Structural and electrical properties of ZnO varistors containing different spinel phases

Structural and electrical properties of ZnO varistors were investigated as a function of spinel composition. Six varistor mixtures differing only in chemical composition of spinel, were prepared by mixing separately synthesized constituent phases (DSCP method). Compositions of constituent phases in sintered samples were investigated by changes of lattice parameters of the phases, as well as by EDS analysis of the constituent phases. It was found that compositions of ZnO, intergranular and spinel phases were partially changed during sintering due to redistribution of additives, that was controlled by starting spinel composition and its stability. Electrical characterization showed significant difference in electrical properties of investigated varistors: nonlinearity coefficients ranging from 22 to 55 and leakage currents differing by the order of magnitude. Activation energies of conduction were obtained from ac impedance spectroscopy measurements. Calculated values of activation energies were in the range 0.61-1.0 eV confirming difference in defect structure of ZnO grain boundaries in varistors containing different spinel phases. (C) 2001 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Sintering of tin oxide using zinc oxide as a densification aid

The physicochemical electronic characteristics of SnO2 render it useful in many technical applications, including ceramic varistors, stable electrodes used in electric glass-melting furnaces and electrometallurgy of aluminum, transparent windows and chemical sensors. The use of ZnO as a sintering aid was explored in this study to obtain SnO2 as a dense ceramic. Compacts were obtained by mechanical mixing of oxides, isostatic pressing at 210 MPa and sintering in situ inside a dilatometer at heating rates of 10degreesC/min. The grain size and microstructure were investigated by scanning and transmission electron microscopy (SEM/TEM). The phases and chemical composition were analyzed by energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The results indicated that ZnO acts as a densification aid for SnO2, improving its grain growth with additions of up to 2 mol%. ZnO forms a solid solution with SnO2 UP to 1 mol%, above which SnZnO3 precipitates in the grain boundary, potentially inhibiting shrinkage and grain growth. (C) 2004 Kluwer Academic Publishers

Microstructural evolution during sintering of CoO doped SnO2 ceramics

Addition of 0.5 mol% of CoO into SnO2 promotes densification of this oxide to 99% of the theoretical density during sintering. TEM in this system reveals that after sintering at 1210 degrees C a secondary phase of Co2SnO4 is precipitated at the SnO2 grain boundaries during cooling. This phase is formed by diffusion of Co ions from the bulk to the grain boundary during sintering leaving needle-like defects at the grain bulk. The high resolution TEM micrograph of this system sintered at 1210 degrees C and 1400 degrees C showed an amorphous grain boundary region low in cobalt, indicating that the Co2SnO4 phase is precipitated from this region. (C) 1999 Elsevier B.V. Limited and Techna S.r.l. All rights reserved.

The effect of ZnO on the sintering and stabilization of ZrO2 center dot MgO system

The sintering of ZrO2. MgO . ZnO powder has been investigated by TMA (Thermal Mechanical Analyser) and its phases analysed by XRD (X-ray diffraction pattern). The data obtained from sintering was studied by the Bannister equation and its dominant sintering mechanism was calculated. It was observed that the ZnO addition in the ZrO2. MgO solid solution lead to increased zirconia stabilization, According to the vacancies model, the ZnO addition did not lead to zirconia phases stabilization (PSZ). An analysis of the rate control in the initial stage of the sintering (region I) showed a mechanism of volume diffusion type. In other regions (regions II and III), the grain growth did lead to the Bannister equation deviation, which was observed by SEM (Scanning Electron Microscopy). These results were different from those demonstrated by other authors who studied the ZrO2. Y2O3 solid solution and obtained a mechanism of grain boundary diffusion type. (C) 1999 Published by Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Sintering of ultrafine undoped SnO2 powder

