Nanocrystalline anatase thin films prepared from redispersible sol-gel powders

Transparent thin films of nanocrystalline anatase were obtained by dip-coating process using an ethanolic suspension of redispersed nanoparticles. This suspension was prepared by sol-gel route and their redispersability achieved by surface grafting of para-toluene-sulfonic acid and acetylacetone. The effects of the acetylacetone content on the powder redispersibility and on the structural evolution of films were determined by small angle X-ray scattering, X-ray reflectometry and X-ray diffraction for different firing temperatures. The results demonstrated that the porous structure of the studied films consist of agglomerates of primary particles with two levels of porosity. The control of the amount of capping ligand allows for a fine-tuning of the average pore size of the dried films. Upon increasing the firing temperature up to 500 degrees C, progressive increase in apparent density, average pore size of films and average crystallite size of powders were observed. (c) 2005 Elsevier Ltd. All rights reserved.

Dynamical scaling properties of nanoporous undoped and Sb-doped SnO2 supported thin films during tri- and bidimensional structure coarsening

The coarsening of the nanoporous structure developed in undoped and 3% Sb-doped SnO2 sol-gel dip-coated films deposited on a mica substrate was studied by time-resolved small-angle x-ray scattering (SAXS) during in situ isothermal treatments at 450 and 650 degrees C. The time dependence of the structure function derived from the experimental SAXS data is in reasonable agreement with the predictions of the statistical theory of dynamical scaling, thus suggesting that the coarsening process in the studied nanoporous structures exhibits dynamical self-similar properties. The kinetic exponents of the power time dependence of the characteristic scaling length of undoped SnO2 and 3% Sb-doped SnO2 films are similar (alpha approximate to 0.09), this value being invariant with respect to the firing temperature. In the case of undoped SnO2 films, another kinetic exponent, alpha('), corresponding to the maximum of the structure function was determined to be approximately equal to three times the value of the exponent alpha, as expected for the random tridimensional coarsening process in the dynamical scaling regime. Instead, for 3% Sb-doped SnO2 films fired at 650 degrees C, we have determined that alpha(')approximate to 2 alpha, thus suggesting a bidimensional coarsening of the porous structure. The analyses of the dynamical scaling functions and their asymptotic behavior at high q (q being the modulus of the scattering vector) provided additional evidence for the two-dimensional features of the pore structure of 3% Sb-doped SnO2 films. The presented experimental results support the hypotheses of the validity of the dynamic scaling concept to describe the coarsening process in anisotropic nanoporous systems.

Structural characterization of undoped and Sb-doped SnO2 thin films fired at different temperatures

SnO2 thin films were obtained by the sol-gel method starting from inorganic precursor solutions. In this work, we compare the structure of undoped and Sb-doped SnO2 films prepared by dip-coating. The films were deposited on quartz substrates and then fired at different temperatures ranging from 383 up to 1173 K. The density and the thickness of the films were determined by X-ray reflectivity (XRR) and their porous nanostructure was characterized by grazing-incidence small angle X-ray scattering (GISAXS). XRR results corresponding to undoped and Sb-doped samples indicate a monotonous decrease in film thickness when they are fired at increasing temperatures. At same time, the apparent density of undoped samples exhibits a progressive increase while for Sb-doped films it remains invariant up to 973 K and then increases for T = 1173 K. Anisotropic GISAXS patterns of both films, Sb-doped and undoped, fired above 573 K indicate the presence of elongated pores with their major axis perpendicular to the film surface. For all firing temperatures the nanopores in doped samples are larger than in undoped ones. This suggests that Sb-doping favours the pore growth hindering the film densification. At the highest firing temperature (1173 K) this effect is reversed.

Differential effects of novel wasp toxin on rat hippocampal interneurons

We studied the effects of a wasp toxin beta-pompilidotoxin (beta-PMTX) on rat hippocampal CA1 interneurons by the current-clamp technique. The firing patterns of pyramidal neurons and pyramidale interneurons were not affected by beta-PMTX, but in oriens and radiatum interneurons, beta-PMTX converted the action potentials to prolonged depolarizing potentials by slowing the inactivation of Na+ channels. In lacunosum moleculare interneurons, beta-PMTX induced initial bursting spikes followed by block of succeeding spikes. Comparison of beta-PMTX with a sea anemone toxin, ATX 11, revealed that ATX 11 altered the firing properties of pyramidal neurons and pyramidale interneurons that were unchanged by beta-PMTX. Our results suggest that beta-PMTX modulates Na+ currents in CAl interneurons differently in various CAl neurons and the toxin is useful to classify Na+ channel subtypes. (C) 2002 Elsevier B.V. Ireland Ltd. All rights reserved.

