Short Range Order Evolution in the Preparation of SnO2 Based Materials

The evolution of Eu3+ doped SnO2 xerogels to the cassiterite structure observed during sintering was studied by means of Eu3+ spectroscopy, XRD and EXAFS at the Sn K-edge. Eu3+ ions adsorbed at the surface of colloidal particles present a broad distribution of sites, typical of oxide glasses. With sintering at 300°C, this distribution is still broadened. Crystallization is clearly observed by the three techniques with increasing sintering temperature. It is found that the addition of Eu3+ limits the crystallite growth.

EXAFS and XRD Study of the Structural Evolution during Isothermal Sintering of SnO2 Xerogels

The formation of an ordered (crystalline) phase during isothermal sintering of SnO2 monolithic xerogels, at 200, 250, 300, 400, 500, 600 and 700°C, has been analyzed by the combined use of EXAFS and XRD techniques. For the desiccated gel (110°C), EXAFS results show the formation of small microcrystallites with the incipient cassiterite structure. Between 110 and 250°C, the dehydratation reaction leads to an amorphization evidenced by a decrease of the long and short range crystallographic order. It is due to fissure formation in the xerogel network. For higher temperatures, a continuous coagulation of the crystallites occurs, leading to grain growth. Grain and pore growth obeys the same kinetic relation, so that the microstructure grows by simple enlargement while its morphology is static.

Influence of viscoelastic characteristics of the colloidal suspensions on the formation of SnO2 supported membranes

SnO2 supported membranes have been prepared by sol-casting on alumina tubular substrate, using aqueous colloidal suspensions prepared by sol-gel route. The viscoelastic behaviour during sol ageing was analyzed by dinamic rheologial measurements. The complex viscosity and the storage and loss moduli have been followed during the sol-gel transition and the results have been correlated with the linear aggregates growth and the scalar percolation models. The scanning electron microscopy has evidenced that the homogeneity and thickness of the membrane depend on the sol ageing time. Crack-free and homogeneous membranes have been obtained for coated layers of 0.5μm thickness. © 1997 Trans Tech Publications.

Electrical properties of the SnO2-based varistor

The non-linear electrical properties of CoO-doped and Nb205-doped SnO2 ceramics were characterized. X-ray diffraction and scanning electron microscopy indicated that the system is single phase. The electrical conduction mechanism for low applied electrical field was associated with thermionic emission of the Schottky type. An atomic defect model based on the Schottky double-barrier formation was proposed to explain the origin of the potential barrier at the ceramic grain boundaries. These defects create depletion layers at grain boundaries, favouring electron tunnelling at high values of applied electrical field. © 1998 Chapman & Hall.

Effect of atmosphere and dopants on sintering of SnO2

Tin oxide is an n-type semiconductor material with a high covalent behavior. Mass transport in this oxide depends on the surface state promoted by atmosphere or by the solid solution of a non-isovalent oxide doping The sintering and grain growth of this type of oxide powder is then controlled by atmosphere and by extrinsic oxygen vacancy formation. For pure SnO2 powder the surface state depends only on the interaction of atmosphere molecules with the SnO2 surface. Inert atmosphere like argon or helium promotes oxygen vacancy formation at the surface due to reduction of SnO2 to SnO at the surface and liberation of oxygen molecules forming oxygen vacancies. As consequence surface diffusion is enhanced leading to grain coarsening but no densification. Oxygen atmosphere inhibits the SnO2 reduction decreasing the surface oxygen vacancy concentration. Addition of dopants with lower valence at sintering temperature creates extrinsic charged oxygen vacancies that promote mass transport at grain boundary leading to densification and grain growth of this polycrystalline oxide.

Ceramic coating for refractories protection against carbon oxidation, Part 1: Protection mechanisms

For retarding carbon oxidation in refractories during the preheating of metallurgical furnaces, a ceramic coating, made mainly of sodium phosphosilicate and clay was developed. The coating presents high adherence to the substrate with no swelling. The coating was characterized by thermal analysis, X-ray diffraction at room temperature (XRD) and at high temperature (HTXRD), X-ray fluorescence and scanning electronic microscopy (SEM). The glass transition temperature is reached at 800 °C and only glassy phase is observed above this temperature. Thus the mechanism of protection seems to be the formation of a glassy phase on the surface of the refractory, and the coating tends to be more efficient at temperatures higher than 800 °C.

