantially affected by particle size development of TiO₂ nanopowders. The product milled in corundum and annealed at 700 °C outperforms more than twice the photochemical activity of TiO₂ Degussa P25 standard.     

Interaction of water molecules with bare and deuterated polycrystalline diamond surface studied by high resolution electron energy loss and X-ray photoelectron spectroscopies

In this work we study the interaction of water molecules with deuterated and bare polycrystalline diamond surfaces upon exposure to water vapor by X-ray photoelectron spectroscopy (XPS) and high resolution electron energy loss spectroscopy (HR-EELS). To distinguish the molecular origin of hydrogen bonds (i.e. C–H, O–H, C–O–H, etc.) formed on the diamond surface upon interaction with the water molecules, deuterated and hydrogenated gases were used in our experiments. Diamond films were deposited from a deuterated gas mixture to induce C(di)-D surface terminations. Water adsorption on bare diamond surface gives rise to the appearance of well defined and pronounced C–H and C–OH vibrational HR-EELS peaks and an intense O (1s) XPS peak. These chemically adsorbed water fragments survive 300 °C anneal temperature under ultra-high vacuum conditions. Annealing at 600 °C of the water exposed bare diamond surface results in disappearance of the C–OH vibrational modes alongside with a pronounced reduction of the C–H vibrational modes, whilst only upon annealing to ~ 800 °C the O (1s) XPS peak decreased substantially in intensity. We associate these effects with dissociative adsorption of the water molecules on the bare diamond surfaces.Water exposure onto a deuterated surface, on the other hand, does not result in the appearance of the C–OH vibrational peaks but only to an increase of the C–H vibrational HR-EELS mode along side with the appearance of a weaker XPS O (1) peak, as compared to the same experiment, performed on the bare surface. 300 °C anneal significantly diminishes surface oxygen concentration, as monitored by XPS. We associate these results with H₂O decomposition reactions and also with molecular adsorption on deuterated diamond surfaces. Annealing of the water exposed deuterated diamond surface, results in a pronounced decrease and disappearance of the O (1s) XPS peak at a temperature of ~ 800 °C.     

Effect of calcination temperature on phase transformation,structural and optical properties of sol–gel derived ZrO2 nanostructures

Zirconia (ZrO₂) nanostructures of various sizes have been synthesized using sol–gel method followed by calcination of the samples from 500 to 700 °C. The calcined ZrO₂ powder samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infra-red spectroscopy (FT-IR), UV–visible spectroscopy (UV–vis.), Raman spectroscopy (RS) and thermogravimetric analysis (TGA). The phase transformation from tetragonal (t) to monoclinic (m) was observed. The average diameter of the ZrO₂ nanostructures calcined at 500, 600 and 700 °C was calculated to be 8, 17 and 10 nm, respectively. The ZrO₂ sample calcined at 500 °C with tetragonal phase shows a direct optical band gap of 5.1 eV. The value of optical band gap is decreased to 4.3 eV for the ZrO₂ calcined at 600 °C, which contains both tetragonal (73%) and monoclinic (27%) phases. On further calcination at 700 °C, where the ZrO₂ nanostructures have 36% tetragonal and 64% monoclinic phases, the optical band gap is calculated to be 4.8 eV. The enhancement in optical band gap for ZrO₂ calcined at 700 °C may be due to the rod like shape of ZrO₂ nanostructures. The tetragonal to monoclinic phase transformation was also confirmed by analyzing Raman spectroscopic data. The TG analysis revealed that the ZrO₂ nanostructure with dominance of monoclinic phase is found to be more stable over the tetragonal phase. In order to confirm the phase stability of the two phases of ZrO₂, single point energy is calculated corresponding to its monoclinic and tetragonal structures using density functional theory (DFT) calculations. The results obtained by theoretical calculations are in good agreement with the experimental findings.     

InSb grown on Cd0.955Zn0.045Te by liquid phase epitaxy

InSb has been grown by liquid phase epitaxy using indium rich solutions with a supercooling of 2–5 °C onto (1 1 1) oriented Cd_0.955Zn_0.045Te substrates at 400–405 °C. The resulting epitaxial layers were extensively characterized using X-ray diffraction, optical microscopy, Raman spectroscopy and photoluminescence.     

Thermoluminescence,photoluminescence and EPR studies on Mn2+ activated yttrium aluminate (YAlO3) perovskite

Thermoluminescence (TL) measurements were carried out on undoped and Mn²⁺ doped (0.1 mol%) yttrium aluminate (YAlO₃) nanopowders using gamma irradiation in the dose range 1–5 kGy. These phosphors have been prepared at furnace temperatures as low as 400 °C by using the combustion route. Powder X-ray diffraction confirms the orthorhombic phase. SEM micrographs show that the powders are spherical in shape, porous with fused state and the size of the particles appeared to be in the range 50–150 nm. Electron Paramagnetic Resonance (EPR) studies reveal that Mn ions occupy the yttrium site and the valency of manganese remains as Mn²⁺. The photoluminescence spectrum shows a typical orange-to-red emission at 595 nm and suggests that Mn²⁺ ions are in strong crystalline environment. It is observed that TL intensity increases with gamma dose in both undoped and Mn doped samples. Four shouldered TL peaks at 126, 240, 288 and 350 °C along with relatively resolved glow peak at 180 °C were observed in undoped sample. However, the Mn doped samples show a shouldered peak at 115 °C along with two well defined peaks at ～215 and 275 °C. It is observed that TL glow peaks were shifted in Mn doped samples. The kinetic parameters namely activation energy (E), order of kinetics (b), frequency factor (s) of undoped, and Mn doped samples were determined at different gamma doses using the Chens glow peak shape method and the results are discussed in detail.     