Structural and electrical properties of SrBi2Nb2O9 thin films prepared by chemical aqueous solution at low temperature

SrBi2Nb2O9 (SBN) thin films were prepared by the polymeric precursors method and deposited by dip coating onto Pt/Ti/SiO2/Si(100) substrates. The dip-coated films were specular and crack-free and crystallized during firing at 700 degrees C. Microstructure and morphological evaluation were followed by grazing incident X-ray diffraction (GIXRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The films exhibited somewhat porous grain structure with rounded grains of about 100 nm. For the electrical measurements, gold electrodes of 300 mu m in diameter were sputter deposited on the top surface, forming a metal-ferroelectric-metal (MFM) configuration. The remanent polarization (P-r) and coercive field (E-c) were 5.6 mu C/cm(2) and 100 kV/cm, respectively. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Characterization of the porosity developed in a new titania-alumina catalyst support prepared by the sol gel route

Titanium oxide (TiO2) is a good candidate for support of hydrotreating catalysts but has the disadvantage of presenting a low surface area and a poor thermal stability when compared with Al2O3. A mixed TiO2-Al2O3 support was proposed as an alternative that is expected to be free from these drawbacks. The variation during firing of the nanoporous texture of supports composed of TiO2-Al2O3, TiO2 and Al2O3 was studied by small angle X-ray scattering (SAXS). The supports were prepared by the sol-gel route using Ti and Al isopropoxides. We have particularly analyzed the effects of acid and basic hydrolysis on the nanostructural features of catalyst supports fired at different temperatures. The nanopore radius distribution functions were determined from SAXS results assuming a simple model of spherical nanopores embedded in a homogeneous solid matrix. The modal pore radius in both pure TiO2 and pure Al2O3 supports grows from 1.3 to 2.2 nm as the firing temperature increases from 673 to 973 K. on the other hand, the modal pore radius in the mixed TiO2-Al2O3 support remains below 1.2 nm over the same range of firing temperatures. These results demonstrate the good thermal stability of the nanoporous texture of mixed TiO2-Al2O3 supports.

Evaluation of shear bond strength at the interface of two porcelains and pure titanium injected into the casting mold at three different temperatures

Statement of problem. Titanium has physical and mechanical properties, which have led to its increased use in dental prostheses despite casting difficulties due to high melting point and formation of oxide layers which affect the metal-ceramic bond strength.Purpose. This in vitro study evaluated the shear bond strength of the interface of 2 dental porcelains and pure titanium injected into a mold at 3 different temperatures.Material and methods. Using commercially pure (cp) titanium bars (Titanium, Grade I) melted at 1668degreesC and cast at mold temperatures of 430degreesC, 700degreesC or 900degreesC, 60 specimens were machined to 4 x 4 mm, with a base of 5 x 1 mm. The 4-mm surfaces were airborne-particle abraded with 100 mum aluminum oxide before applying and firing the bonding agent and evaluating the 2 porcelains (Triceram/Triline ti and Vita Titankeramik). Ten specimens were prepared for each temperature and porcelain combination Shear bond testing was performed in a universal testing machine, with a 500-kg load cell and crosshead speed of 0.5 mm/min. The specimens were loaded until failure. The interfaces of representative fractured specimens of each temperature were examined with a scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). Data for shear bond strength (MPa) were statistically analyzed by 2-way ANOVA and the Tukey test (alpha = .05).Results. The results showed significant differences for the metal/porcelain interaction effect (P = .0464). There were no significant differences for the 2 porcelains (P = .4250). The Tukey test showed a significant difference between the pair cp Ti 430degreesC Triceram and cp Ti 900degreesC Triceram, with respective mean values and SDs of 59.74 +/- 11.62 and 34.03 +/- 10.35 MPa.Conclusion. Triceram porcelain showed a bond strength decrease with an increase in the mold temperature for casting titanium. The highest bond strength for Vita porcelain and the best metal-ceramic interface observed with the SEM were found with the mold temperature of 700degreesC.

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.

X-ray reflectivity of zirconia based sol-gel coatings on borosilicate glasses

In this work the technique of X-ray reflectometry was applied to study zirconiumsulfate films deposited by sol-gel dip-coating process on a borosilicate glass surface. The influence of withdrawal speed and temperature of thermal treatment on the film structure are analyzed. The thermal evolution of the density and thickness of the film was compared with these properties measured for a monolithic xerogel by helium picnometry and thermomechanical analysis. The fitting of experimental curves by classical reflectivity model showed the presence of an additional layer at the top surface of the coating. Layer thickness increases with increase of withdrawal speed in agreement with the Landau-Levich model. The apparent and real densities are similar for coatings fired below 400 degrees C, which shows that the films are free of pores. The shrinkage during firing is anisotropic, occurring essentially perpendicular to the coating surface. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Structural features of phosphate and sulfate modified zirconia prepared by sol-gel route

This paper describes the effect of sulfate, phosphate and nitrate complexing ligands on the structural features of amorphous xerogels and on the crystallization of metastable zirconia phases during the xerogel-ceramic conversion. Powdered samples were prepared by a sol-gel route using zirconyl chloride precursors chemically modified by complexing ligands. The structural evolution of ZrO2 phases as function of firing temperature was analyzed by XRPD, EXAFS and P-13 NMR/MAS. The experimental results show the formation of metastable t-ZrO2 during the low firing temperature of xerogels modified by sulfate or phosphate groups. The martensitic tetragonal-monoclinic transformation occurs during desorption of sulfate groups. The largest temperature interval of stability of metastable tetragonal zirconia was observed for phosphate-modified xerogels.

