Sinterização e caracterização de segunda fase em sistemas SnO2-ZnO

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Synthesis and sintering of PZT ceramics

Lead zirconate powder, with Zr/Ti ratio of 50/50 was prepared by polymeric precursor method and doped with 3, 5 and 7 mol% of Sr+2 Or Ba+2, as well as by 0.2 to 5 mol% of Nb+5. The powder was calcined at 750 degrees C by 4 hours and milled during 1.5 h in isopropilic alcohol. Powders were characterized by surface area measurements (BET method), by infrared spectroscopy and by X-ray diffraction to characterize the crystal structure. Isostatically pressed samples were sintered in a dilatometer furnace by using a constant heating rate of 10 degrees C/min from ambient to 1200 degrees C. Synthetic air and air with water vapor were used as atmospheres. Both Sr+2 and Ba+2 substitute Pb+2 and favor the formation of rhombohedral phase. Otherwise, Nb+5 substitute preferentially Zr+4 favoring tetragonal phase. The concentration of dopants and the atmosphere influence the densification and the microstructure of the PZT, which alters the dielectric and piezoelectric properties of the ceramics.

WO3 and ZnO-doped SnO2 ceramics as insulating material

SnO2 ceramics doped with ZnO and WO3 were prepared by mixed oxide method. The effect of ZnO and WO3 additives could be explained by the substitution of Sn4+ by Zn2+ and W6+. The addition of WO3 inhibits the grain growth due to the segregation of SnZnWO8 and ZnWO6 at the grain boundaries without strong influence on the densification process. The electrical characterization (log E x log J) shows that the ternary system SnO2-ZnO-WO3 exhibits a very high resistivity of around 10(14) Omega M. Independently of the WO3 concentration, the electrical conductivity of the Sn02-ZnO-WO3 system is always lower than that of the undoped tin dioxide. (C) 2005 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

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.

Effect of La2O3 doping on the microstructure and electrical properties of a SnO2-based varistor

The effect of La2O3 addition on the densification and electrical properties of the (0.9895 - x) SnO2 + 0.01 CoO + 0.0005 Nb2O5 + x La2O5 system, where x = 0.0005 or 0.00075, was considered in this study. The samples were sintered at 1300 degreesC for 2 and 4 h and a single SnO2 phase was identified by X-ray diffraction. Microstructure analysis by scanning electron microscopy showed that the affect of La2O3 addition is to decrease the SnO2 grain size. J versus E curves indicated that the system exhibits a varistor behavior and the effect of La2O3 is to increase both the non-linear coefficient (alpha) and the breakdown voltage (E-2). Considering the Schottky thermionic emission model the potential height and the width were estimated. The addition of small amounts of La2O3 to the basic system increases the potential barrier height and decreases both grain size and potential barrier width. (C) 2001 Kluwer Academic Publishers.

Er3+/Yb3+ co-activated silica-alumina monolithic xerogels

Monolithic silica xerogels doped with different concentrations of Er3+, Yb3+ and Al3+ were prepared by sol-gel route. Densification was achieved by thermal treatment in air at 950degreesC for 120 h with a heating rate of 0.1degreesC/min. We studied the luminescence properties of the I-4(13/2)-->I-4(15/2) emission band of Er3+ as a function of the Al/Er/Yb concentration and we paid particular attention to the alumina effects. Raman spectroscopy and Vis-NIR absorption were used to monitor the degree of densification of the glasses and the residual OH content.

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.

Clustering of rare earth in glasses, aluminum effect: experiments and modeling

Luminescent spectra of Eu3+-doped sol-gel glasses have been analyzed during the densification process and compared according to the presence or not of aluminum as a codoping ion. A transition temperature from hydrated to dehydroxyled environments has been found different for doped and codoped samples. However, only slight modifications have been displayed from luminescence measurements beyond this transition. To support the experimental analysis, molecular dynamics simulations have been performed to model the doped and codoped glass structures. Despite no evidence of rare earth clustering reduction due to aluminum has been found, the modeled structures have shown that the luminescent ions are mainly located in aluminum-rich domains. The synthesis of both experimental and numerical analyses has lead us to interpret the aluminum effect as responsible for differences in structure of the luminescent sites rather than for an effective dispersion of the rare earth ions. (C) 2004 Elsevier B.V. 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.

