In situ UV-vis and EXAFS studies of ZnO quantum-sized nanocrystals and Zn-HDS formations from sol-gel route

We have pointed Out that. zinc-based particles obtained from zinc acetate sol-gel route is a mixture of quantum-sized ZnO nanoparticles, zinc acetate, and zinc hydroxide double salt (Zn-HDS). Aiming the knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, the thermohydrolysis of ethanolic zinc acetate solutions induced by lithium hydroxide ([LiOH]/[Zn2+] = 0.1) or water ([H2O]/[Zn2+] = 0.05) addition was investigated at different isothermal temperatures (40, 50, 60 and 70 degrees C) by in situ measurements of turbidity, UV-vis absorption spectra and extended X-ray absorption fine structures (EXAFS). Only the growth of ZnO nanoparticles was observed in sol prepared with LiOH, while a two-step process was observed in that prepared with water addition, leading the fast growth of Zn-HDS and the formation of ZnO nanoparticles at advanced stage. A mechanism of dissolution/reprecipitation governed by the water/ethanol proportion is proposed to account for relative amount of ZnO. (c) 2007 Elsevier Ltd. All rights reserved.

Functionalized silica synthesized by sol-gel process

This work considers some aspects of the chemistry involved in the preparation and description of silicon oxide functionalized by sol-gel process. In this work we studied the synthesis and measured the properties of silicon oxide functionalized with 3-chloropropyl, through a sol-gel process. Thermogravimetic analysis, infrared spectra, and elemental analyses were measured. The samples were prepared in the following proportions of tetraethylorthosilicate (TEOS): 3-chloropropyl trimethoxisilane molar ratio: 1:0, 1:1, 2:1, 3:1 and 4:1. The thermogravimetric data for the resulting materials established the 'minimum formulae' 2:0, 3:1, 4.1, 7:1 and 11:1, respectively. As expected, the relative amount of water is inversely proportional to the presence of propyl groups. Infrared data show Si-C and -CH2-vibration modes at 1250 to 1280 and 2920 to 2940 cm(-1), respectively. Thermogravimetric data and infrared spectra showed that inorganic polymers contained organic polymers. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Synthesis of hybrid silicates containing porphyrins incorporated by a sol-gel process and their properties

Porphyrin was incorporated in a silicate network, via a covalent bond, by grafting a functional group with 3-aminopropyltriethoxysilane, using a sol-gel process. We have carried out the synthesis and measured the absorption spectra, nuclear magnetic resonance spectra, infrared (IR) spectra, luminescence spectra and lifetime of these hybrid silicates, porphyrinosilicas. These samples contained the following free-base porphyrins: meso-tetrakis-p-chlorobenzoylporphyrin, meso-tetrakis-2,6-dichloro-3-chlorosulfonylphenylporphyrin. The obtained porphyrinosilicas have similar absorption and luminescence spectra to the free base porphyrins in solution. IR spectra confirm the formation of monomeric species. Lifetime measurement for porphyrinosilica reveals that 32% +/- 2% of porphyrin is covalently bonded to the silica network. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Electron scattering and effects of sources of light on photoconductivity of SnO2 coatings prepared by sol-gel

Electro-optical properties of sol-gel derived 2 mol% antimony or niobium doped tin dioxide films have been measured. The electron density has been calculated considering all the relevant scattering mechanisms and experimental conductivity data measured in the range -197 to 25 degrees C. The results support the hypothesis that both ionised impurity scattering and grain boundary scattering have comparable effects in the resistivity of coatings, for free electron density congruent to 5 x 10(18) cm(-3). We have measured variation of photoconductivity excitation with wavelength using xenon and deuterium lamp as light sources. Results show that the main band in the photoconductivity spectrum is dependent on the spectral light source emission, the excitation peak reaching 5 eV (deuterium lamp). This band is due to the recombination process involving oxygen species and photogenerated electron-hole pairs. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Preparation and characterization of spherical silica-porphyrin catalysts obtained by the sol-gel methodology

This work describes the synthesis of a first-generation iron porphyrin catalyst entrapped in a silica matrix by the sol-gel route, leading to spherical particles. The catalyst was synthesized by the method of Stober, through hydrolysis and condensation of the alkoxysilane TEOS in a mixture of alcohol, water and ammonia, in the presence of the iron porphyrin Fe(TPP)Cl. The relation between particle morphology and catalytic activity of the different Fe(TPP)-SiO2, obtained using different H2O/silane molar ratios and ammonia concentrations in the xerogel syntheses, was studied.The obtained catalysts were characterized by UV-vis spectroscopy, NMR Si-29. thermogravimetric analysis and transmission electron microscopy. Their ability to catalyze (Z)-cyclooctene epoxidation and cyclohexane oxidation was tested using iodosylbenzene as oxygen donor; the oxidation products were analyzed by gas chromatography and the catalysts obtained in a form of particles spherical and monodispersed showed to be a promising catalytic system for selective oxidation. (c) 2005 Elsevier B.V. All rights reserved.

