VPO catalysts synthesized on substrates with modified activated carbons

VPO catalysts were prepared on oxidized and unoxidized activated carbons differing in initial porous structure. Carbons were oxidized under relatively soft (30% H₂O₂, 200 °C) and hard (50% H₂O₂, 350 °C) conditions. Carbon modification was carried out hydrothermally in a traditional autoclave (HTT) or a microwave reactor (MWT). The synthesis was also carried out under hydrothermal (HTS or MWS) conditions. V₂O₅ and NH₄VO₃ were used as precursors. The samples are characterized by diversified porous structure at S_BET = 732-1617 m²/g and V_por = 0.44-0.90 cm³/g, as well as various degree of VPO crystallinity. Possibility of preparation of the VPO catalysts under ecologically appropriate conditions, i.e. in aqueous solutions, was shown.     

Er‐ and Eu‐doped GaP‐oxide porous composites for optoelectronic applications

We demonstrate the controlled preparation of Er‐ and Eu‐doped GaP‐oxide porous composites. The fabrication procedure entails the use of porous semiconductor templates and the impregnation of rare earth ions from a rare earth salt solution in alcohol and thermal treatment. The composites exhibit strong green and red emission that comes from finely dispersed ErPO₄ and EuPO₄ oxide submicron phases in the composite. These materials may prove useful in future generations of optoelectronic and photonic devices. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of nanostructured Ag on porous titania

In this work, porous titania was prepared on bulk Ti by chemical oxidation, and then nanostructured silver (Ag) was deposited on titania surface by ion beam sputtering. After annealing treatment, Ag/TiO₂ composites were characterized using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Results indicated that a nano-porous titania layer with mean pore size of 150 nm and thickness of 1 μm was formed by chemical oxidation at 80 °C for 45 min. There were three Ag species (Ag (0), Ag (1+), and Ag (2+)) on composites surface after annealing treatment, and metallic Ag content achieved maximum value with annealing temperature of 500 °C in air. Ag showed high thermal stability being partly attributed to the inhibiting the diffusion of Ag by the underlying porous titania.     

Formation and bioactivity of porous titania containing nanostructured Ag

In this work, porous titania were prepared on bulk Ti via chemical oxidation, and then nanostructured Ag was deposited on the surface of titania by ion beam sputtering. After annealing treatment, the nanostructured Ag titania were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), electron probe micro-analyzer (EPMA), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The influence of nanostructured Ag on the morphology, grain growth, phase transformation, and bioactivity of titania was investigated.     

Influence of water cavitation peening with aeration on fatigue behaviour of SAE1045 steel

Water cavitation peening (WCP) with aeration is a recent potential method in the surface enhancement techniques. In this method, a ventilation nozzle is adopted to improve the process capability of WCP by increasing the impact pressure, which is induced by the bubble collapse on the surface of components in the similar way as conventional shot peening. In this paper, fatigue tests were conducted on the both-edge-notched flat tensile specimens to assess the influences of WCP on fatigue behaviour of SAE1045 steel. The notched specimens were treated by WCP, and the compressive residual stress distributions in the superficial layer were measured by X-ray diffraction method. The tension-tension (R = S_min/S_max = 0.1, f = 10 Hz) fatigue tests and the fracture surfaces observation by scan electron microscopy (SEM) were conducted. The experimental results show that WCP can improve the fatigue life by inducing the residual compressive stress in the superficial layer of mechanical components.     

Preparation of activated carbons previously treated with hydrogen peroxide: Study of their porous texture

Cedar wood was used as raw material for the preparation of activated carbons by treatment with hydrogen peroxide of different concentrations. The samples were next carbonised and activated under CO₂ atmosphere. The activated carbons were characterised by means of the adsorption isotherms of N₂ at 77 K, as well as by applying the Density Functional Theory (DFT) method and mercury porosimetry. The experimental results corresponding to the activated samples indicate a more remarkable porous development as a consequence of the treatment with hydrogen peroxide, probably due to the elimination of surface complexes produced during the activation step. The DFT diagrams point out that the activating treatment favours the development of medium and narrow-size micropores whereas the carbonisation process leads to the development of wide micropores of size close to that corresponding to mesopores.     

