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.

Photodesorption and electron trapping in n-type SnO2 thin films grown by dip-coating technique

Thin films of undoped and Sb-doped (2 atg%) SnO2 have been prepared by sol-gel dip-coating technique on borosilicate glasses. Variation of photoconductivity excitation with wavelength and optical absorption indicate indirect bandgap transition with energy of ≅ 3.5 eV. Conductance as function of temperature indicates two levels of capture with 39 and 81 meV as activation energies, which may be related to an Sb donor and oxygen vacancy respectively. Electron trapping by these levels are practically destroyed by UV photoexcitation (305 nm) and heating in vacuum to 200°C. Gas analysis using a mass spectrometer indicates an oxygen related level, which may not be desorbed in the simpler O2 form.

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.

Improved Conductivity Induced by Photodesorption in SnO2 Thin Films Grown by a Sol-Gel Dip Coating Technique

Thin films of undoped and Sb-doped SnO2 have been prepared by a sol-gel dip-coating technique. For the high doping level (2-3 mol% Sb) n-type degenerate conduction is expected, however, measurements of resistance as a function of temperature show that doped samples exhibit strong electron trapping, with capture levels at 39 and 81 meV. Heating in a vacuum and irradiation with UV monochromatic light (305 nm) improve the electrical characteristics, decreasing the carrier capture at low temperature. This suggests an oxygen related level, which can be eliminated by a photodesorption process. Absorption spectral dependence indicates an indirect bandgap transition with Eg ≅ 3.5 eV. Current-voltage characteristics indicate a thermionic emission mechanism through interfacial states.

Oxygen related defects excitation and photoconductivity dependence of SnO2 sol-gel films with several light sources

Since oxygen vacancies act as donors in SnO2, the electrical properties are related to deviation from stoichiometric composition. Depending on stoichiometry SnO2 can be highly insulating or may exhibit fairly high n-type conductivity. Since bandgap transitions are in the ultraviolet range, its photoconductivity is strongly dependent on the excitation source. We have measured variation of photoconductivity excitation with wavelength for tin dioxide grown by dip-coating sol-gel technique using several light sources: tungsten lamp, xenon, mercury and deuterium, and present selected results. The main band is obtained in the range 3-4eV according to light source spectrum in the ultraviolet range. The presence of oxygen in the cryostat also affects the spectrum since electron-hole pairs react with adsorbed oxygen specimens. © 1999 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint.

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.

Evaluation of plasma membrane integrity of frozen-thawed goat spermatozoa with or without seminal plasma

The aim of the present work was to evaluate plasma membrane integrity, motility, vigor and morphology of fresh and frozen goat spermatozoa with or without seminal plasma. Semen samples were diluted in Tris solution, before and after thawing, with a combination of carboxifluorescein diacetate and propidium iodide. The results showed differences (P < 0.01) for motility and minor defects in the presence or absence of seminal plasma, for both fresh and frozen samples. Periods of collection had a significant effect on motility, probably due to changes in the photoperiod. Plasma membrane integrity was significantly reduced by the freezing process, whether seminal plasma was present or absent. In conclusion, removal of seminal plasma decreased motility and vigor rates in frozen samples. The photoperiod probably decreased the testosterone level, contributing negatively to the high percentage of sperm abnormalities, mainly damaged membranes. The use of fluorescent probes allowed a better estimation of the percentage of functional cells, instead of only estimating the percentage of motile cells or morphology defects. © 2001 Elsevier Science B.V. All rights reserved.

Histologic Evaluation of the Osteoinductive Property of Autogenous Demineralized Dentin Matrix on Surgical Bone Defects in Rabbit Skulls Using Human Amniotic Membrane for Guided Bone Regeneration

The aim of this investigation was to evaluate the osteoinductive property of autogenous demineralized dentin matrix (ADDM) on experimental surgical bone defects in the parietal bone of rabbits using the guided bone regeneration (GBR) technique incorporating human amniotic membrane (HAM). Thirty-six rabbits were divided into 2 groups, HAM and ADDM+HAM. It was possible to conclude that HAM did not interfere with bone repair and was resorbed. Slices of ADDM induced direct bone formation and were incorporated by the newly formed bone tissue and remodeled. The bone defects healed faster in the ADDM+HAM group than in the group with HAM only.

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.

Spectrophotometric flow-injection determination of sulphite in white wines involving gas diffusion through a concentric tubular membrane

A flow-injection system is proposed for the spectrophotometric determination of sulphite in white wines. The method involves analyte conversion to SO2, gas diffusion through a Teflon® semi-permeable membrane, collection into an alkaline stream (pH 8), reaction with Malachite green (MG) and monitoring at 620 nm. With a concentric tubular membrane, the system design was simplified. Influence of reagent concentrations, pH of donor and acceptor streams, temperature, timing, surfactant addition and presence of potential interfering species of the wine matrix were investigated. A pronounced (ca. 100%) enhancement in sensitivity was noted by adding cetylpyridinium chloride (CPC). The proposed system is robust and baseline drift is not observed during 4 h operating periods. Only 400 μL of sample and 0.32 mg MG are required per determination. The system handles 30 samples per hour, yielding precise results (r.s.d. < 0.015 for 1.0 - 20.0 mg L-1 SO2) in agreement with those obtained by an alternative procedure.