Small angle X-ray scattering study of surface modified tin oxide nanoparticles prepared by sol-gel route

The surface properties of SnO2 nanoparticles were modified by grafting ionic (Tiron (R). (OH)(2)C6H2(SO3Na)(2)(H2O)-H-.) or non-ionic (Catechol (R). C6H4-1,2-(OH)(2)) capping Molecules during aqueous sol-gel processing to improve the redispersibility of powdered xerogel. The effect of the amount of grafted organic molecules on the redispersibility of powders in aqueous solution at several basic pH values was Studied. The nanostructural features of the colloidal suspensions were analyzed by small angle X-ray scattering (SAXS) measurements. Irrespective of the nature and amount of grafted molecules, complete redispersion was obtained in aqueous solution at pH = 13. The redispersion at pH = 11 results in a mixture of dispersed primary particles and aggregates. The proportion of well dispersed nanoparticles and aggregates (and their average size) can be tuned by the quantity of grafted ionic molecules.

Dynamical study of ZnO nanocrystal and Zn-HDS layered basic zinc acetate formation from sol-gel route

We have pointed out that zinc based particles obtained from ethanolic solution of a zinc acetate derivative (zinc oxy-acetate, Zn4O(Ac)(6)) are a mixture of nanometer sized ZnO, zinc oxy-acetate, and zinc hydroxide double salt (Zn-HDS). The knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, and the evolution of Zn species in reaction medium was monitored in situ during 14 h by simultaneous measurements of UV-vis absorption and extended X-ray absorption fine structures (EXAFS) spectra. This spectroscopic monitoring was initialized just after the addition of an ethanolic lithium hydroxide solution ([LiOH]/[Zn] = 0. 1) to the reaction medium kept under controlled temperature (40 degrees C). This study points out the first direct evidence of the reaction between ZnO nanoparticles and unreacted zinc oxy-acetate to form a Zn-HDS phase. The dissolution of ZnO and the reprecipitation of Zn-HDS are induced by the gradual release of water mainly produced by ethanol esterification well evidenced by gas chromatography coupled to mass spectroscopy and FT-IR measurements.

Sol-gel prepared Pt-modified oxide layers: Synthesis, characterization, and electrocatalytic activity

Thin films of pure RuO2 and IrO2 and mixed Ru0.5Ir0.5O2 oxide modified with Pt particles were prepared by a sol-gel method in the form of thin films of similar to 2 mu m thickness on Ti substrates. Surface morphology of these Pt- modified oxides was examined by scanning electron microscopy and was found to exhibit a significant influence of the chemical composition of the oxide matrix. Element mapping showed homogeneous distribution of the metals. X- ray diffraction and X- ray photoelectron spectroscopy analyses showed that these films consist of metallic Pt particles dispersed in an oxide matrix. Cyclic voltammetry in acid solutions showed that the sol- gel prepared layers have relatively high Pt surface areas. The electrocatalytic activity of these materials toward the anodic oxidation of formaldehyde and methanol was compared in terms of onset potential and current density and was found to follow the sequence: Pt- Ru0.5Ir0.5O2/ Ti > Pt- RuO2/ Ti > Pt- IrO2/ Ti.

