Preparation of ceramic membranes from surface modified tin oxide nanoparticles

The preparation of crack-free SnO2 supported membranes requires the development of new strategies of synthesis capable to allow controlled changes of surface chemistry and to improve the processability of supported layers. In this way, the controlled modification of the SnO2 nanoparticle surface by adding capping molecules like Tiron(R) ((OH)(2)C6H2(SO3Na)(2)) during the sol-gel process was studied, aiming to obtain high performance membranes. Colloidal suspensions were prepared by hydrolyzing SnCl4.5H(2)O aqueous solution with NH4OH in presence of Tiron(R). The effect of the amount of Tiro(R) (from I to 20 wt.%) on the structural features of nanoparticles, powder redispersability and particle-solution interface properties was investigated by X-ray powder diffraction (XRPD), extended X-ray absorption fine structure (EXAFS), quasi-elastic light scattering and electrophoretic mobility measurements. XRPD and EXAFS results showed that the addition of Tiron(R) up to 20 wt.% to colloidal suspensions does not affect the crystallite size of SnO2 primary particles, determined around 2-3 nm. This value is comparable to the hydrodynamic size measured after redispersion of powder prepared with amount of Tiro(R) higher than 7.5 wt.%, indicating the absence of condensation reactions between primary particles after the initial precipitation step. As a consequence the powder with amount of Tiron(R) > 7.5 wt.%, can be fully redispersed in aqueous solution at pH greater than or equal to I I until a nanoparticle concentration of 6 vol.%. The electrophoresis measurements showed a decrease of the isoelectric point by increasing the amount of grafted Tiron(R) at the SnO2 nanoparticle surface, resulting in negatively charged particle-solution interface in all the studied pH range (2-11). These features govern the gelation process favoring the preparation of crack-free SnO2 supported membranes. The control exercised by Tiron(R) modifying agent in the aggregation process allows the fine-tuning of the porosity, from 0.124 to 0.065 cm(3) g(-1), and mean pore size, from 6.4 to 1.9 nm, as the amount of grafted molecules increases from 0 to 10 wt.%. In consequence, the membrane cut-off determined by filtration of polyethylene glycol standard solutions can be screened from 1500 to 3500 g mol(-1). (C) 2002 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.

Pyrosol preparation and structural characterization of SnO2 thin films

Polycrystalline tin oxide thin films were prepared from ethanol solution of SnCl2.H2O (concentrations: 0.05, 0.1, 0.2 and 0.4 mol/dm(3)) at different substrate temperatures ranging from 300 to 450 degreesC. The kinetic deposition processes were studied in terms of various process parameters. The crystal phases, crystalline structure, grain size and surface morphology are revealed in accordance to X-ray diffractometry and scanning electron microscopy (SEM). Texture coefficients (TCs) for (110), (2 0 0), (2 11) and (3 0 1) reflections of the tetragonal SnO2 were calculated. Structural characteristics of deposited films with respect to varying precursor chemistry and substrate temperature are presented and discussed. (C) 2003 Published by Elsevier B.V.

Polyol-mediated synthesis of ultrafine tin oxide nanoparticles for reversible Li-ion storage

A simple, cheap and versatile, polyol-mediated fabrication method has been extended to the synthesis of tin oxide nanoparticles on a large scale. Ultrafine SnO2 nanoparticles with crystallite sizes of less than 5 nm were realized by refluxing SnCl2 . 2H(2)O in ethylene glycol at 195 degrees C for 4 h under vigorous stirring in air. The as-prepared SnO2 nanoparticles exhibited enhanced Li-ion storage capability and cyclability, demonstrating a specific capacity of 400 mAh g(-1) beyond 100 cycles. (c) 2006 Elsevier B.V. All rights reserved.