Understanding the solar photo-catalytic activity of TiO2-ITO nanocomposite deposited on low cost substrates

In this work, we report on the photo-catalytic properties of TiO₂-ITO nanocomposite deposited on low cost conventional clay ceramic substrates. The nanocomposite was formed by spraying a solution prepared from the P25 TiO₂ powder (Degussa) mixed with an organometallic paste of a dissolved combination of indium and tin. A TiO₂-ITO powder-like nanocomposite was prepared for X-ray diffraction (XRD) and transmission electron microscopy (TEM) characterization. The mean particle size of the TiO₂-ITO nanocomposite was found to be larger than that of pure TiO₂. The optical features of TiO₂-ITO-based layers (deposited on glass substrates) were investigated using UV-vis spectroscopy. The TiO₂-ITO nanocomposite deposited layers were found to have higher light absorption than the P25 TiO₂ powder. The photo-catalytic properties of the TiO₂-ITO nanocomposite (deposited on low cost clay ceramic substrates) were tested under solar irradiation using a well-known polluting dye. It was shown that the TiO₂-ITO nanocomposite exhibits higher degradation rates towards the pollutant dye than the P25 TiO₂ powder. The optical band gap of the TiO₂-ITO nanocomposite (2.79 eV) was found to be lower than that of pure TiO₂ (3.1 eV), while ITO (indium tin oxide) has a band gap of about 4.2 eV. ITO was found to be entirely transparent to sun light, while it exhibits a slight photo-catalytic activity, signifying the possible existence of an indirect photo-catalysis phenomenon (sensitized semiconductor photocalysis) and potential degradation (oxidation) of the pollutant through electron transfer from the dye to conduction band of the semiconductor. All photo-catalytic activity results were discussed in light of the optical band gap of the various compounds.     

Microwave plasma synthesis of nano‐crystalline YSZ

Nanocrystalline yttria‐stabilized zirconia (YSZ) powder and compacts have been successfully synthesized by microwave plasma synthesis co‐evaporating Y and Zr precursors from a single source. Both liquid and solid mixtures of chemically homologous precursors were tested. Electron micrographs and X‐ray diffraction studies reveal small crystallites in the range 3–4 nm with a narrow size distribution. Crystallite sizes smaller than 25 nm are preserved even after subsequent annealing at temperatures up to 950 °C. A comparison with other gas‐phase synthesis routes of nanocrystalline YSZ is given. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Cathodoluminescence and structural studies of nitrided 3D gallium structures grown by MOCVD

Cathodoluminescence (CL) spectrum imaging and grazing incidence X-ray diffraction (GIXRD) are employed to investigate nitride three-dimensional (3D) gallium structures. The metallic precursors are naturally obtained on a large variety of substrates by metal-organic chemical vapor deposition (CVD) with different shape/size controlled by the growth conditions, especially the temperature. These 3D metallic structures are subsequently exposed to a nitridation process in a conventional CVD reactor to form GaN nanocrystals, as confirmed by GIXRD measurements. CL spectroscopy shows visible light emission (2.5-2.8 eV) excited from the GaN in the 3D structures.     

Effect of the crystallite size in the structural and textural properties of sulfated and phosphated titania

Sulfated and phosphated titania (TiO₂) were obtained by the sol-gel method. The sulfation was prepared in situ using sulfuric acid as hydrolysis catalyst, or by impregnation with ammonium sulphate. Phosphated sol-gel titania was synthesized with phosphoric acid. Long thermal treatments were carried out from 100 to 1000 °C to study the crystallization process of titania. All present phases were nanocrystalline, and the anatase-rutile polymorphic transformation was dependent on the crystallite size of the materials and on the preparation method. The smallest crystallite values were obtained for the phosphated samples. Titania sulfated by impregnation was found to be an efficient and selective catalyst towards propene, whereas di-isopropylether was obtained only in the catalyst prepared in situ with H₂SO₄.     