Effect of Fe2O3 doping on the electrical properties of a SnO2 based varistor

The effect of Fe2O3 addition on the densification and electrical properties of the (0.9895 - x) SnO2 + 0.01CoO + 0.005Nb(2)O(5) + xFe(2)O(3) system, where x = 0.005 or 0.01, was considered in this study. The samples were sintered at 1300degreesC for 2 h. Microstructure analysis by scanning electron microscopy showed that the effect of Fe2O3 addition is to decrease the SnO2 grain size. J x E curves indicated that the system exhibit a varistor behavior and the effect of Fe2O3 is to increase both, the non-linear coefficient (alpha) and the breakdown voltage (E-r). Considering the Schottky thermionic emission model the potential height and width were estimated. Small amount addition of Fe2O3 to the basic system increases both the potential barrier height and width. (C) 2002 Kluwer Academic Publishers.

Erbium-activated HfO2-based waveguides for photonics

Silica-based sol-gel waveguides activated by Er3+ ions are attractive materials for integrated optic devices. 70SiO(2)-30HfO(2) planar waveguides, doped with Er3+ concentrations ranging from 0.01 to 4 mol%, were prepared by sol-get route. The films were deposited on v-SiO2 and silica-on-silicon substrates, using dip-coating technique. The waveguides show a homogeneous surface morphology, high densification degree and uniform refractive index across the thickness. Emission in the C-telecommunication band was observed at room temperature for ill the samples upon excitation at 980 nm. The shape is found to be almost independent on erbium content, with a FWHM between 44 and 48 nm. The I-4(13/2) level decay curves presented a single-exponential profile, with a lifetime ranging between 1.1 and 6.7 ms, depending on the erbium concentration. The waveguide deposited on silica-on-silicon substrate supports one single propagation mode at 1.5 mum with a confinement coefficient of 0.85, and a losses of about 0.8 dB/cm at 632.8 nm. (C) 2003 Elsevier B.V. All rights reserved.

Structural and microstructural behaviour of SnO2 dense ceramics doped with ZnO and WO3

SnO2-based varistors doped with ZnO and WO3 were prepared by mixed oxide method. Experimental evidence shows that the increase in ZnO amount increases the volume and microstrain of unit cell while the WO3 promotes a decrease. The effect of ZnO and WO3 additives could be explained by the substitution of Sn4+ by Zn2+ and W6+. The addition of WO3 inhibits the grain growth due to the segregation in the grain boundary without influence in the densification of the samples. Besides that, an increase in the electrical resistance of the SnO2-ZnO-WO3 system was observed independent of the WO3 concentration. (c) 2005 Elsevier B.V. All rights reserved.

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.

Dielectric properties of Na1-xLixNbO3 ceramics from powders obtained by chemical synthesis

Ultra-fine powders of Na1-xLixNbO3 (x=0; 0.06; 0.09; 0.12) were synthesized by the Polymeric Precursors Method. Such powders had their orthorhombic structures determined by X-ray diffraction and their surface area determined by BET isotherms (less than 10 m(2) g(-1)). Densification was followed by dilatometric study. The powders, calcined at 700 degrees C for 5 h, were sintered at 1290 degrees C during 2 h under ambient atmosphere with no application of extra pressure. The samples with relative densities higher than 95% were analyzed by impedance spectroscopy at room temperature, under a signal amplitude of 1 V-rms. Dielectric constants of about 180 and dielectric loss factor of about 0.03 were measured showing small dependence with frequency. The electrical properties were similar to those obtained for samples sintered by hot pressing. (C) 1999 Elsevier B.V. Limited and Techna S.r.l. 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.