Synthesis of Y2O3:Eu phosphors by bicontinuous cubic phase process

A novel approach for preparation of red-emitting europium-doped yttrium oxide phosphor (Y₂O₃:Eu) by using the bicontinuous cubic phase (BCP) process was reported in this paper. The BCP system was composed of anionic surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and aqueous yttrium nitrate/europium nitrate solution. Energy dispersive spectrometer analysis revealed the homogeneous precipitation occurred in the BCP structure. Thermogravimetric analysis measurements indicated the precursor powder was europium-doped yttrium hydroxide, Y_1−xEu_x(OH)₃. Scanning electron microscopy micrographs showed the precursor powder had a primary size about 30 nm and narrow size distribution. After heat treatment in furnace above 700 °C for 4 h, high crystallinity Y₂O₃:Eu phosphors was obtained. However, the primary size of particles grew to 50–200 nm and the dense agglomerates with a size below 1 μm were formed. X-ray diffraction patterns indicated the crystal structure of precursor powders and Y₂O₃:Eu phosphors were amorphous and body-centered cubic structure, respectively. The photoluminescence analysis showed that the obtained Y₂O₃:Eu phosphor had a strong red emitting at 612 nm and the quenching started at a Eu concentration of 10 mol%. This study indicated that the BCP process could be used to prepare the highly efficient oxide-based phosphors.     

Rheological behavior of alkali-activated metakaolin during geopolymerization

The dynamic rheological behavior of geopolymers, inorganic materials synthesized by activation of an aluminosilicate source by an alkaline solution, is described. The pastes studied were mixtures of an activation solution (alkali + silica) and metakaolin. The influence of the activation solution (NaOH vs. KOH), the silica (Aerosil vs. Tixosil), and the temperature on the evolution of the elastic modulus (G′) and viscous modulus (G′) over time were studied in the linear viscoelastic range. The results show that the nature of the silica has little influence on the viscous and elastic moduli when the geopolymer is activated by KOH, and that the setting time is faster with sodium hydroxide and at higher temperatures regardless of the geopolymer. In addition, during geopolymerization the stepwise variation of the modulus values indicates that the formation of the 3D network occurs in several steps. Moreover, geopolymers activated by potassium hydroxide exhibit slower kinetics but the interactions between constituents are stronger, as the loss tangent (tanδ = G″/G′) is lower. Finally, the maximum loss tangent, tanδ, was also used as a criterion to determine the temperature dependence of the geopolymers synthesized. This criterion is a precursor of the transition to the glassy state. The activation energies could thus be determined for the geopolymers synthesized with potassium hydroxide or sodium hydroxide.     

Influence of precursor concentration on structural,morphological and electrical properties of spray deposited ZnO thin films

Nanostructured ZnO thin films were coated on glass substrate by spray pyrolysis using Zinc acetate dihydrate as precursor. Effect of precursor concentration on structural, morphological, optical and electrical properties of the films was investigated. The crystal structure and orientation of the ZnO thin films prepared with four different precursor solution concentrations were studied and it was observed that, the prepared films are polycrystalline in nature with hexagonal wurzite structure. The peaks are indexed to (100), (002), (101), (102) and (110) planes. Grain size and texture coefficient (TC) were calculated and the grain size found to increase with an increase in precursor concentration. Presence of Zn and O elements was confirmed with EDAX spectra. Optical absorption measurements were carried out in the wavelength region of 380 to 800 nm and the band gap decreases as precursor concentration increases. The current‐voltage characteristics were observed at room temperature and in dark. It was found that for the films deposited at four different precursor concentrations, the conductivity improves as precursor concentration increases. As trimethyl amine TMA is a good marker for food quality discrimination, sensing behavior of the films at an optimized operating temperature of 373 K, towards various concentrations of (TMA) was observed and reported. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rheology of the gelation of fluorine-doped silica sols

Dynamic oscillatory shear measurements are used to probe the gelation kinetics of aqueous sols composed of either particulate silica or silicon alkoxide solution. Unlike steady shear measurements, these dynamic tests do not alter the structure and kinetics of the sol-gel process. The dynamic storage moduli of both systems show sharp transitions at the onset of gelation. However, the gelation kinetics of the two systems are very different; the modulus of alkoxide system remains unchanged until the gel point is reached, whereas that of the particulate system increases with time even below the gel point as the colloid cluster grow. Unlike the alkoxide gel, the particulate gel reverses to a sol upon shearing. The gelation kinetics of a resheared sample is slower than that of a fresh sample. The structures associated with the sol-gel transition for this particulate system have been monitored using freeze fracture microscopy and correlate with rheological observations. The gelation times for both sols are varied by changing the fluoride ion content.     

