Layer-by-layer hybrid films of polyaniline and vanadium oxide

Supramolecular structures of polyaniline (PANI) and vanadium oxide (V2O5) have been assembled via the electrostatic layer-by-layer (LBL) technique. The films were characterized by vibrational analyses which indicated that the interactions between the two components lead to different properties in the films when compared to sol-gel films. of the neat compounds. In particular, using surface enhanced Raman scattering we were able to probe LBL film properties that depend on which material comprises the topmost layer.

A theoretical analysis of the TiO2/Sn doped (110) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO2/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO2 is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sri, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices. (c) 2005 Elsevier B.V. All rights reserved.

The influence of internal surface treatments on tensile bond strength for two ceramic systems

Statement of the Problem: the ceramic composition and surface microstructure of all-ceramic restorations are important components of an effective bonding substrate. Hydrofluoric acid and sandblasting are well-known procedures for surface treatment; however, surface treatment for high alumina-containing and lithium disilicate ceramics have not been fully investigated.Purpose: This in vitro study evaluated the tensile bond strength of resin cement to two types of ceramic systems with different surface treatments.Methods and Materials: Thirty specimens of each ceramic system were made according to the manufacturer's instructions and embedded in polyester resin. Specimens of In-Ceram Alumina [1] and IPS Empress 2 [E] were distributed to three groups with differing surface treatments (n=10): sandblasting with 50 jam aluminum oxide (APA); sandblasting with 110 pm aluminum oxide modified with silica particles (ROCATEC System-RS); a combination of sandblasting with APA and 10% hydrofluoric acid etching (HA) for two minutes on In-Ceram and for 20 seconds for IPS Empress 2. After the respective surface treatments, all the specimens were silanated, and Rely-X resin cement was injected onto the ceramic surface and light polymerized. The specimens were stored in distilled water at 37 degrees C for 24 hours and thermally cycled 1,100 times (5 degrees C/55 degrees C). The tensile bond strength test was performed in a universal testing machine at a 0.5 mm/minute crosshead speed.Results: the mean bond strength values (AWa) for IPS Empress 2 were 12.01 +/- 5.93 (EAPA), 10.34 +/- 1.77 (ERS) and 14.49 +/- 3.04 (EHA). The mean bond strength values for In-Ceram Alumina were 9.87 +/- 2.40 JAPA) and 20.40 +/- 6.27 (IRS). All In-Ceram specimens treated with 10% hydrofluoric acid failed during thermal cycling.Conclusion: the Rocatec system was the most effective surface treatment for In-Ceram Alumina ceramics; whereas, the combination of aluminum oxide sandblasting and hydrofluoric acid etching for 20 seconds worked more effectively for Empress 2 ceramics.

Sintering and crystallite growth of nanocrystalline copper doped tin oxide

The effect of Cu2+ contents and of firing temperature on sintering and crystallite growth of nanocrystalline SnO2 xerogels was analyzed by thermoanalysis (mass loss (TG), linear shrinkage, and differential thermal analysis (DTA)), X-ray powder diffraction (XRPD), and EXAFS (extended X-ray absorption fine structures) measurements. Samples were prepared by two methods: (a) coprecipitation of a colloidal suspension from aqueous solution containing both Sn(IV) and Cu(II) ions and (b) grafting copper(II) species on the surface of tin pride gel. The thermoanalysis has shown that the shrinkage associated with the mass loss decreases by increasing the amount of copper. The EXAFS measurements carried out at the Cu K edge have evidenced the presence of copper in substitutional solid solution for the dried xerogel prepared with 0.7 mol % of copper, while for higher concentration of doping, copper has been observed also at the external surface of crystallites. The solid solution is metastable and copper migrates toward the surface during firing. The XRPD and DTA results have shown a recrystallization process near 320 degrees C, which leads to crystallite growth. The presence of copper segregated near the crystallite surface controls its growth.