Low voltage electroluminescence of terbium- and thulium-doped zinc oxide films

Strong interest in developing technology for visual information. stimulates research for thin film electroluminescent devices. Here, for the first time, we report that thulium- and terbium-doped zinc-oxide films are suitable for electroluminescence applications. Two different devices were assembled as lTO/LiF/ZnO:RE/LiF/Al or ITO/SiO2/ZnO:RE/SiO2/Al, where ZnO:RE is a film of zinc oxide containing 10 at% of Tb3+ or Tm3+. Electroluminescence spectra show that besides a broad emission band with maximum around 650 nm assigned to ZnO, also emission lines from Tb3+ at 484 nm (D-5(4) -> F-7(6)), 543 nm (D-5(4) -> F-7(6)), and 589 nm (D-5(4) -> F-7(4)), or from Tm3+ at 478 nm ((1)G(4) -> H-3(6)), and 511 mn (D-1(2) -> H-3(5)) were detected. Intensity of emission as function of applied voltage and current-voltage characteristic are shown and discussed. (c) 2005 Elsevier B.V. All rights reserved.

Wettability and photodegradation activity of sol-gel dip-coated zinc oxide films

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Tin oxide nanoparticle formation using a surface modifying agent

This work presents results concerning the preparation of redispersible tin oxide nanoparticles achieved by using Tiron molecule ((OH)(2)C(6)H(2) (SO(3)Na)(2)) as surface modifying agent. The adsorption isotherm measurements show that an amount of 10 wt.% of Tiron is need to recover the SnO(2) nanoparticles surface with a monolayer. These nanoparticles can be easily redispersed in tetramethyl ammonium hydroxide at pH greater than or equal to11 until a powder concentration of 12 vol.% of tin. Under these conditions, hydrodynamic particle size is about 7 nm and increases until 52 nm at pH 6 due to the aggregation phenomenon. The time evolution of the viscoelastic properties indicates that the suspensions at pH 12.5, containing 12 vol.% tin oxide and 10 wt.% of surface modifier are kinetically stable. After thermal treatment at different temperature the powder characterisation evidences that the presence of Tiron monolayer at the nanoparticles surface increases the thermal stability of the porous texture and prevent the micropore size growth. This set of results contributes to satisfy the demand for more controlled synthesis of nanoparticles with high thermal stability as required for fabrication of ultrafiltration ceramic membranes. (C) 2004 Elsevier Ltd. All rights reserved.

Influence of the morphology and microstructure on the photocatalytic properties of titanium oxide films obtained by sparking anodization in H3PO4

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Controlled growth of anodic aluminium oxide films with hexagonal array of nanometer-sized pores filled with textured copper nanowires

Anodic aluminium oxide (AAO) films exhibiting a homogeneous morphology of parallel pores perpendicular to the surface were prepared in a two-step anodization process and filled with copper by electrochemical deposition. The optimum growth conditions for the formation of freestanding AAO films with hexagonal compact array of cylindrical pores were studied by field emission scanning electron microscopy and small angle X-ray scattering. The results show well-defined periodic structures with uniform pores size distribution for films with pore diameters between 40 and 70 nm prepared using different voltages and temperatures during the second anodization step. X-ray photoelectron spectroscopy and X-ray diffraction analysis of AAO films filled with copper show the formation of nanowires with high structural order, exhibiting a preferential crystalline orientation along the (2 2 0) axis and only small fraction of copper oxides. The best results for textured Cu nanowires were obtained at a reduction potential of -300 mV. (C) 2009 Elsevier Ltd. All rights reserved.

Bacterial cellulose membrane as flexible substrate for organic light emitting devices

Bacterial cellulose (BC) membranes produced by gram-negative, acetic acid bacteria (Gluconacetobacter xylinus), were used as flexible substrates for the fabrication of Organic Light Emitting Diodes (OLED). In order to achieve the necessary conductive properties indium tin oxide (ITO) thin films were deposited onto the membrane at room temperature using radio frequency (r.f) magnetron sputtering with an r.f. power of 30 W, at pressure of 8 mPa in Ar atmosphere without any subsequent thermal treatment. Visible light transmittance of about 40% was observed. Resistivity, mobility and carrier concentration of deposited ITO films were 4.90 x 10(-4) Ohm cm, 8.08 cm(2)/V-s and -1.5 x 10(21) cm(-3), respectively, comparable with commercial ITO substrates. In order to demonstrate the feasibility of devices based on BC membranes three OLEDs with different substrates were produced: a reference one with commercial ITO on glass, a second one with a SiO(2) thin film interlayer between the BC membrane and the ITO layer and a third one just with ITO deposited directly on the BC membrane. The observed OLED luminance ratio was: 1; 0.5; 0.25 respectively, with 2400 cd/m(2) as the value for the reference OLED. These preliminary results show clearly that the functionalized biopolymer, biodegradable, biocompatible bacterial cellulose membranes can be successfully used as substrate in flexible organic optoelectronic devices. (C) 2008 Elsevier B.V. All rights reserved.