Effect of processing temperature on the superconducting properties of acetone doped MgB2 tapes

Correlation of phase formation, critical transition temperature T_c, microstructure, and critical current density J_c with sintering temperature has been studied for acetone doped MgB₂/Fe tapes. Sintering was performed at 600–850 °C for 1 h in a flowing Ar atmosphere. High boron substitution by carbon was obtained with increasing the sintering temperature; however, the acetone doped samples synthesized at 800 °C contain large size MgB₂ grains and more MgO impurities. Incomplete reaction for the acetone doped samples heated at 600 °C result in bad intergrain connectivity. At 4.2 K, the best J_c value was achieved in the acetone doped sample sintered at 700 °C, which reached 24,000 A/cm² at 10 T and 10,000 A/cm² at 12 T, respectively. Our results indicate that the small grain size and less impurity were also important for the improvement of J_c–B properties besides the substitutions of B by C.     

Application of indium tin oxide (ITO) thin film as a low emissivity film on Ni-based alloy at high temperature

Indium tin oxide (ITO) films as the low emissivity coatings of Ni-based alloy at high temperature were studies. ITO films were deposited on the polished surface of alloy K424 by direct current magnetron sputtering. These ITO-coated samples were heat-treated in air at 600–900 °C for 150 h to explore the effect of high temperature environment on the emissivity. The samples were analyzed by X-ray diffraction (XRD), SEM and EDS. The results show that the surface of sample is integrity after heat processing at 700 °C and below it. A small amount of fine crack is observed on the surface of sample heated at 800 °C and Ti oxide appears. There are lots of fine cracks on the sample annealed at 900 °C and a large number of various oxides are detected. The average infrared emissivities at 3–5 μm and 8–14 μm wavebands were tested by an infrared emissivity measurement instrument. The results show the emissivity of the sample after annealed at 600 and 700 °C is still kept at a low value as the sample before annealed. The ITO film can be used as a low emissivity coating of super alloy K424 up to 700 °C.     

ESR spectra and thermal diffusivity of Zn–Al layered double hydroxide

Zn–Al–NO₃–LDH was synthesized using the co-precipitation method at pH 7±0.1 and ratio Zn/Al=4. The heat treatment of LDH was studied by X-ray diffraction (XRD) and thermogravimetric analysis (TGA/DTG) to investigate the stability of the LDH structure. The in situ electron spin resonance (ESR) spectra of fresh LDH from room temperature up to 190 °C were obtained, which are due to the presence of nitrate radicals in LDH interlayer. ESR spectra of sintered LDH below 200 °C (ex situ ESR spectra) were investigated, which are also due to the nitrate radicals. However, at 200 °C and above, spectra were due to the oxygen vacancies of ZnO, which was formed during the thermal treatment of LDH. Thermal diffusivity of LDH as a function of in situ temperatures results in a nonlinear relation, which is due to the changing water content of LDH when temperature increases. However, thermal diffusivity of LDH as a function of sintered temperatures showed a linear relation and the slope of these data demonstrated the dependency between thermal diffusivity and water content of LDH below 200 °C. For temperature above 180 °C, the thermal diffusivity behavior was mainly due to the ZnO phase in LDH.     

Influence of rapid thermal annealing on electrical and structural properties of double metal structure Au/Ni/n-InP (1 1 1) diodes

The effect of rapid thermal annealing on the electrical and structural properties of Ni/Au Schottky contacts on n-InP have been investigated by current–voltage (I–V), capacitance–voltage (C–V), auger electron spectroscopy (AES) and X-ray diffraction (XRD) techniques. The Au/Ni/n-InP Schottky contacts are rapid thermally annealed in the temperature range of 200–500 °C for a duration of 1 min. The Schottky barrier height of as-deposited Ni/Au Schottky contact has been found to be 0.50 eV (I–V) and 0.86 eV (C–V), respectively. It has been found that the Schottky barrier height decreased with increasing annealing temperature as compared to as-deposited sample. The barrier height values obtained are 0.43 eV (I–V), 0.72 eV (C–V) for the samples annealed at 200 °C, 0.45 eV (I–V) and 0.73 eV (C–V) for those at 400 °C. Further increase in annealing temperature to 500 °C the barrier height slightly increased to 0.46 eV (I–V) and 0.78 eV (C–V) compared to the values obtained for the samples annealed at 200 °C and 400 °C. AES and XRD studies showed the formation of indium phases at the Ni/Au and InP interface and may be the reason for the increase in barrier height. The AFM results showed that there is no significant degradation in the surface morphology (rms roughness of 1.56 nm) of the contact even after annealing at 500 °C.     

