Improvement of the chemical resistance of zirconium fluoride glasses coated with a Tiron (R) modified tin oxide layer prepared by the sol-gel process

In order to improve the chemical resistance of zirconium fluoride glass a protective transparent SnO2 layer was deposited by the solgel dip-coating process in the presence of Tiron (R) as particle surface modifier agent. After water immersion for different periods of time, both coated and non-coated fluoride glasses were analyzed by scanning electron microscopy, mass loss evaluation, infrared spectroscopy and X-ray photoelectron spectroscopy. In contrast to the effects occurring for non-coated glass, where the surface undergoes a rapid selective dissolution of the most soluble species, the results for the SnO2-coated glass showed that the filling of the film nanopores by dissolved glass material results in a hermetic barrier protecting the glass surface. The selective glass dissolution was confirmed by liquid chromatography measurements of the etching solution after each exposure time. (c) 2006 Elsevier B.V. All rights reserved.

Sol-gel transition in SnO2 colloidal suspensions: viscoelastic properties

This paper describes particle aggregation process during gelation of SnO2 hydrosols. The effect of the concentration of SnO2 colloidal particles on the kinetics of gelation of hydrosols containing PVA (poly(vinyl alcohol)) was analysed by dynamic rheological measurements. The complex viscosity and the storage and loss moduli have been measured during the sol-gel transition and the results correlated to mass fractal growth, nearly linear growth models, and scalar percolation theory. The analysis of the experimental results shows that a linear aggregation occurs in the initial step of the gelation followed by a fractal growth to form a three-dimensional network. Near the gel point this physical gel exhibits the typical scaling expected from an electrical percolation analogy. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Tuning the acidic properties of aluminas via sol-gel synthesis: New findings on the active site of alumina-catalyzed epoxidation with hydrogen peroxide

This study answers several pending questions about alumina-catalyzed epoxidation with aqueous 70 wt% H2O2. To evaluate the effect of the water-to-aluminum tri-sec-butoxide molar ratio, this was systematically changed from 1 to 24. The xerogels were calcined at 450 degrees C and gave different gamma-Al2O3's with distinct textural and acidic properties. A combination of Al-27 MAS NMR and TPD-NH3 results of calcined aluminas allowed us to assign the type la. Al-OH sites as the catalytic sites for epoxidation. The type Ib Al-OH sites have no function in catalytic epoxidation, because ethyl acetate poisons these sites. The strong acid sites of types IIa, IIb, and III Al-OH groups are responsible for the undesired H2O2 decomposition and decreased oxidant selectivity. (c) 2006 Elsevier B.V. All rights reserved.

Transparent and conductive ZnO : Al thin films prepared by sol-gel dip-coating

Aluminum doped zinc oxide polycrystalline thin films (AZO) were prepared by sol-gel dip-coating process. The sol was prepared from an ethanolic solution of zinc acetate using lithium hydroxide or succinic acid as hydrolytic catalyst. The quantity of aluminum in the sol was varied from 1 to 10 mol%. The structural characteristics studied by X-ray diffractometry were complemented by resistivity measurements and UV-Vis-NIR spectroscopy. The films are transparent from the near ultraviolet to the near infrared, presenting an absorption cut-off at almost 290 nm, irrespective of the nature of the catalyst and doping level. The best conductors were obtained for the AZO films containing 3 mol% of aluminum, prepared under acidic and basic catalysis and sintered at 450 degreesC. Their optical band-gap of 4.4 eV calculated from the absorption cut-off is larger than the values for band-gap widening predicted by the standard model for polar semiconductors. These polycrystalline films are textured with preferential orientation of grains along the wurtzite c-axis or the (100) direction. (C) 2003 Elsevier Ltd. All rights reserved.

Sol-gel entrapped cobalt complex

This work describes optimized conditions for preparation of a cobalt complex entrapped in alumina amorphous materials in the form of powder. The hybrid materials, CoNHG, were obtained by a nonhydrolytic sol-gel route through condensation of aluminum chloride with diisopropylether in the presence of cobalt chloride. The materials were calcined at various temperatures. The presence of cobalt entrapped in the alumina matrix is confirmed by ultraviolet visible spectroscopy. The materials have been characterized by X-ray diffraction (XRD), surface area analysis, thermogravimetric analysis (TGA), differential thermal analyses (DTA) and transmission electron microscopy (TEM). The prepared alumina matrix materials are amorphous, even after heat treatment up to 750 degreesC. The XRD, TGA/DTA and TEM data support the increase of sample crystallization with increasing temperature. The specific surface area, pore size and pore diameter changed as a function of the heat treatment temperature employed. Different heat treatment temperatures result in materials with different compositions and structures, and influence their catalytic activity. The entrapped cobalt materials calcined at 750 degreesC efficiently catalyzed the epoxidation of (Z)-cyclooctene using iodozylbenzene as the oxygen donor. (C) 2003 Elsevier B.V. All rights reserved.