Morphology and crystal phase evolution of doctor-blade coated CuInSe2 thin films

CuInSe₂ (CIS) chalcopyrite thin films were prepared using a low-cost, non-vacuum doctor-blade coating and the thermal annealing method. An acetone-based precursor solution containing copper chloride, indium chloride, selenium chloride, and an organic binder was deposited onto a Mo-sputtered soda lime glass substrate using a doctor-blade coating method. After coating, the precursor films were annealed in a quartz tube furnace under low vacuum without the use of a Se atmosphere or reduction conditions. Evolution of the morphology, crystal structure, and thermal decomposition behavior of the films was analyzed by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis, and the film formation mechanism was suggested. The as-deposited precursor film gradually decomposed with increase in temperature and formed Cu_2−xSe and In₂Se₃ nuclei on the surface of the film. Incorporation of Cu_2−xSe with In₂Se₃ yielded a chalcopyrite CIS phase, which crystallized on annealing above 400 °C. The obtained CIS film showed low-resistive ohmic behavior with a Mo electrode and a high absorption efficiency for visible–infrared (IR) light, making it suitable for use in photovoltaic applications.     

Multinuclear NMR study of phosphosilicate gels derived from POCl3 and Si(OC2H5)4

Solid state ¹H, ²⁹Si and ³¹P MAS NMR have been used to investigate the microstructure of phosphosilicate gels prepared by a modified sol-gel method involving hydrolysis of silicon precursors in a solely aqueous environment at 50 °C. Gels with molar compositions 5, 10, 20 and 30 mol% P₂O₅ in P₂O₅-SiO₂ were studied. After drying to 400 °C the gels have very similar structures formed by a siloxane framework containing silanol groups and trapped molecules of orthophosphoric acid together with a very small amount, of pyrophosphoric acid. Unlike the gel samples previously synthesized by the hydrolysis of the silicon precursor in alcoholic solution at room temperature, the co-polymerization of phosphorus and silicon is much reduced. Although co-polymerization increases with phosphorus content, it still represents less than 50% of the phosphorus in the 30 mol% P₂O₅ gel. Furthermore there is no evidence for six-coordinated silicon in the glassy matrix.     

Sol–gel derived yttrium doped ZnO nanostructures

Yttrium doped ZnO nanostructures were synthesized at room temperature by sol–gel technique. The sols were prepared using zinc acetate di-hydrate and ethanol as the precursors with yttrium nitrate hexahydrate as the dopant. Lactic acid with water was used as the acidic catalyst to control the hydrolysis reaction. Ammonia was added to vary the pH of the solution and the shape of the nanostructures changed with the change in pH of the solution. The films were deposited on ultrasonically cleaned glass substrates by dip coating technique. X-ray diffraction patterns indicated that the obtained nanostructures were polycrystalline in nature with (1 0 0), (0 0 2) and (1 0 1) reflections of hexagonal ZnO crystal structure. The ZnO films exhibited nanostructures with a rod/lathe like morphology on changing the yttrium concentration. The diameters of the structures varied from 100 nm to 250 nm and the aspect ratio was found to be in the range of 50–70.     

Preparation of CeO2-TiO2 coatings by the sol-gel process

Yellow coatings have been prepared from titanium tetraisopropoxide and cerium chloride by the sol-gel dip-coating process, and the transmittance, chromaticity, thickness and acidic durability of the coating films produced on glass or aluminum were studied. The effects of the pH of the solution on the preparation of the transparent and homogeneous coating films were studied by adding the alkali or acid, and as a result transparent and homogeneous yellow coating films were prepared by dipping the substrate in a solution containing acetic acidic solution. The acidic durability of the aluminum foil was improved by dip-coating the brilliant yellow CeO₂-TiO₂ coating three times.     