Consistent determination of photoluminescence quantum efficiency for phosphors in the form of solution, plate, thin film, and powder

We have developed an improved method for easily determining the photoluminescence quantum efficiencies of transparent materials, such as solutions, glass plates, and thin films on a substrate, having various absorbances from ca. 0.05 to 1.0 at the excitation wavelength when reabsorption is negligible. The estimated accuracy for emitting semiconductor nanocrystals is ±5% for solutions. The efficiencies of non-transparent material, such as powder, together with the above-mentioned transparent materials were measured using the traditional integrating sphere method. Comparison of the two values showed that the traditional integrating sphere method usually underestimates the efficiency of powder samples ca. 10-20% depending on the optical density of the powder. This is because the emissions from more than ca. 0.2 mm deep do not leave the powder sample due to internal scattering. We also developed a method to overcome this problem.     

Versatile synthesis of rectangular shaped nanobat-like CuO nanostructures by hydrothermal method; structural properties and growth mechanism

This paper describes a simple and versatile method for growing highly anisotropic rectangular shaped nanobat-like CuO nanostructures by simple, low temperature and cost effective hydrothermal method. Field emission scanning electron microscopy illustrated that these CuO nanostructures have diameter of ∼70 nm, thickness of ∼8 nm and length of ∼174 nm. Structural analysis reveals that the CuO nanostructures have a high crystal quality with monoclinic crystal structure. X-ray photoelectron spectroscopy studies demonstrate that the sample is composed of CuO. The Raman study also indicates the single phase property and high crystallinity of as-grown CuO nanostructures. The plausible growth mechanism for the formation of nanobat-like CuO structure is proposed.     

Morphological and structural characterizations of CrSi2 nanometric films deposited by laser ablation

The structure and morphology of chromium disilicide (CrSi₂) nanometric films grown on 〈1 0 0〉 silicon substrates both at room temperature (RT) and at 740 K by pulsed laser ablation are reported. A pure CrSi₂ crystal target was ablated with a KrF excimer laser in vacuum (∼3 × 10⁻⁵ Pa). Morphological and structural properties of the deposited films were investigated using Rutherford backscattering spectrometry (RBS), grazing incidence X-ray diffraction (GID), X-ray reflectivity (XRR), scanning (SEM) and transmission electron microscopy (TEM). From RBS analysis, the films’ thickness resulted of ∼40 nm. This value is in agreement with the value obtained from XRR and TEM analysis (∼42 and ∼38 nm, respectively). The films’ composition, as inferred from Rutherford Universal Manipulation Program simulation of experimental spectra, is close to stoichiometric CrSi₂. GID analysis showed that the film deposited at 740 K is composed only by the CrSi₂ phase. The RT deposited sample is amorphous, while GID and TEM analyses evidenced that the film deposited at 740 K is poorly crystallised. The RT deposited film exhibited a metallic behaviour, while that one deposited at 740 K showed a semiconductor behaviour down to 227 K.     

Study of the pore size distribution and fractal dimension of HNO3-treated activated carbons

In the present work, the effect of the oxidizing treatment with nitric acid on three activated carbon samples has been studied. The influence of the acid treatment on the surface groups of the different samples has been investigated by means of FT-IR spectroscopy. The pore size distributions of the different samples were determined by means of the HK and DFT methods. The HK method points out a moderate increment of the microporosity due to the action of the nitric acid, whereas the DFT method shows an increase in the microporosity range above 17 Å. Finally, the values of the fractal dimension reveal that the treatment of the samples with nitric acid leads to chemical reactions of a limited extent.     

Characterization of Fe and Fe50Ni50 ultrafine nanoparticles synthesized by inert gas-condensation method

Nanoparticles of Fe and Fe₅₀Ni₅₀ were synthesized by inert gas-condensation method under pure helium atmosphere. The prepared nanoparticles samples were examined by high-resolution transmission electron microscopy, X-ray diffraction and Mössbauer spectroscopy. The synthesized nanoparticles consisted of core-shell type structure nearly spherical shape with a size comprised within the range 4-70 nm and they occur as clusters or chains. The Mössbauer measurements as well as X-ray diffraction showed, in both cases, the presence of iron-oxide phases.     