The sintering process of nanometric undoped SnO2 powder was studied. No macroscopic shrinkage was observed during the sintening process. Grain growth kinetics investigation showed that surface diffusion is the dominant mechanism in the temperature range 500-1300 degreesC. For temperatures higher than 1300 degreesC, high weight loss was measured, suggesting evaporation-condensation as the dominant mass-transport mechanism. Thermogravimetric analysis (TG) and mass spectroscopy studies showed that the surface contamination of the SnO2 particles by chemical species like H2O, OH- and CO2, has a strong influence on the role of mass transport controlled by surface diffusion. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Sintering mechanisms of ZrO2 center dot MgO with addition of TiO2 and CuO

Substitutions of Ti and Cu in ZrO2.MgO (Z), cause transformation from monoclinic (m) to cubic (c) and tetragonal (t). According to the vacancy model and solid Solution formation models, neither CuO nor TiO2 cause zirconia stabilization, which derives front other phenomena. Data analysis by TMA using the CRH (constant rate of heating) method shows a solid state reaction of ZrO2.MgO.TiO2 (Z.TiO2) demonstrating a dominant mechanism of volume diffusion (n = 1). However, the sintering of ZrO2.MgO.CuO (Z.CuO) shows a viscous flow mechanism (n = 0), a similar phenomena to that of by sintering of glass. Transformations, such as: CuO to Cu2O at 1000 degreesC, ZrO2 (m) to ZrO2 (t) at 1100 degreesC and Cu2O (s) to Cu2O (l) at 1230 degreesC cause successive rearrangements of microstructure inside of region I (sintering process) and lead to interpretation errors when the Bannister equation is used. (C) 2003 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Mechanical properties, hydrophilicity and water activity of starch-gum film: effect of additives and deacetylated xanthan gum

The effect of deacetylated xanthan gum, additives (sucrose, soybean oil, sodium phosphate and propylene glycol) and pH modifications on mechanical properties, hydrophilicity and water activity of cassava starch-xanthan gum films has been studied. Sucrose addition resulted in the highest effect observed on cassava starch films elongation at break. The deacetylated xanthan gum had higher effect on elongation at break when comparing to the acetylated gum, although both gums presented an inferior effect in relation to the obtained with sucrose. However, when comparing to the control and PVC films, lower tensile strength resistance values were observed when adding sucrose. Increased water activity was observed for films added with sucrose, thus, increasing the material biodegradation. Sucrose and deacetylated xanthan gum addition resulted in a slight hydrophilicity increase. (C) 2004 Elsevier Ltd. All rights reserved.

Sintering of ZnO doped SnO2

Dense SnO2 ceramics were obtained by doping with ZnO concentrations varies from 0.5 to 5.0 mel. The obtained powder was isostaticaly pressed to 210MPa in cylindrical shape and sintered from ambient to 1.500 degrees C using constant heating rate of 10 degrees C/min. Densities above 97% were obtained depending on the ZnO doping concentration. A maximum density was reached with the addition of 2 mol%. It can be concluded from shrinkage data and the observed microstructure obtained by SEM that the solid solution limit for ZnO in SnO2 is about 1.0 mol%. Above this concentration the formation of a second ceramic phase is observed.

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.

Sintering and characterization of PLZT (9/65/35)

PLZT(9/65/35) obtained by association between the Pechini method (ZT) and partial oxalate (PLZT) was prepared. The stoichiometric phase and monophasic (cubic) PLZT obtained by calcination did not occur after sintering. The sintering process, by using two stages, caused a liquid phase formation due to a PbO excess (5 and 10 wt%). Samples with high density (similar to 8 g/cm(3)) and optical transparency(similar to 12%) were obtained. However, an equilibrium between the excess of PbO of sample/atmosphere PbO leads to a segregated PbO phase on the boundaries of the microstructure. A diffusion of Zr, Ti and La ions from PLZT to PbO phase promoted a stoichiometric deviation of the matrix and modified the optical and dielectric characteristics. (C) 2000 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Effect of ceria content on the sintering of ZrO2 based ceramics synthesized from a polymeric precursor