Precipitation and characterization of hollow calcite nanoparticles

A method for preparation of significant amount of hollow rhombohedral calcite nanoparticles, based on carbonation of calcium hydroxide suspension, is described. The mineralogical and morphological analyses of the precipitate confirmed the existence of exclusively stable polymorphic modification, calcite, with the mean particle size of about 100 nm and the diameter of the holes observed at the surfaces that are about 50 nm. The analysis of carbonation kinetics pointed out to a complex mechanism of hollow particles formation at high initial supersaturation, that assumed nucleation of amorphous precursor calcium carbonate phase and its solution mediated transformation into nanosized crystalline calcite. The holes obtained at the calcite surfaces are most probably the imprints remained after the dissolution of amorphous calcium carbonate particles.     

溶胶-凝胶法制备纳米ZnO薄膜的结构和光学性质

采用溶胶-凝胶方法制备纳米ZnO薄膜。X射线衍射(XRD)结果表明，薄膜具有六角纤锌矿多晶结构，且随水解时间的增加，粒子尺寸逐渐增大。室温下，观察到近带边紫外发射和较强的可见区(2．45eV)发射。红外吸收光谱研究表明ZnO薄膜表面存在单齿、双齿和桥状结构的醋酸锌副产物，阐述了不同结构醋酸锌副产物对ZnO薄膜可见区发光性质的影响。     

Structural and optical properties of thin films prepared from surface modified ZrO2

This paper describes the preparation and characterization of ZrO₂ thin films deposited on silicon wafer by spin coating method. Nanocrystalline ZrO₂ was synthesized by hydrothermal method using zirconium (IV)-n-propoxide as a precursor material. Surface of the ZrO₂ particles was then modified with 2-acetoacetoxyethyl methacrylate used as a copolymer for coatings. The optical properties, nanostructure and surface morphology of the thin films prepared from surface modified ZrO₂ nanoparticles were examined by optical spectroscopy, X-ray diffraction and scanning electron microscopy, respectively. It was found that the films deposited on silicon wafer have crystalline structure of monoclinic (111) at temperature of 150 °C. It was observed that films depict very dense material that does not present any granular or columnar structure. It was found that optical transparency of thin ZrO₂ films distributed in the range of 30-40 percent in the spectral range 400-800 nm. Refractive index of ZrO₂ films were determined as functions of ZrO₂ content and it was found that the refractive index increases from 1.547 to 1.643 with increased ZrO₂ content.     

Characterisation of semiconducting V2O5–Bi2O3–TeO2 glasses through ultrasonic measurements

Tellurite containing vanadate (50−x)V₂O₅–xBi₂O₃–50TeO₂ glasses with different bismuth (x=0, 5, 10, 15, 20 and 25 wt%) contents have been prepared by rapid quenching method. Ultrasonic velocities (both longitudinal and shear) and attenuation (for longitudinal waves only) measurements have been made using a transducer operated at the fundamental frequency of 5 MHz in the temperature range from 150 to 480 K. The elastic moduli, Debye temperature, and Poisson’s ratio have been obtained both as a function of temperature and Bi₂O₃ content. The room temperature study on ultrasonic velocities, attenuation, elastic moduli, Poisson’s ratio, Debye temperature and glass transition temperature show the absence of any anomalies with addition of Bi₂O₃ content. The observed results confirm that the addition of Bi₂O₃ modifier changes the rigid formula character of TeO₂ to a matrix of regular TeO₃ and ionic behaviour bonds (NBOs). A monotonic decrease in velocities and elastic moduli, and an increase in attenuation and acoustic loss as a function of temperature in all the glass samples reveal the loose packing structure, which is attributed to the instability of TeO₄ trigonal bipyramid units in the network as temperature increases. It is also inferred that the glasses with low Bi₂O₃ content are more stable than with high Bi₂O₃ content.     