EPR of Mn as densifying agent in SnO2 powders

Electron Paramagnetic Resonance (EPR) spectra have been obtained at room temperature and at X-band in powders of SnO2 doped with Mn from 0.3 to 10% and submitted to heat treatment from 500 to 900 °C. Mn ions are probably located at particle surfaces as Mn2+, evidenced by its single EPR line which narrows by the exchange interaction effect due to particle growth observed by the BET technique. In samples doped above 1% formation Of Mn3O4 is detected on particle surfaces and a small quantity of Mn is thermally diffused into the bulk as Mn4+. Powders compacted and sintered at 1300 °C confirmed that Mn2+ ions remain at grain boundaries acting as densifying agent.

Evolution of the viscoelastic properties of SnO2 colloidal suspensions during the sol-gel transition

This paper describes the effect of the concentration of electrolyte and pH on the kinetics of aggregation and gelation processes of SnO2 colloidal suspensions. Creep, creep-recovery, and oscillatory rheological experiments have been done in situ during aggregation and gelation. A phenomenological description of the structure of the colloidal system is given from the time evolution of rheological parameters. The dependence of the equilibrium steady-state shear compliance on the terminal region of clusters or aggregates seems to be a way to determine the beginning of interconnection of aggregates and the gel point. We propose that at this point the equilibrium steady-state compliance is a minimum. The steady-state viscosity determined from creep experiment can be fit with a power law with the extent of the transformation, giving critical exponent s = 0.7 ± 0.1. The value of the critical exponent Δ = 0.78 ± 0.05 was determined from oscillatory experiment. These results indicate that gelation of SnO2 colloidal suspension exhibits the typical scale expected from the scalar percolation theory. © 2000 Elsevier Science B.V. All rights reserved.

Effect of powder milling and dopant addition on the current-voltage characteristics of SnO2-based ceramics

Non-linear electrical properties of SnO2-based ceramics were investigated as a function of powder agglomeration condition and as a function of dopant addition. All doped powders presented a single phase, cassiterite, as evidenced by X-ray diffraction analysis. The effect of milling was quite evident, with non-milled powder showing higher agglomerated particle size than milled powder. Cr addition seemed to increase the non-linear coefficient. Cu and Mn rendered dense ceramics, but α values for systems with Mn were higher than for systems with Cu.

MnO2 influence on the electrical properties of SnO2-based ceramic systems

Tin dioxide is an n-type semiconductor that when doped with other metallic oxides exhibits non-linear electric behavior with high non-linear coefficient values typical of a varistor. In this work, electrical properties of the SnO2.CoO.Ta2O5 and SnO2.CoO.MnO2.Ta2O5 ceramics systems were studied with the objective of analyzing the influence of MnO2 on sintering behavior and electrical properties of these systems. The compacts were prepared by powder mixture process and sintered at 1300°C for 1 hour, in air, using a constant heating rate of 10°C/min. The morphological and structural properties were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The densities of the sintered ceramics were measured using the Archimedes method. The SnO2.CoO.Ta2O5 and SnO2.CoO.MnO2.Ta2O5 systems presented breakdown fields (Eb) about 3100 V.cm-1 and 3800 V.cm-1, respectively, and non-linear coefficient (α) about 10 and 20, respectively.

Effects of tungsten carbide thermal spray coating by HP/HVOF and hard chromium electroplating on AISI 4340 high strength steel