Zirconia-ceria powders with ceria concentration varying from 0 to 12 mol% were synthesized using a polymeric precursor route based on the Pechini process. Powder characteristics were evaluated with regard to the crystallite size, BET surface area, phase distribution, nitrogen adsorption/desorption behavior, and agglomeration state. Sintering was studied considering the shrinkage rate, densification, grain size, and phase evolution. It was demonstrated that the synthesis method is effective to prepare nanosized powders of tetragonal zirconia single-phase. Sinterability mainly depended on the agglomeration state of powders and the monoclinic phase content, fully tetragonal zirconia ceramic, with grain size of 2.4 mu m, was obtained after addition of at least 9 mol% ceria and sintering at 1500 degrees C for 4 h. (C) 2000 Elsevier B.V. Ltd. 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.

Structural effects of Li and K additives on the columbite precursor and 0.9PMN-0.1PT powders

Single-phase perovskite 0.9Pb(Mg1/3Nb2/3)O-3-0.1PbTiO(3) (PMN-PT) powders were prepared by using a Ti-modified columbite precursor (MNT) obtained by the polymeric precursor method. The innovation consists in the preparation of Ti-modified columbite in order to react directly with a stoichiometric amount of PbO to obtain pyrochlore-free PMN-PT powders. It has been shown that titanium oxide forms a solid solution with columbite (MN) and does not affect the obtaining of a single-phase columbite precursor. Thus, a high amount of perovskite phase can be obtained by reaction with PbO at 800 degreesC for 2 h. Effects of K and Li additives on the structure of MNT and PMN-PT were studied. X-ray diffraction studies were carried out to verify the phase formation at each processing step and these data were used for structural refinement by the Rietveld method. Both K and Li additives increase the crystallinity of MNT powders, being this effect more intense for the Li-doped samples. For PMN-PT samples the additives cause an insignificant decrease in the amount of perovskite phase. The morphology of the PMN-PT powder depends on the type of the additive. (C) 2003 Elsevier B.V All rights reserved.

The role of oxygen vacancies on the microstructure development and on the electrical properties of SnO2-based varistors

Variations on the microstructure development and on the electrical properties of SnO2-based varistors are discussed on the basis of the oxygen vacancies created or annihilated by the presence of different additives. Electron paramagnetic resonance (EPR) analysis of sintered samples evidenced a substantial increase in the paramagnetic oxygen vacancies concentration when Nb2O5 is added to the SnO2 center dot Co3O4 system. on the other hand, the observed diminution in the concentration of such species after the addition of Fe2O3 indicates solid solution formation. The quantification of paramagnetic oxygen vacancies allowed to confirm the proposed substitutions taking place in the lattice during sintering. These findings are supported by scanning electron microscopy, by density measurements and by current density versus electric field curves. The characterization of secondary phases through EDS assisted SEM and TEM is also reported in this work.

Evaluation of the influences of solution path length and additives concentrations on the solar photo-Fenton degradation of 4-chlorophenol using multivariate analysis

This study reports the photodegradation of 4-chlorophenol (4-CP) in aqueous solution by the photo-Fenton process using solar irradiation. The influence of solution path length, and Fe(NO3)(3) and H2O2 concentrations on the degradation of 4-CP is evaluated by response surface methodology. The degradation process was monitored by the removal of total organic carbon (TOC) and the release of chloride ion. The results showed a very important role of iron concentration either for TOC removal or dechlorination. on the other hand, a negative effect of increasing solution path length on mineralization was observed, which can be compensated by increasing the iron concentration. This permits an adjustment of the iron concentration according to the irradiation exposure area and path length (depth of a tank reactor). Under optimum conditions of 1.5 mM Fe(NO3)(3), 20.0 mM H2O2 and 4.5 cm solution path length, 17 min irradiation under solar light were sufficient to reduce a 72 mg C L-1 solution of 4-CP by 91 (c) 2006 Elsevier B.V. All rights reserved.