Anodic oxidation of formaldehyde on Pt-modified SnO2 thin film electrodes prepared by a sol-gel method

Pt-modified SnO2 electrodes were prepared onto titanium substrates in the form of thin films of similar to2 mum at different temperatures in the range from 200 to 400degreesC. Surface morphology was examined by scanning electron microscopy (SEM). It was found that Pt-SnO2 sol-gel layers are significantly rough and have a low porosity. X-ray diffraction (XRD) studies showed that the films consist of Pt nanoparticles with average size varying from about 5 to 10 nm, depending on the preparation temperature, and amorphous tin oxide. X-ray photoelectron spectroscopy (XPS) was employed to determine the superficial composition of the electrodes and demonstrated the presence of Sn4+ in all the samples. XPS spectra of the Pt 4f electrons showed the presence of Pt in the zero-valence state as well as in ionic forms. The general electrochemical behavior was characterized by cyclic voltammetry in 1 mol l(-1) HClO4 and the electrocatalytic activity towards the oxidation of formaldehyde was investigated by potential sweeps and chronoamperometry. The results obtained show that the Pt-SnO2/Ti system exhibits a significant catalytic activity for the oxidation of formaldehyde, with an onset potential below 0.1 V. (C) 2004 Elsevier Ltd. All rights reserved.

Characterization of an all sol-gel electrochromic device WO3/Ormolyte/CeO2-TiO2

Electrochemical lithium intercalation in thin films of CeO2-TiO2 and WO3, prepared by the sol-gel technique was investigated with cyclic voltammetry and spectroelectrochemical techniques in propylene carbonate solutions. A solid state system having the configuration WO3/Ormolyte/CeO2-TiO2 has been assembled. The solid electrolyte, an organically modified electrolyte (ormolyte), was prepared with different [O]/[Li] ratios. The transmittance variation of this system during a potentiostatic step from -0.7 V to 0.8 V was about 35% at 550 nm.

Preparation and characterization of erbium and ytterbium co-doped sol-gel SiO2 : HfO2 films for planar waveguides

This work reports on the preparation of erbium and ytterbium co-doped SiO2:HfO2 single mode planar waveguides using the sol-gel method. Silica nanoparticles were prepared from tetraethylorthosilicate in basic media and the films were characterized by transmission electron microscopy, scanning electron microscopy, mechanical profilometry, M-lines spectroscopy based on prism coupling technique, X-ray diffractometry, infrared spectroscopy and photoluminescence spectroscopy. The film thicknesses and the refractive indexes were adjusted in order to satisfy a future efficient coupling to single mode optical fiber. Films suitable for both weak and strong light confinement were prepared varying hafnia concentration into the silica matrix. The lifetime values of erbium I-4(13/2) state were measured in order to investigate the influence of clustering and hydroxyl groups on the fluorescence quantum efficiency of the I-4(13/2) level, responsible for the emission at 1.55 mu m attributed to the I-4(13/2) -> I-4(15/2) transition. The high lifetime values suggest the absence of erbium clusters and the elimination of hydroxyl groups by rapid thermal process. (c) 2007 Elsevier B.V. All rights reserved.

Sol-gel Eu3+/Tm3+ doped transparent glass-ceramic waveguides

Eu3+ and Tm3+ doped lanthanum fluoride and lanthanum oxyfluoride are obtained from Eu3+, Tm3+ containing lanthanum fluoracetate solutions. The nature of the crystal phase obtained could be controlled by the temperature of heat treatment. Spectral characteristics of Eu3+ doped crystal phases were sufficiently different to allow utilization of Eu3+ as structural probes. Tm3+ emission at the technologically important spectral region of 1450nm could be observed for the fluoride and oxyfluoride crystal phases. The large bandwidth obtained (around 120nm) suggests potential applications in optical amplification. SiO2-LaF3-LaOF composite materials were also prepared. It is observed that for heat treatments above 800degreesC, fluorine loss, probably in the form of SiF4 hinder the observation of Tm3+ emission. Eu3+ spectroscopic characteristics clearly show the evolution of a fluoride like environment to an amorphous oxide one as the temperature of heat treatment increased. Thin films obtained by dip-coating on V-SiO2 substrates and treated at 300degreesC, 500degreesC and 800degreesC display guided modes in the visible and infrared regions. Optical characteristics (refractive index and films thickness) were obtained at 543.5, 632.8 and 1550nm. Attenuation as low as 1.8dB/cm was measured at 632.8nm. (C) 2004 Published by Elsevier B.V.

