Formation of zirconia foams using the thermostimulated sol-gel transition

In this paper we describe the production of zirconia-based foams by a novel thermostimulated sol-gel route, that employs the foaming of colloidal suspensions prior to the sol-gel transition promoted by small increase of temperature (congruent to3 degreesC). This method produces gelled bodies having porosity >70% in the wet stage, and can be used to produce complex-shaped components. The effect of a foaming agent (Freon11 or CCl3F) and surfactant content on the formation and stability of the foams was analyzed. The rheologic measurements demonstrate that by increasing the surfactant concentration, the gelation time decreases increasing foam stability. As the surfactant concentration and quantity of foaming agent increase, the density decreases and the porosity increases. Hg porosimetry results show that the dry foam presents a bimodal pore size distribution. The family of sub-micrometer pores was attributed to the formation of a microemulsion between Freon11 and water. Scanning electron microscopy analysis shows that the foam structure consists of a three-dimensional network of spherical pores, which may be open and interconnected or closed, at larger or smaller porosities, respectively. Finally these results show that the thermostimulated sol-gel transition provides a potential route for ceramic foam manufacture. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Planar waveguides based on nanocrystalline and Er3+ doped SnO2

Luminescent SnO2: x%mol Er3+ (x=0.1-2.0) thin films have been spin coated on borosilicate and silica substrates from water colloidal suspensions that could be prepared containing up to 40% in weight SnO2 nanocrystalline powders. High Resolution Transmission Electron Microscopy results show the well known SnO2 cassiterite structure and nanocrystallites around 10 nm in diameter, corroborating results from X-ray diffraction. Mono and multi layers have been prepared from the stable colloidal suspensions and films thickness was observed to increase linearly, up to 200 nm, with the colloidal suspensions nanoparticles amount. Excitation and emission spectra have been measured and Er3+ ions were found to be essentially incorporated into the cassiterite structure, substituting for Sn4+, for doping concentration lower than 0.05 mol%. Er3+ ions also appear segregated at the grains surface for higher doping concentration. The optical parameters (refractive index, thickness and propagating modes) of a waveguide sample were measured at 632.8 and 543.4 nm by the prism coupling technique. A monomodal waveguide was obtained with attenuation loss of 3.5 dB/cm along a 2.5 cm optical path.

Microstructural investigation of the PZT films prepared from the suspension of nanocrystalline powders

PZT thin films of composition Pb(Zr0.52Ti0.48)O-3 were prepared by a novel method from the suspension of nanocrystalline PZT powders. The powders were obtained by mechanochemical synthesis. Films were deposited on silicon (100) and platinum covered silicon substrates (Pt (111) /Ti/SiO2/Si) Using spin-on technique. Substrate type has influence on films crystallinity, orientation and can react with the films changing its phase composition. Films microstructure strongly depends on thermal treatment conditions due to phase and compositional changes of the films. (C) 2003 Elsevier Ltd. All rights reserved.

Chemical vapor deposition of multi-walled carbon nanotubes from nickel/yttria-stabilized zirconia catalysts

Multi-walled carbon nanotubes (MWNT) were produced by chemical vapor deposition using yttria-stabilized zirconia/nickel (YSZ/Ni) catalysts. The catalysts were obtained by a liquid mixture technique that resulted in fine dispersed nanoparticles of NiO supported in the YSZ matrix. High quality MWNT having smooth walls, few defects, and low amounts of by-products such as amorphous carbon were obtained, even from catalysts with large Ni concentrations (> 50 wt.%). By adjusting the experimental parameters, such as flux of the carbon precursor (ethylene) and Ni concentration, both the MWNT morphology and the process yield could be controlled. The resulting YSZ/Ni/MWNT composites can be interesting due to their mixed ionic-electronic transport properties, which could be useful in electrochemical applications.

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.

Room temperature co-precipitation of nanocrystalline CeO2 and Ce0.8Gd0.2O1.9-delta powder

This paper describes a simple method to co-precipitate CeO2 and Ce0.8Gd0.2O1.9-delta with ammonium hydroxide from solvents such as: water, ethylene glycol, ethyl alcohol and isopropyl alcohol. Characterization by Raman spectroscopy and XRD evidenced the formation of a solid solution of gadolinium-doped ceria at room temperature. Nanometric particles with crystallite size of 3.1 nm were obtained during synthesis using ethyl alcohol as solvent. This is a promising result compared with those mentioned in the literature, in which the smallest crystallite size reported was, 6.5 nm. (c) 2006 Elsevier B.V. All rights reserved.