A spectroscopic ellipsometry study of TiO2 thin films prepared by ion-assisted electron-beam evaporation

Film characterization based on variable-angle spectroscopic ellipsometry (VASE) is desirable in order to understand physical and optical characteristics of thin films. A number of TiO₂ film samples were prepared by ion-assisted electron-beam evaporation with 200-nm nominal thickness, 2.0 Å/s deposition rate and 8 sccm oxygen flow rate. The samples were maintained at 250 °C during the deposition, and annealed in air atmosphere afterwards. As-deposited and annealed films were analyzed by VASE, spectrophotoscopy and X-ray diffractometry. From ellipsometry modeling process, the triple-layer physical model and the Cody–Lorentz dispersion model offer the best results. The as-deposited films are inhomogeneous, with luminous transmittance and band gap of 62.37% and 2.95 eV. The 300 °C and 500 °C are transition temperatures toward anatase and rutile phases, respectively. Increasing temperature results in an increase of refractive index, transmittance percentage and band gap energy. At 500 °C, the highest refractive index and band gap energy are obtained at 2.62 and 3.26 eV, respectively. The developed VASE-modeling process should be able to characterize other TiO₂ films, using similar physical and optical modeling considerations.     

Structural evolution,growth mechanism and photoluminescence properties of CuWO4 nanocrystals

Copper tungstate (CuWO₄) crystals were synthesized by the sonochemistry (SC) method, and then, heat treated in a conventional furnace at different temperatures for 1 h. The structural evolution, growth mechanism and photoluminescence (PL) properties of these crystals were thoroughly investigated. X-ray diffraction patterns, micro-Raman spectra and Fourier transformed infrared spectra indicated that crystals heat treated and 100 °C and 200 °C have water molecules in their lattice (copper tungstate dihydrate (CuWO₄·2H₂O) with monoclinic structure), when the crystals are calcinated at 300 °C have the presence of two phase (CuWO₄·2H₂O and CuWO₄), while the others heat treated at 400 °C and 500 °C have a single CuWO₄ triclinic structure. Field emission scanning electron microscopy revealed a change in the morphological features of these crystals with the increase of the heat treatment temperature. Transmission electron microscopy (TEM), high resolution-TEM images and selected area electron diffraction were employed to examine the shape, size and structure of these crystals. Ultraviolet–Visible spectra evidenced a decrease of band gap values with the increase of the temperature, which were correlated with the reduction of intermediary energy levels within the band gap. The intense photoluminescence (PL) emission was detected for the sample heat treat at 300 °C for 1 h, which have a mixture of CuWO₄·2H₂O and CuWO₄ phases. Therefore, there is a synergic effect between the intermediary energy levels arising from these two phases during the electronic transitions responsible for PL emissions.     

Thermal oxidation-grown vanadium dioxide thin films on FTO (Fluorine-doped tin oxide) substrates

By deposition of metallic vanadium on FTO substrate in Argon atmosphere at room temperature, the sample was then annealed in furnace for 2 h at the temperature of 410 °C in air ambient. (1 1 0) -orientated vanadium dioxide films were prepared on the FTO surface. A maximum transmittance of ∼40% happened at 900–1250 nm region at room temperature. The change of optical transmittance at this region was ∼25% between semiconducting and metallic states. In particular, vanadium dioxide thin films on FTO exhibit semiconductor–metal phase transition at ∼51 °C, the width of the hysteresis loop is ∼8 °C.     

Effect of ultrasound and centrifugal force on carambola (Averrhoa carambola L.) slices during osmotic dehydration

Osmotic dehydration (OD) of carambola slices were carried out using glucose, sucrose, fructose and glycerol as osmotic agents with 70 °Bx solute concentration, 50 °C of temperature and for time of 180 min. Glycerol and sucrose were selected on the basis of their higher water loss, weight reduction and lowers solid gain. Further the optimization of OD of carambola slices (5 mm thick) were carried out under different process conditions of temperature (40–60 °C), concentration of sucrose and glycerol (50–70 °Bx), time (180 min) and fruit to solution ratio (1:10) against various responses viz. water loss, solid gain, texture, rehydration ratio and sensory score according to a composite design. The optimized value for temperature, concentration of sucrose and glycerol has been found to be 50 °C, 66 °Bx and 66 °Bx respectively. Under optimized conditions the effect of ultrasound for 10, 20, 30 min and centrifugal force (2800 rpm) for 15, 30, 45 and 60 min on OD of carambola slices were checked. The controlled samples showed 68.14% water loss and 13.05% solid gain in carambola slices. While, the sample having 30 min ultrasonic treatment showed 73.76% water loss and 9.79% solid gain; and the sample treated with centrifugal force for 60 min showed 75.65% water loss and 6.76% solid gain. The results showed that with increasing in treatment time the water loss, rehydration ratio were increased and solid gain, texture were decreased.