Electrochemical stability of anodic titanium oxide films grown at potentials higher than 3 V in a simulated physiological solution

The cathodic behaviour of oxides formed on titanium electrodes in physiological solutions at potentials between 3 and 5 V (vs. SCE) was studied by cyclic voltammetry. In case of anodic polarization at potentials higher than 3 V (vs. SCE), a cathodic peak at similar to 0.4 V (vs. SCE) appears in the cathodic scan, which could be due to the reduction of unstable peroxides. The results show that this peak depends on the anodic potential and the oxidation time. This behaviour supposedly is due to the formation of unstable titanium peroxides like TiO3 during anodization. Based on repetitive oxidation-reduction processes can be concluded that the created amount of TiO3 inside of the TiO2 surface layer seems to be constant. (c) 2006 Elsevier Ltd. All rights reserved.

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.

Theoretical analysis on TiO(2)(110)/V surface

Theoretical analysis based on the Hartree-Fock method were performed in order to study the stoichiometric TiO(2) (110) surface and the vanadium substituted system. The Pople with polarization 3-21G* basis set level was used. The TiO(2) (110) surface was modeled using a (TiO(2))(15) cluster model. In order to take into account the finite size of the cluster, we have studied two different models: the point charge and the hydrogen saturated methodologies. The charge values used in the point charge calculations were optimized. The density of states, orbital self-consistend field (SCF) energies, and Mulliken charge values were analyzed. The method and model's dependence on the analyzed results are discussed. The theoretical results are compared with available experimental data. (C) 2001 John Wiley & Sons, Inc.

SAXS study of formation and growth of tin oxide nanoparticles in the presence of complexing ligands

The effect of acetylacetone (acac) complexing ligand on the formation and growth of tin oxide-based nanoparticles during thermohydrolysis at 70 degreesC of a tin precursor SnCl4-n(acac)(n) (0 less than or equal to n less than or equal to 2) solution was analyzed by in situ small-angle X-ray scattering. A. transparent and stable sol was obtained after 2 h of thermohydrolysis at 70 degreesC, allowing the quantitative determination of the particle volume distribution function and its variation with the reaction time. The number of colloidal particles for equivalent thermohydrolysis temperature and time decreases as the [acac]/[Sn] ratio in initial solution increases from 0.5 to 6. Instead, the amount of soluble species remaining in solution increases for increasing [acac]/[Sn] ratio within the same range. This indicates that increasing amounts of Sn-acetylacetone complexes partially prevent the hydrolysis and consequent formation of colloidal particles. The N-2 adsorption isotherm characterization of freeze-dried powders demonstrates that the average pore size is approximately equal to the average size (approximate to9 Angstrom) of the colloidal primary particles in the sol, and that the porosity and surface area (approximate to200 m(2) g(-1)) are independent of the acac content in the initial solution.

Structural and surface properties of thermally prepared Ti/RhxTi(1-x)Oy electrodes: I - influence of preparation parameters

Electrodes of RhxTi(1-x) O-y nominal composition were prepared by thermal decomposition of the chloride or nitrate precursor salts dissolved in strongly acidic medium and applied by brush to both sides of a Tidegrees support. A systematic study of the influence of calcination temperature and time as well as oxygen flux was conducted. The coatings were characterised by SEM, EDAX, XRD, open circuit potential measurements and cyclic voltammetry (CV). Visible-ultraviolet spectrophotometry was employed to identify the chemical form of the precursor in solution while thermogravimetric analysis (TGA) was used to assess the decomposition temperature ranges. Optimisation of the coating preparation parameters showed coatings obtained from [Rh(H2O)(6)](NO3)(3) precursor dissolved in HNO3 1:2 (v/v) and fired at 430 degreesC for 2 h in a 5 1 min (-1) oxygen stream-furnished stable electrodes having the highest electrochemically active surface area. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Influence of ambient gas on the growth and properties of porous tin-doped indium oxide thin films made by pulsed laser deposition

The laser ablation method was used for depositing porous nanocrystalline indium-tin oxide thin films for gas sensing applications. Samples were prepared at different pressures using three gases (O-2, 0.8N(2):0.2O(2), N-2) and heat-treated in the same atmosphere used for the ablation process. X-ray diffraction results show that the films are not oriented and the grain sizes are in the range between 15 and 40 nm. The grains are round shaped for all samples and the porosity of the films increases with the deposition pressure. The degree of sintering after heat treatment increases for lower oxygen concentrations, generating fractures on the surface of the samples. Film thicknesses are in the range of I pm for all gases as determined from scanning electron microscopy cross-sections. Electrical resistance varies between 36.3 ohm for the film made at 10 Pa pressure in N-2 until 9.35 x 10(7) ohm for the film made at 100 Pa in O-2. (C) 2007 Elsevier B.V. All rights reserved.