Sintering of zirconia composites obtained by slip casting

Composites containing a matrix of nanometric Ce-stabilized zirconia with an addition of micrometric monoclinic zirconia were processed by slip casting and sintered at a relatively low temperature. The ratio between nanometric and micrometric particles was determined according to the viscosity of the suspensions and the final density of the pellets. An optimum amount of micrometric particles was necessary to achieve improved suspension dispersion and higher pellet density. The amount of deflocculant in the suspensions containing the mixture of micrometric and nanometric particles was optimized by viscosity measurements. The pellets were characterized by dilatometry, Hg porosimetry, density measurement (the Archimedes method) and scanning electron microscopy. Despite the low green density obtained (35-38% of the theoretical density), densities as high as 97.5% were achieved after sintering. (C) 2001 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Zirconia needles synthesized inside hexagonal swollen liquid crystals

We report the synthesis of zirconia microneedles by the direct nucleation of particles inside a hexagonal swollen liquid crystal (SLC) (cell parameter a = 27 nm) prepared by mixing with the proper ratio, an aqueous solution of sulfated zirconium colloids, a cationic surfactant (cetylpyridinium chloride), cychlohexane as swelling agent with an oil over water ratio of 2.5 (vol.), and 1-pentanol as cosurfactant. After a slow crystallogenesis that can be enhanced by an initial induction step under moderate temperature, particles in the centimeter range can be obtained, with a very high shape ratio (over 100). These particles are made of crystalline octahydrate zirconium oxychloride containing pores of 20 nm diameter, aligned along the main axis of the liquid crystal, as the fingerprint of the oil cylinders present in the hexagonal phase. The morphology of these particles confirms that the shaping mechanism is based on true liquid crystal templating (TLCT). Further thermal treatment of these particles, after extraction from the SLC, leads to the crystallization of zirconia with the same needlelike morphology as the zirconium oxychloride.

Electrical measurements in doped zirconia-ceria ceramics

Zirconia-ceria powders with 12 mol % of CeO2 doped with 0.3 mol% of iron, copper, manganese and nickel oxides were synthesized by the conventional mixed oxide method. These systems were investigated with regard to the sinterability and electrical properties. Sintering was studied considering the shrinkage rate, densification, grain size, and phase evolution. Small amount of dopant such as iron reduces sintering temperature by over 150degreesC and more than 98% of tetragonal phase was retained at room temperature in samples sintered at 1450degreesC against 1600degreesC to stabilize the tetragonal phase on pure ZrO2-CeO2 system. The electrical conductivity was measured using impedance spectroscopy and the results were reported. The activation energy values calculated from the Arrhenius's plots in the temperature range of 350-700degreesC for intragrain conductivities are 1.04 eV.

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.

Dielectric and piezoelectric properties of the mechanochemically prepared PZT ceramics

Mechanochemical synthesis was applied to obtain nanocrystalline powders of composition Pb(Zr0.52Ti0.48)O-3 (PZT). Milling was performed in a planetary ball mill using vials and balls made of zirconia or steel-in order to investigate influence of milling media on the electrical properties of resulting ceramics. PZT ceramics showed high values for dielectric constant (epsilon(r)), reaching 970 at room temperature, as well as low dielectric loss (tandelta) under the optimal processing conditions. High values of remanent polarization (P-r) indicate high internal polarizability. The best samples showed piezoelectric strain constant d(33) = 347 pC/N and planar coupling factor k(P) = 0.44. Milling in ZrO2 medium prevents powder contamination and provides reproducibility of milling process. Also, PZT obtained from the powders milled in ZrO2 exhibited lower values of dielectric loss, in comparison with the PTZ obtained from the powders milled in Fe. This suggests that contamination of the powder with Fe could result in an increase of conductivity in final product. (C) 2004 Kluwer Academic Publishers.

Properties and in vivo investigation of nanocrystalline hydroxyapatite obtained by mechanical alloying

Mechanical alloying has been used successfully to produce nanocrystalline powders of hydroxyapatite (HA) using three different procedures. The milled HA was studied by X-ray diffraction, Infrared, Raman scattering spectroscopy and Scanning Electron Microscopy (SEM). We obtained HA with different degrees of crystallinity and time of milling. The grain size analysis through SEM and XRD shows particles with dimensions of 36.9, 14.3 and 35.5 nm (for (R1), (R2) and (R3), respectively) forming bigger units with dimensions given by 117.2, 110.8 and 154.4 nm (for (R1), (R2) and (R3), respectively). The Energy-Dispersive Spectroscopy (EDS) analysis showed that an atomic ratio of Ca/P= 1.67, 1.83 and 1.50 for reactions (R1), (R2) and (R3), respectively. These results suggest that the R1 nanocrystalline ceramic is closer to the expected value for the ratio Ca/P for hydroxyapatite, which is 513 congruent to 1.67. The bioactivity analysis shows that all the samples implanted into the rabbits can be considered biocompatible, since they had been considered not toxic, bad not caused inflammation and reject on the part of the organisms of the animals, during the period of implantation. The samples implanted in rabbits had presented new osseous tissue formation with the presence of osteoblasts cells. (C) 2004 Elsevier 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.

On the stabilizing behavior of zirconia: A combined experimental and theoretical study

Reactive zirconia powder was synthesized by the complexation of zirconium metal from zirconium hydroxide using a solution of 8-hydroxiquinoline. The kinetics of zirconia crystallization was followed by X-ray diffraction, scanning electron microscopy and surface area measured by the nitrogen adsorption/desorption technique. The results indicated that zirconia with a surface area as high as 100 m(2)/g can be obtained by this method after calcination at 500degreesC. Zirconia presents three polymorphic phases (monoclinic, tetragonal and cubic), which are reversibly interconversible. The cluster model Zr4O8 and Z(r)4O(7)(+2) was used for a theoretical study of the stabilization process. The ab initio RHF method was employed with the Gaussian94 program and the total energies and the energy gap of the different phases were calculated and compared with the experimental energy gap. The theoretical results show good reproducibility of the energy gap for zirconia. (C) 2004 Kluwer Academic Publishers.