In cases of decorative and functional applications, chromium results in protection against wear and corrosion combined with chemical resistance and good lubricity. However, pressure to identify alternatives or to improve conventional chromium electroplating mechanical characteristics has increased in recent years, related to the reduction in the fatigue strength of the base material and to environmental requirements. The high efficiency and fluoride-free hard chromium electroplating is an improvement to the conventional process, considering chemical and physical final properties. One of the most interesting, environmentally safer and cleaner alternatives for the replacement of hard chrome plating is tungsten carbide thermal spray coating, applied by the high velocity oxy-fuel (HVOF) process. The aim of this study was to analyse the effects of the tungsten carbide thermal spray coating applied by the HP/HVOF process and of the high efficiency and fluoride-free hard chromium electroplating (in the present paper called 'accelerated'), in comparison to the conventional hard chromium electroplating on the AISI 4340 high strength steel behaviour in fatigue, corrosion, and abrasive wear tests. The results showed that the coatings were damaging to the AISI 4340 steel behaviour when submitted to fatigue testing, with the tungsten carbide thermal spray coatings showing the better performance. Experimental data from abrasive wear tests were conclusive, indicating better results from the WC coating. Regarding corrosion by salt spray test, both coatings were completely corroded after 72 h exposure. Scanning electron microscopy technique (SEM) and optical microscopy were used to observe crack origin sites, thickness and adhesion in all the coatings and microcrack density in hard chromium electroplatings, to aid in the results analysis. © 2001 Elsevier Science B.V. All rights reserved.

Influencia del tratamiento térmico en la cristalización y rugosidad de películas delgadas de LiNbO3 depositadas por el método Spin Coating

Lithium niobate (LiNbO3) thin films with 1/1 stoichiometry were prepared by a spin-coating from polymeric precursor method. The films deposited on silicon (100) substrates, were thermally treated from 400° to 600°C for 3 hours in order to study the influence of thermal treatment on the crystallinity, microstructure, grain size and roughness. X-ray diffraction (XRD) results showed that LiNbO3 phase crystallizes at low temperature (400°C). It was observed by scanning electron microscopy (SEM) that it is possible to obtain dense thin films at temperatures around 500°C. The atomic force microscopy (AFM) results showed that the grain size and roughness are strongly influenced by the annealing temperature.

Contribution of oxygen related defects to the electronic transport in SnO2 sol-gel films

SnO2 deposited by sol-gel is a polycrystalline film with small grain size. Oxygen present at a less grain boundary traps electrons and then the depletion layer around the potential barrier of the grain boundary becomes wider, comparable to the grain size. We have modeled the conductivity taking into account the trapped charge at the depletion layer of the grain boundary and other scattering mechanisms such as ionized impurity and polar optical. Experimental data of photoconductivity of SnO2 sol-gel films are simulated considering the dominant scattering at grain boundary and crystallite bulk. The fraction of trapped charge at the grain boundary depends on temperature and wavelength of irradiating light, being as high as 50% for illumination in the range 500-600 nm for SnO2-2%Nb as grown sample annealed in air to 550°C. This fraction can be quite reduced depending on exposure to light and annealing under different oxygen partial pressure conditions.

Effect of atmosphere and dopants on sintering of SnO2

Tin oxide is an n type semiconductor material with a high covalent behavior. Mass transport in this oxide depends on the surface state promoted by atmosphere or by the solid solution of aliovalent oxide doping. The sintering and grain growth of this type of oxide powder is then controlled by atmosphere and by extrinsic oxygen vacancy formation. For pure SnO2 powder the surface state depends only on the interaction of atmosphere molecules with the SnO2 surface. Inert atmosphere like argon or helium promotes oxygen vacancy formation at the surface due to reduction of SnO2 to SnO at the surface and liberation of oxygen molecules forming oxygen vacancies. As a consequence surface diffusion is enhanced leading to grain coarsening but no densification. Oxygen atmosphere inhibits SnO2 reduction by decreasing the surface oxygen vacancy concentration. Addition of dopants with lower valence at the sintering temperature creates extrinsic charged oxygen vacancies that promote mass transport at the grain boundary leading to densification and grain growth of this polycrystalline oxide.

Spectroscopic studies of SnO2 doped with Cr, Co or Nb

SnO2 ceramics doped with different amounts of Co, Cr or Nb were investigated using visible and infrared spectroscopy at room temperature. Based on the observed d-d transitions the valence states of incorporated dopants were determined. Values of the optical band-gap were calculated in all samples. The infrared spectra of the samples displayed variations in the position, relative intensity and width of the bands, which were attributed to the presence of dopants.