Interactions of germanium atoms with silica surfaces

GeH₄ is thermally cracked over a hot filament depositing 0.7-15 ML Ge onto 2-7 nm SiO₂/Si(1 0 0) at substrate temperatures of 300-970 K. Ge bonding changes are analyzed during annealing with X-ray photoelectron spectroscopy. Ge, GeH_x, GeO, and GeO₂ desorption is monitored through temperature programmed desorption in the temperature range 300-1000 K. Low temperature desorption features are attributed to GeO and GeH₄. No GeO₂ desorption is observed, but GeO₂ decomposition to Ge through high temperature pathways is seen above 750 K. Germanium oxidization results from Ge etching of the oxide substrate. With these results, explanations for the failure of conventional chemical vapor deposition to produce Ge nanocrystals on SiO₂ surfaces are proposed.     

Growth of AlGaN Epitaxial Film with Chemical Vapour High A1 Content by Metalorganic Deposition

A high-Al-content AlGaN epilayer is grown on a low-temperature-deposited AlN buffer on （0001） sapphire by low pressure metalorganic chemical vapour deposition. The dependence of surface roughness, tilted mosaicity, and twisted mosaicity on the conditions of the AlGaN epilayer deposition is evaluated. An AlGaN epilayer with favourable surface morphology and crystal quality is deposited on a 2Onto low-temperature-deposited AlN buffer at a low V/Ⅲ flow ratio of 783 and at a low reactor pressure of 100 Torr, and the adduct reaction between trimethylaluminium and NH3 is considered.     

Plasma-electrolytic formation, composition and catalytic activity of manganese oxide containing structures on titanium

In the present work, we report the data about formation of TiO₂-rutile or TiO₂ and Mn₂O₃, Mn₃O₄ containing oxide structures on titanium in aqueous electrolytes by means of plasma-electrolytic deposition. The layers formed are characterized by X-ray diffraction, electron probe microanalysis and scanning electron microscopy methods. The PEO coatings on titanium formed in sodium tetraborate solution contain the TiO₂ stabile rutile modification that is important when utilizing such a structure as a catalyst carrier. Manganese acetate adding into the electrolyte leads to formation of layers that contain Mn₂O₃, Mn₃O₄ and TiO₂-rutile in outer region. The manganese content in the surface layer depends on the formation conditions as well as on manganese acetate concentration in the electrolyte. Catalytic activity of the layers in CO → CO₂ reaction is studied in the static and flow conditions. The manganese-containing layers obtained possess the catalytic activity in CO → CO₂ oxidation reaction at the temperature range of 250-350 °C. The catalytic activity depends on the concentration and surface distribution of manganese as well as on the layers morphology.     

3D structure of dendritic and hyper-branched macromolecules by X-ray diffraction

The atomic ordering in dendritic and hyper-branched macromolecules has been determined by X-ray diffraction. The approach of the atomic pair distribution function technique has been used due to the lack of 3D periodicity in these polymeric materials. Dendrimers are found to possess a semi-regular structure riddled with nanosize cavities. The cavities are joined into channels connecting dendrimer's surface and core. In contrast, hyper-branched polymers are rather irregular at the atomic scale and with less accessible interior.     

Room temperature chemical synthesis of lead selenide thin films with preferred orientation

Room temperature chemical synthesis of PbSe thin films was carried out from aqueous ammoniacal solution using Pb(CH₃COO)₂ as Pb²⁺ and Na₂SeSO₃ as Se²⁻ ion sources. The films were characterized by a various techniques including, X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), Fast Fourier transform (FFT) and UV-vis-NIR techniques. The study revealed that the PbSe thin film consists of preferentially oriented nanocubes with energy band gap of 0.5 eV.