The crystallisation of the yttrium–sialon glass: Y15.2Si14.7Al8.7O54.1N7.4

The development of microstructure during crystallisation of a glass with composition Y_15.2Si_14.7Al_8.7O_54.1N_7.4 has been studied by analytical and high resolution transmission electron microscopy. Crystal nucleation at temperatures in the range 965–1050°C occurs by the heterogeneous nucleation of lenticular-shaped yttrium, silicon and aluminium containing crystals on silicon-rich clusters that formed during glass preparation. The lenticular crystals have a wide range of composition after heat treatment at 1050°C; the yttrium cation percentage varies around that of the expected B-phase composition Y₂SiAlO₅N but the aluminium content is lower and the silicon content generally significantly higher than that. The crystals display the hexagonal crystal structure of B-phase, although the results from EDX analysis imply that the atomic arrangement of the lattice is not the previously proposed B-phase structure. Crystal growth during prolonged heat treatment at 1050°C occurs to a significant extent by coalescence.     

Formation and characterization of a SnO2-Al2O3 system derived from a sol-gel process based on different tin precursors

A series of SnO₂-Al₂O₃ samples with SnO₂ to Al₂O₃ molar ratio of 1:1, 0.5:1, 0.25:1 and 0.1:1, have been synthesized by the sol-gel technique using Al(C₃H₇O)₃ and tin (IV) dihydroxy 2,4-pentanedione acetate as precursors. Samples of the above series were characterized by thermal analysis, X-ray diffraction, Fourier transform infrared spectroscopy and nitrogen adsorption to establish their porous structure. The structures of the binary gel systems obtained were found to differ from those of the analogous series in which Sn(ac)₄ (acetic series) was used as precursor. The tin component introduced into the samples of both series was responsible for the narrowing of the range of diameters of the pores (contributing to the highest extent to the cumulative pore volume) relative to their range in pure aluminum gel. The range of the dominant pore diameters was at the same time shifted towards smaller values, but these changes were more pronounced for (ac) series. The use of β-diketonate complexes of tin instead of Sn(ac)₄, leads also to changes in the character of OH group on the surface of the binary gel samples. For this series (acac) of binary gels in the whole range of concentrations of the tin component only one type of hydroxyl groups appears, not present in the monocomponent aluminum gel and in the binary gels of (ac) series.     

Sol-gel processing of TeO2-TiO2-PbO thin films

TeO₂-TiO₂-PbO thin films were prepared by sol-gel processing from tellurium(IV) isopropoxide precursor and their transmittance spectrum was measured, from which the refractive index was calculated. The hydrolysis of tellurium(IV) isopropoxide and the decomposition process of its hydrolysis product were investigated. The discrepancy between the observed hydrolysis behavior of tellurium(IV) isopropoxide and the partial charge model on the reactivity of metal alkoxides toward hydrolysis, being calculated with the Pauling electronegativity, is explained by a combination of the inductive and steric effects of isopropoxide groups and the electronic configuration of the tellurium atom with lone pair electrons.     

The glass transition of Pd40Ni10Cu30P20 studied by temperature-modulated calorimetry

The frequency dependence of the heat capacity in the glass-transition region of Pd₄₀Ni₁₀Cu₃₀P₂₀ was studied by temperature-modulated differential scanning calorimetry (TMDSC) during slow heating and cooling. Such data for low frequencies between 0.1 and 0.01 Hz are not available, especially for metallic glasses. A crossover between mixed static/dynamic and purely dynamic response signals was observed for the lowest frequencies between 1/80 and 1/100 s⁻¹, which allows a direct determination of the average relaxation time at a given cooling rate during the static glass transition. Further, these results were used to evaluate the experimental parameters necessary to truly separate the static and dynamic response in low-frequency modulation calorimetry experiments to obtain the moduli of the dynamic specific heat.     