Effect of presence of an acid catalyst on structure and properties of iron-doped siloxane-polyoxyethylene nanocomposites prepared by sol-gel

In this work we investigate the effect of hydrochloric acid (HC) addition on the structure and thermal and magnetic properties of iron-doped siloxane-polyoxyethylene (POE) hybrids prepared by the sol-gel route. X-ray powder diffraction (XRD) and X-ray absorption near edge structure (XANES) results reveal the dominance of ferrihydrite nanoparticles and a mixture of this phase with FeCl4- species in the hybrid prepared without and with HCl, respectively. Thermal analysis reveals the existence of two crystalline polymeric phases in the hybrid prepared with HCl whereas hybrids prepared without HCl are amorphous. The 105 and 60 Angstrom sized ferrihydrite nanoparticles were detected by SAXS analysis of the composite prepared without and with HCl, respectively. The magnetic results suggest that in both samples antiferromagnetic nanoparticles coexist with small clusters/isolated ions. In the sample without HCl addition, larger particles dominate the magnetic behavior, while the opposite occurs for the sample prepared using HCl catalyst. (C) 2004 Elsevier B.V. All rights reserved.

Characterization of tin oxide based sol-gel coatings on borosilicate glasses by X-ray reflectivity

The X-ray reflectivity technique was applied in the study of tin oxide films deposited by sol-gel dip-coating on borosilicate glasses. The influence of the withdrawal speed and temperature of thermal treatment on the film structure was analyzed. We have compared the thermal evolution of the density and the shrinkage of the films with these properties measured for the monolithic xerogel by helium picnometry and thermomechanical analysis. In agreement with the Landau-Levich model, the layer thickness increases by increasing the withdrawal speed. Nevertheless, it decreases with the increase of the thermal treatment temperature, due to the densification process. The values of apparent density are smaller than the skeletal density, which shows that the films are porous. The comparison between the film and the monolith indicates that shrinkage during firing is anisotropic, occurring essentially perpendicular to the coating surface.

Density improvement of the sol-gel dip-coated SnO2 films by chemical surface modification

We compare the effect of organic (Tiron (R)) and inorganic (Mn(11)) additives on the low temperature (< 600 degrees C) densification of the sol-gel dip-coated SnO2 films. The structural and compositional properties of the samples were investigated by X-ray reflectometry (XRR), X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The results suggest that the replacement of hydroxyl groups at the particle surface by Tiron (R) reduces the level of agglomeration of the sol, increasing the particles packing and the apparent density of the coatings. Undoped and Mn-doped films drawn from a Tiron (R) containing suspension show after firing at 500 degrees C a porosity reduction of 12 and 8.6%, respectively. The porosity decrease is less pronounced (4.3%) for the film without additives. Both XAS and XPS data show the presence of trivalent manganese. The formation of a non-homogeneous solid solution characterised by the presence of Mn(111) replacing tin atom near to the crystallite surface was evidenced by XAS. Additionally, XPS results reveal the presence of metallic Sn at the surface of films containing Tirono. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of reaction time on the particle size of ZnO and ZnO : Ce obtained by a sol-gel method

In this work particles of ZnO of size range 33-56 Angstrom were prepared by a sol-gel method. The effect of reaction time on the particle size of ZnO or ZnO:Ce was investigated by transmission electron microscopy measurements, UV-vis absorption and luminescence spectroscopy. A linear increase of the mean particle size is observed as a function of reaction time. The cerium-doped particles are bigger than the pure ZnO ones obtained at the same reaction time. A shift to lower energy at the maximum of the bands is observed in all absorption, emission and excitation spectra as a function of particle growth. From the absorption spectra the optical energy gap values (Eg) for these particles were determined. In the quantum size regime, Eg was found to decrease with particle growth.

Study of the selectivity of SnO2 supported membranes prepared by a sol-gel route

In this work the sol-gel process was used to prepare SnO2 supported membranes with an average pore size of 2.5 nm. The effects of salt concentration (NaCl or CaCl2) and of the pH of the aqueous solutions used on the flux and selectivity through the SnO2 membrane were analyzed by permeation experiments and the results interpreted taking account of the zeta potential values determined from the electrophoretic mobility of the SnO2 powder aqueous dispersion. The results show that the ion flux (Na+, Ca2+ and Cl-) throughout the membrane is determined by the electrostatic repulsion among these species and the surface charge at the tin oxide-solution interface.

Nanostructure and luminescent properties of sol-gel derived europium-doped amine functionalised hybrids

The effect of doping by europium triflate on the nanoscopic structure of organic-inorganic hybrid formed by a siliceous network containing pendant amine-terminated propyl chains, called aminosils, was investigated by Small-Angle X-ray Scattering (SAXS). It appears that the composites exhibit a two-level structure. The first level consists of well-condensed cubic-like siloxane octamers, with a radius of gyration around 2 angstrom. The second level is formed by the aggregation of these siloxane nanodomains to form larger structures, in which the nanodomains are spatially correlated and separated by the organic pendant chains. Europium doping inhibits the aggregation between siloxane octamers, leading to a less compact second-level structure. This can be explained by the Eu3+ stop coordination close to the external surface of the siloxane nanodomains, as detected by luminescence spectroscopy.