Particle growth during calcination of polycation oxides synthesized by the polymeric precursors method

The particle-growth kinetics of sodium niobate and zirconium titanate powders that were processed by the polymeric precursors method were studied. The growth kinetics that were studied for the particle, in the final stage of crystallization, showed that the growth process occurs in two different stages. For temperatures <800°C, the particle-growth mechanism is associated with surface diffusion, with an activation energy in the range of 40-80 KJ/mol. For temprratures >800°C, particle growth is controlled by densification of the nanometric particle cluster and by a neck-size-controlled particle-growth mechanism. The results suggest that this behavior was typical of the synthesis method, because two different polycation oxides presented the same behavior.

Piezoelectric effect in composite polyurethane-ferroelectric ceramics

Flexible and free-standing films of piezoelectric composites made up of lead zirconate titanate (PZT) ceramic powder dispersed in a castor oil-based polyurethane (PU) matrix were obtained by spin coating and characterized as materials for sensor applications. The piezoelectric coefficients d 31 and d 33 were measured with the usual technique. The piezoelectric charge constant d 33 yields values up to ≤24 pC/N, even at lower PZT content (33 vol%). Some desirable properties like piezoelectricity, flexibility and good mechanical resistance show this new material to be a good alternative for use as sensors and actuators.

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.

Preparation and characterization of glass-ceramic materials in the BaO-Li2O-ZrO2-SiO2 system and their dependence on treatment temperatures

The preparation and characterization of transparent glass-ceramics in the composition of 30Li2O:5ZrO2:xBaO:(100-x) SiO2 with x = 0, 5, 10, 15, and 20 mol% are described. Glasses were melted in a platinum crucible at 1100°C for 2 h and then heat-treated at 900°C for 3 h. The characterizations were performed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman and infrared spectroscopy, and scanning electron microscopy (SEM). The experimental results indicate that there was a structural change in the glass-ceramics as the BaO concentration in the mixture increased. In the XRD patterns of samples without heat treatment, only the halo was observed. After heat treatment, the appearance of the materials was verified by X-ray diffraction peaks. The reorganization of the amorphous solid was confirmed by Raman and IR spectroscopy along with XPS and SEM, with a more homogeneous phase formation being observed.

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.

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.

Preparation and characterization of BaBi2Nb2O9(BBN) ceramics synthetized by polymeric precursors method

Pure BBN powders and with addition of 1 and 2 wt% in excess of bismuth were obtained by Pechini Method. The powders calcined at 300°C/4h were analyzed by TG/DTA to study the temperature of organic matter decomposition. A systematic study of calcination temperature and time to the formation of the BBN phase was performed and the phase formation was accompanied by XRD. The calcined powders at 800°C during 2h were analyzed by infrared spectroscopy and by BET. The powders were isostaticaly pressed and sintered at temperatures ranging from 900°C to 1000°C. The ceramics were characterized by XRD to control the crystalline phase and by SEM to analyze the microstructure.

Fractal approach to ac impedance spectroscopy studies of ceramic materials

A novel fractal model for grain boundary regions of ceramic materials was developed. The model considers laterally inhomogeneous distribution of charge carriers in the vicinity of grain boundaries as the main cause of the non-Debye behaviour and distribution of relaxation times in ceramic materials. Considering the equivalent circuit the impedance of the grain boundary region was expressed. It was shown that the impedance of the grain boundary region has the form of the Davidson-Cole equation. The fractal dimension of the inhomogeneous distribution of charge carriers in the region close to the grain boundaries could be calculated based on the relation ds = 1 + β, where β is the constant from the Davidson-Cole equation.

Screen printed barium titanate thick films prepared from mechanically activated powders

Barium titanate thick films were prepared from mechanically activated powders based on BaCO 3 and TiO 2. The thick films were screen-printed on alumina substrates electroded with Ag/Pd. The BT films were sintered at 850°C for 1 hour. The thickness was 30-75 μm depending of number of layers. The microstructure of thick films and the compatibility between BT layers and substrate was investigated by SEM. The dielectric properties were measured and the results were reported.

Influence of barium and strontium addition on the ratio c/a of PZT obtained by the polymeric precursor method

Lead zirconate titanate powder, with Zr/Ti ratio of 50/50 was prepared by Pechini method after adding up to 10,0 mol% of Ba +2 and Sr +2 ions. Tetragonal phase is favored by the increase of barium and strontium concentration in the LiNbO 3 crystal lattice. The ratio c/a for tetragonal phase increases with the content of Ba +2 and Sr +2.

The use of pulsed electric acoustic technique for measuring the polarization reversal in ferroelectric ceramic samples

The pulsed electric acoustic technique, PEA, has been usually applied to probe space charge profiles in polymers. Preliminary PEA results using a ferroelectric ceramic are presented. If the reverse applied electric field i of the order of the coercive field the switching polarization process occurs in a period larger than hundreds of seconds. Such a slow process allows one to use the PEA setup to follow the polarization switching dynamics and determine the electric field profile. The PEA signal obtained in the lead zirconate-titanate doped with niobium ceramic, PZTN, indicates that the polarization distribution and field are not uniform during the switching period. We were also able to observe that the acoustic wave velocity and attenuation depends on the stage of the polarization switching, which agrees with results obtained using the ultrasonic method.

The use of pulsed electric acoustic technique for measuring electric field profiles in ferroelectric ceramic

The pulsed electric acoustic technique, PEA, have been usually applied to probe space charge profiles in polymers. In this work we show preliminary results obtained with lead zirconate-titanate and niobium, PZTN, ferroelectric ceramic samples. Experiments showed that induced charge densities on sample electrodes are mainly due to the ferroelectric polarization of the sample. We present results of the typical PEA response and the procedure to deconvolute the signal in order to obtain the charge densities and the electric field profiles. The PEA setup allows us to show a non-uniform polarization during ferroelectric switching.

Microstructure of doped barium titanate prepared from polymeric precursors

Barium titanate is used extensively as a dielectric in ceramic capacitors, particularly due to its high dielectric constant and low dielectric loss characteristics. It can be made semiconducting by addition of certain dopants and by proper modification of grains and grain boundary properties obtaining very interesting characteristics for various applications. The synthesis method and sintering regime have a strong influence on properties of obtained barium titanate ceramics. Doped barium titanate was prepared with Nb+5 and Y+3 ions as donor dopants, and with Mn+2 ions as acceptor dopant by polymeric precursors method. By this procedure nanosized powders were obtained after calcination. Sintering was performed in the temperature range of 1290°C to 1380°C The microstructure of doped BaTiO3 was performed using scanning electron microscopy. The influence of dopants and sintering temperature on grain size was analysed.

A method for the digital image analysis of ceramic grains based on shape factor segmentation

A very simple and robust method for ceramics grains quantitative image analysis is presented. Based on the use of optimal imaging conditions for reflective light microscopy of bulk samples, a digital image processing routine was developed for shading correction, noise suppressing and contours enhancement. Image analysis was done for grains selected according to their concavities, evaluated by perimeter ratio shape factor, to avoid consider the effects of breakouts and ghost boundaries due to ceramographic preparation limitations. As an example, the method was applied for two ceramics, to compare grain size and morphology distributions. In this case, most of artefacts introduced by ceramographic preparation could be discarded due to the use of perimeter ratio exclusion range.

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.