Physical properties of self-flux and WO3-containing solutions useful for growing type III KGd(PO3)4 single crystals

Density, surface tension and dynamic viscosity of self-flux and WO₃-containing solutions useful for growing type III KGd(PO₃)₄ single crystals have been measured at temperature near the saturation temperature. The thermal behavior of these physical properties has also been studied. Solutions containing WO₃ show a higher density than self-flux solutions and the density decreases linearly when the temperature increases, in the two cases. Near the saturation temperature, self-flux solutions present a surface tension slightly lower than that of WO₃-containing solutions. The dynamic viscosity of WO₃-containing solutions is slightly lower than that of self-flux solutions when this property was measured at the same temperature. We observed that, in WO₃-containing solutions, the saturation temperature is lower than in self-flux solutions. Thus, at the growth temperatures, the two solutions present dynamic viscosities only slightly different, so we expect that the introduction of WO₃ up to 10 mol% in the growth solution does not represent any important improvement in its hydrodynamics and this small change does not compensate for the possibility of introduction of tungsten impurities in the crystal structure affecting the physical properties expected for these crystals. Taking into account the values measured for these physical properties, we choose the initial conditions for growing type III KGd(PO₃)₄ single crystals from self-flux solutions.     

Preparation and physical properties of amorphous V2O5 containing TiO2, Na2O or Li2O

V₂O₅ gels containing up to 18 mol% of TiO₂ were obtained through the simultaneous hydrolysis of alkoxides in ethanol solution. V₂O₅ gels containing Na₂O or Li₂O were obtained through the ion exchange method. The crystallization temperature, T_cr, of the gels increased and the H₂O content of the gels decreased by the addition of TiO₂ or Na₂O. These additives seem to stabilize the amorphous state of the gels. On the other hand, T_cr and the H₂O-content slightly varied with the addition of Li₂O. No ionic polarization was observed in coating films of the gels dried at temperatures below T_cr. The dc conductivity of the films was anisotropic, and increased with the addition of Li₂O or Na₂O. However, it decreased with increasing TiO₂ content. The fiber-like structure of gels was observed by TEM. The gels obtained from alkoxides were thin and short in comparison with the gels obtained through the ion exchange method.     

Structural and optical properties of 6CaO·6SrO·7Al2O3 thin films derived by sol-gel dip coating process

The nanostructured 6CaO·6SrO·7Al₂O₃ (C6S6A7) thin films with cubic structure using calcium, strontium metals, aluminium isopropoxide and ethylene glycol monomethyl ether as stating materials has been fabricated via sol-gel route. Based on hydrolysis of Ca²⁺, Sr²⁺ and Al³⁺ in the sol-gel processing using ethylene glycol monomethyl ether as solvent have been employed as the precursor material. The films were coated on soda lime float glass by the dip coating technique and annealed at 450 °C in air atmosphere. The structure, morphology and composition of the films were investigated by Fourier transformed infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy indicating that the films were composed of C6S6A7 nanoparticles with cubic structure. The spectral transmittance of the films was measured in the wavelength range of 200-1100 nm using an UV-visible spectrometer. It has been found that the optical properties of the films significantly affected by precursor chemistry and annealing temperature due to the improvement of the crystallinity of the films with increasing annealing temperature and became stable when the annealing temperature is higher than 450 °C. The C6S6A7 films annealed at 450 °C had high transparency about 80% in wide visible range.     

Vegetal nanoclusters in hybrid silica films prepared by sol-gel spin coating technique

Hybrid sol-gel films containing Rosemary extract nanoclusters embedded into hybrid silica network have been successfully synthesized using the sol-gel procedure by exploiting the template route, in association with an adequate spin-coating method. Formation of film precursor sols and effect of selected amounts of octyl trimethoxysilane and ethyl oleate succinic anhydride into the starting acid sols on the sol-gel product size have been evaluated by dynamic light scattering technique. The spectral characteristics of hybrid organic-inorganic films have shown that the multiple functional groups from Rosemary extract associated with residual Si-OH groups can cause the increase in the degree of physical interaction. The effect of hybrid sols meaning the silica precursors molar ratio and template concentration on the fluorescence of hybrid films has been also investigated. The fluorescence properties of synthesized films were found to be dependent on template and natural extract concentration. A higher amount of template resulted in doubling the fluorescence intensity in the 400-480 nm domain. The microstructural characteristics of the hybrid films revealed by atomic force microscopy have shown a homogeneous surface morphology with cluster-like structure. Hybrid silica films exhibit a periodic structure with cluster size less than 150 nm.