Effect of atmosphere on the sintering and grain growth of tin oxide

High purity SnO 2 powder (>99.9%) was compacted in cylindrical pellets and sintered in atmospheres of dry argon, argon with water vapor, oxygen and CO 2 using 10 °C/min up to 1200 °C or isotherms in the range of 1000 to 1200 °C. Time, temperature and sintering atmosphere have large influence on grain growth and low influence on densification of this oxide. Surface diffusion is the dominant mechanism up to 1200 °C and evaporation-condensation is dominant above 1200 °C. The maximum linear shrinkage observed was about 2.0% and attributed to structural rearrangement of particles due to high capillary stresses developed with neighboring particles. © 1999 Trans Tech Publications.

Sintering of tin oxide processed by slip casting

Sintering of SnO 2 compacts, obtained through slip casting, was studied by means of dilatometry, Hg porosimetry, scanning electron microscopy, and density measurement (Archimedes method). Sintering is strongly influenced by the green microstructure. Moreover, the sintering mechanisms are not dependent on the slurries' solid content up to 50% of solids in volume. Above this value, agglomerates are formed, leading to differential sintering inside and among the agglomerates. Another important point is the reduction of the temperature of maximum shrinkage rate when compared to tin oxide processed by isostatic pressing. This reduction is more accentuated when ammonium hydroxide is added to the suspension. (C) 2000 Published by Elsevier Science Ltd. All rights reserved.

An improved three-dimensional model for growth of oxide films induced by laser heating

In this paper we consider a three-dimensional heat diffusion model to explain the growth of oxide films which takes place when a laser beam is shined on and heats a metallic layer deposited on a glass substrate in a normal atmospheric environment. In particular, we apply this model to the experimental results obtained for the dependence of the oxide layer thickness on the laser density power for growth of TiO2 films grown on Ti-covered glass slides. We show that there is a very good agreement between the experimental results and the theoretical predictions from our proposed three-dimensional model, improving the results obtained with the one-dimensional heat diffusion model previously reported. Our theoretical results also show the occurrence of surface cooling between consecutive laser pulses, and that the oxide track surface profile closely follows the spatial laser profile indicating that heat diffusive effects can be neglected in the growth of oxide films by laser heating. © 2001 Elsevier Science B.V.

Rheological properties of tin oxide suspensions

The rheological properties of tin oxide slurries were studied experimentally and theoretically. The deflocculants used were ammonium polyacrilate (PAA) and the copolymer poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (PVB-PVA-PVAc), in water and ethanol, respectively. The amount of deflocculant was optimized for different solid contents by means of viscosity measurements. In spite of the high stability of PVB-dispersed slurries, a high solid concentration was not obtained. On the other hand, a slurry with a 56.4 vol.% of solids was attained when PAA was used. A theoretical study of the adsorption of PAA in its dissociated (basic solution) and non-dissociated (acidic solution) forms on SnO 2 (110) is presented. This analysis was made by means of the PM3 method using a large cluster Sn 15O 28 for the surface model. The calculated adsorption energy is larger for the ionized PAA than for the non-ionized form, indicating that alkaline slurries favor PAA adsorption on the SnO 2 surface. © 2002 Elsevier Science Ltd. All rights reserved.

An ellipsometric study of manganese oxide films: In situ characterization of the deposition and electroreduction of MnO2

The electrodeposition of manganese oxide films onto a platinum substrate was investigated by means of in situ ellipsometry. In the thickness range from 0 to 150 nm, the anodic oxide behaves as an Isotropic single layer with optical constants that are independent of thickness. Deviations at higher thickness are explained in terms of anisotropic properties of the film. The electroreduction of thin films (up to ca. 150 nm) in an alkaline electrolyte leads to a decrease in both the refractive index and the extinction coefficient and is accompanied by a thickness increase of ca. 10%. The Mn(IV) to Mn(III) conversion takes place from the oxide/electrolyte interface inwards. © 2004 The Electrochemical Society. All rights reserved.