Densification and electrical conductivity of fast fired manganese-doped ceria ceramics

Reactive pure and manganese-doped (5% and 10 at.%) ceria nanosized powders were prepared by the polymeric precursor technique. Physical properties of powder materials were studied by X-ray diffraction, nitrogen adsorption, and diffuse reflectance infrared Fourier transform spectroscopy. Characterization of powder compacts after fast firing at 1200 degrees C for 5 min was carried out by scanning electron microscopy and impedance spectroscopy measurements. The bulk apparent density of sintered pellets was determined for pellets of different compositions sintered at 1200 degrees C. A gradual decrease of the particle size occurs with increasing doping content. Relatively high values of apparent density were obtained after fast firing doped specimens at 1200 degrees C. DRIFT spectra evidence that a fraction of Mn ions was segregated onto particles surface. The electrical resistivity of sintered pellets reveals different mechanisms of conduction depending on the Mn content. (C) 2005 Elsevier B.V All rights reserved.

Structure of SnO2 alcosols and films prepared by sol-gel dip coating

To obtain SnO2 films to be used for surface protection of fluoride glasses, a non-aqueous sol-gel route for the preparation was developed. An ethanolic SnO2 colloidal suspension was prepared by thermohydrolysis of SnCl4 solution at 70 degreesC. By using this procedure, redispersable powders with nanometer sized particles were obtained. Films were obtained by dip coating on glass and mica substrates. The structures of the ethanolic precursor suspension and films were compared to those of similar samples prepared by the classical aqueous sol-gel route. Comparative analyses performed by photon correlation spectroscopy demonstrated that the powders obtained by freeze-drying are fully redispersable either in aqueous or in alcoholic solutions at pH greater than or equal to 8. As prepared sols and redispersed colloidal suspensions have hydrodynamic radius distribution (2-14 nm) with an average size close to 7 nm. The variations in film structures with firing temperature were investigated by small-angle X-ray scattering and X-ray reflectometry. The experimental results show that the films have a two level porous structure composed of agglomerates of primary colloidal particles. The sintering of the primary particles leads to the densification of agglomerates and to the formation of inter-agglomerate spatially correlated pores. The volume fraction of intra-agglomerate pores is reduced from approximate to 50% to approximate to 30% by the precipitation of precursor salts partially hydrolyzed in ethanolic solution. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Nucleation and growth of mullite whiskers from lanthanum-doped aluminosilicate melts

Nucleation and growth of mullite whiskers in the La2O3-Al2O3-SiO2 system were investigated in the 1500degrees-1700degreesC temperature range. A differential thermal analysis (DTA) showed that the mullitization temperature decreases from 1350degreesC to 1240degreesC as a result of lanthania doping. In the temperature range of 1250-1500degreesC, most of the mullite grains have an Al2O3/SiO2 = 1.5 composition throughout the ceramic body; however, from 1400degreesC upward, the number of anisotropic grains with the Al2O3/SiO2 = 1.3 composition begins to increase. The concentration of alumina in the composition of the grain-boundary phase decreases as firing temperatures increase. At temperatures > 1500degreesC, alumina grains and whiskers grow on the internal and external surfaces of the ceramic body with the characteristic Al2O3/SiO2 = 1.3 composition. Removal of the mullite whisker layer by acid attack revealed an alumina-rich, rosace-like patterned microstructure correlated with the process of whisker nucleation and growth. In the early stages, whisker growth rates were found to be near 60 mum/h. Experimental evidence pointed to nucleation inside the thin glass layer on the external surface.

Mullite whiskers grown from erbia-doped aluminum hydroxide-silica gel

Mullite whiskers and anisotropic grains that were derived from erbia-doped aluminum hydroxide-silica gel were studied. Firing 3.0-mol%-erbia-doped isostatically pressed pellets at 1600 degrees C for 1.0-8.0 h resulted in a high surface concentration of mullite whiskers. Their c-axes were aligned preferentially along the pellet surface; the maximum length was 50 mu m, and the maximum aspect ratio was 23. The pellet surface was fully covered by mullite whiskers, and small anisotropic grains with a low aspect ratio were observed in the bulk. The voids that were observed in the fracture surfaces were covered fully by mullite whiskers. The large number of voids resulted in an apparent density of 1.60 g/cm(3) in the sintered pellets. The molar ratio of alumina to silica in the whiskers was in the range of 1.30-1.45 tan average value of 1.31), regardless of whether the alumina/silica powder compositions were mixed in a 3:2 or 2:1 ratio.

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.