Microwave synthesis of YAG : Eu by sol-gel methodology

Yttrium-aluminum oxides are interesting compounds and they have been extensively used as host for lasers and phosphors, due to their stable physical and chemical properties. The fabrication of yttrium-aluminum garnet (YAG) has been investigated thoroughly. Single-crystal YAG is expensive and to produce it a new way has been investigated. This process consists of modifying the methodology of reagents mixture and the process of heating them. The microwave irradiation is used to heat-treat the oxide mixture. The traditional synthesis of YAG powders occurs through the reaction of aluminum and yttrium powders at high temperatures. With this work we investigated the preparation of YAG by non-hydrolytic sol-gel route as an alternative methodology to obtain yttrium-aluminum matrix from inorganic precursors (yttrium and aluminum chloride). The preparation of the gel was carried out in an oven-dried glassware. The AlCl3, YCl3 and ethanol were reacted in reflux under argon atmosphere. Europium III chloride was added as a structural probe. The powder was dried and heat-treated in modified microwaves. The samples were pre-treated at 50 and 800 C during I h and then heated in microwaves for 30 s, 2 and 4 min. The formation process and structure of the powders were studied by means of X-ray diffraction (XRD), photoluminescence (PL) and transmission electronic microscopy (TEM). XRD presents only picks corresponding to the YAG phase and confirmed by TEM. PL date showed that the YAG phase was formed in 2 min with the samples pre-treated at 50 C. For the samples pretreated at 800 degrees C, the YAG phase appears in 30s. The excitation spectra present a maximum of 394 nm corresponding to the L-5(6) level and emission spectra of Eu III ion present bands characteristic transitions arising from the D-5(0) -> F-7(J) (J= 1, 2, 3, 4) monifolds excited at their maximum. The magnetic dipole D-5(0) -> F-7(1) transition presents more intensity than the electric dipole D-5(0) -> F-7(2) transition. This methodology showed efficiency in obtaining YAG phase. (c) 2006 Elsevier B.V. All rights reserved.

Localized mechanics of dentin self-etching adhesive system

The bond strength of composite resins (CRs) to dentin is influenced by the interfacial microstructure of the hybrid layer (HL) and the resin tags (TAG). The contemporary self-etching primer adhesive systems overcame the inconvenient of the etch-and-rinse protocol. Studies, however, have demonstrated that HL thickness and TAG length vary according to the wetting time and additional use of acid-etching prior to self-etching primers. This study investigated the localized stress distribution in the HL and the dentin/adhesive interface. Two HL thicknesses (3 or 6 mu m), two TAG lengths (13 or 17 mu m) and two loading conditions (perpendicular and oblique-25 degrees) were investigated by the finite element (FE) analysis. Five two-dimensional FE models (M) of a dentin specimen restored with CR (38 x 64 mu m) were constructed: M1 - no HL and no TAG; M2 - 3 mu m of HL and 13 mu m of TAG; M3 - 3 mu m of HL and 17 mu m of TAG; M4 - 6 mu m of HL and 13 mu m of TAG; and M5 - 6 mu m of HL and 17 mu m of TAG. Two distributed loadings (L) (20N) were applied on CR surface: L1 - perpendicular, and L2 - oblique (25 degrees). Fixed interfacial conditions were assigned on the border of the dentin specimen. Ansys 10.0 (Ansys (R), Houston, PA, USA) software was used to calculate the stress fields. The peak of von Mises (sigma(vM)) and maximum principal stress (sigma(max)) was higher in L2 than in L1. Microstructures (HL and TAG) had no effect on local stresses for L1. Decreasing HL decreased sigma(vM) and sigma(max) in all structures for L2, but the TAG length had influence only on the peributular dentin. The thickness of HL had more influence on the sigma(vM) and sigma(max) than TAG length. The peritubular dentin and its adjacent structures showed the highest sigma(vM) and sigma(max), mainly in the oblique loading.

Microleakage of hydrophilic adhesive systems in Class V composite restorations

Purpose: To investigate the microleakage of four hydrophilic adhesive systems: one multiple-bottles (Scotchbond Multi-Purpose Plus); two one-bottle (Single Bond, Stae); and one self-etching (Etch & Prime 3.0). Materials and Methods: 120 bovine incisor teeth were divided into four groups (n = 30) and Class V cavities were prepared at the cemento-enamel junction. The cavities were restored with the adhesive systems and with Z100 composite. The teeth were thermocycled 1,000 times between 5 +/- 2 degreesC and 55 +/- 2 degreesC with a dwell time of 1 min, and then placed in a 2% methylene blue dye (pH 7.0) for 4 hrs, washed and sectioned vertically through the center of the restorations. The qualitative evaluation was made by three examiners who distributed pre-established scores (0-4) for each tooth using a stereomicroscope at x30 magnification. Results: In enamel margins little microleakage was observed and the Kruskal-Wallis analysis did not show differences. In dentin margins the KruskaI-Wallis and multiple comparison analyses were applied: microleakage was significantly greater with Stae (median 3) and Scotchbond MP Plus (median 4). Single Bond (median 1) and Etch & Prime 3.0 (median 2) showed the best results in dentin margins, and the statistical analysis did not demonstrate differences in microleakage among these groups.