Surface protection of fluoroindate glasses by sol-gel dip-coated SnO2 thin layers

SnO2 coatings were deposited by a sol-gel dip-coating process to shield fluoroindate glasses (40In-F-3:16BaF(2):20SrF(2):20ZnF(2):2NaF:2GaF(3)) against corrosion in aqueous environments. The effect of the number of coating applications and of the withdrawal speed on the thickness, density and roughness of tin oxide films was investigated by X-ray reflectivity. Film thickness increases both with the number of coating applications and the withdrawal speed. The aqueous leaching of uncoated and SnO2-coated fluoroindate glasses was studied by scanning electron microscopy (SEM) and infrared spectroscopy (FTIR), showing that the glass surface was protected against hydrolytic attack. (C) 1999 Elsevier B.V. B.V. All rights reserved.

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.

Surface modification of Ti dental implants by Nd: YVO4 laser irradiation

Surface modifications have been applied in endosteal bone devices in order to improve the osseointegration through direct contact between neoformed bone and the implant without an intervening soft tissue layer. Surface characteristics of titanium implants have been modified by addictive methods, such as metallic titanium, titanium oxide and hydroxyapatite powder plasma spray, as well as by subtractive methods, such as acid etching, acid etching associated with sandblasting by either AlO2 or TiO2, and recently by laser ablation. Surface modification for dental and medical implants can be obtained by using laser irradiation technique where its parameters like repetition rate, pulse energy, scanning speed and fluency must be taken into accounting to the appropriate surface topography. Surfaces of commercially pure Ti (cpTi) were modified by laser Nd:YVO4 in nine different parameters configurations, all under normal atmosphere. The samples were characterized by SEM and XRD refined by Rietveld method. The crystalline phases alpha Ti, beta Ti, Ti6O, Ti3O and TiO were formed by the melting and fast cooling processes during irradiation. The resulting phases on the irradiated surface were correlated with the laser beam parameters: the aim of the present work was to control titanium oxides formations in order to improve implants osseointegration by using a laser irradiation technique which is of great importance to biomaterial devices due to being a clean and reproducible process. (c) 2007 Elsevier B.V. All rights reserved.

Rhodamine B-containing silica films from TEOS precursor: Substrate surface effects detected by photoluminescence

This work presents the study of substrate surface effects on rhodamine B-containing silica films obtained from TEOS (tetraethylorthosilicate) acid hydrolysis. Soda-lime glass substrates were treated with basic solution under different reaction times and temperatures. Rhodamine B-containing silica films were deposited on pre-treated substrates by the spin-coating method. The substrate surface directly affects film morphology and homogeneity. The films are formed by packed silica spheres which protect the dye against acid-base attack. Luminescence spectra present shifts on the dye emission maximum as expected for different pH values on the substrate surface depending on the alkaline treatment. (c) 2006 Elsevier B.V. All rights reserved.

XPS study on water corrosion of fluorzirconate glasses and their protection by a layer of surface modified tin dioxide nanoparticles

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, Z-BLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)), and the corrosion protection efficiency of a nanocrystalline transparent SnO2 layer were investigated by X-ray photoelectron spectroscopy. The tin oxide film was deposited by the sol-gel dip-coating process in the presence of Tiron(R) as particle surface modifier agent. The chemical bonding structure and composition of the surface region of coated and non-coated ZBLAN were studied before water contact and after different immersion periods (5-30 min). In contrast to the effects occurring for non-coated glass, where the surface undergoes a rapid selective dissolution of the most soluble species inducing the formation of a new surface phase consisting of stable zirconium oxyfluoride, barium fluoride and lanthanum fluoride species, the results for the SnO2-coated glass showed that the hydrolytic attack induces a filling of the film nanopores by dissolved glass material and the formation of tin oxylluoride and zirconium oxyfluoride species. This process results in a modified film, which acts as a hermetic diffusion barrier protecting efficiently the glass surface. (C) 2006 Elsevier B.V. All rights reserved.