Electrical characterization of lead zirconate titanate prepared by organic solution route

Two series of lead zirconate titanate (PZT) ceramics with composition Zr/Ti approximate to 53/47 have been prepared by the organic solution route. The effects on the electrical properties of calcination temperature in one series and of sintering time period in the other were examined. Dielectric constant, electrical conductivity and impedance spectroscopy results differed from one series to the other, probably due to differences in structure of the precursor powders, as seen by X-ray diffraction. Tetragonal and rhombohedral phases predominate in the powders used, respectively, in the calcined and sintered series. Physical and electrical behavior of ceramics prepared from predominantly rhombohedral powder suggests the evaporation of PbO. The presence of two semi-circles in impedance plots leads to the association of the low frequency semi-circle to the presence of PbO, which, apparently, was not eliminated from ceramics prepared from predominantly tetragonal powder. (C) 2001 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Microstructural, dielectric and ferroelectric properties of calcium-modified lead titanate thin films derived by chemical processes

Ferroelectric Pb1-xCaxTiO3 (x = 0.24) thin films were formed on a Pt/Ti/SiO2/Si substrate by the polymeric precursor method using the dip-coating technique for their deposition. Characterization of the films bq X-ray diffraction showed a perovskite single phase with a tetragonal structure after annealing at 700 degreesC. Atomic force microscopy (AFM) analyses showed that the film had a smooth and crack-free surface with low surface roughness. In addition, the PCT thin film had a granular structure with an 80 nm grain size. The thickness of the films observed by the scanning electron microscopy (SEM) is 550 nm and there is a good adhesion between the film and substrate. For the electrical measurements metal-ferroelectric-metal of the type capacitors were obtained, where the thin films showed good dielectric and ferroelectric properties. The dielectric constant and dissipation factor at 1 kHz and measured at room temperature were found to be 457 and 0.03. respectively. The remanent polarization and coercive field for the: deposited films were P-r = 17 muC/cm(2) and E-c = 75 kV/cm, respectively. Moreover. The 550-nm-thick film showed a current density in the order of 10(-8) A/cm(2) at the applied voltage of 2 V. The high values of the thin film's dielectric properties are attributed to its excellent microstructural quality and the chemical homogeneity obtained by the polymeric precursor method. (C) 2001 Elsevier science Ltd. All rights reserved.

Electric measurements with constant current: A practical method for characterizing dielectric films

This article assesses the use of the constant current (CC) method for characterizing dielectric films. The method is based on charging the sample with a constant current (current stress) and measuring the corresponding voltage rise under the closed circuit condition. Our article shows that the CC method is an alternative to the constant voltage stressing method to study the electric properties of nonpolar, ferroelectric, and polar polymers. The method was tested by determining the dielectric constant of polytetrafluoroethylene, and investigating the electric conduction in poly(ethylene terephthalate). For the ferroelectric polymer poly(vinylidene fluoride), it is shown that hysteresis loops and the dependence of the ferroelectric polarization on the electric field can be obtained. (C) 2001 American Institute of Physics.

A sensor for monitoring the volume of nutrient in a solid substrate-based growth media by using electrochemical admittance spectroscopy

A sensor was fashioned to monitor the volume of nutrient in a solid substrate-based growth media by using electrochemical admittance spectroscopy. Several experimental parameters were investigated (i.e. The use of two- or three-electrode cells, the superficial area of the electrode, the amount of nutrient solution added to the growth media, and the influence of varying the dc and ac potential) to assess how these variables affect the admittance of the system. A linear correlation was observed between the maximum of the imaginary admittance and the volume of nutrient present. The response factor was 2.8 x 10(-5) S cm(-2) ml(-1) and the limit of detection (LOD) was 0.54 ml. The humidity of the growth media does not change the response of the nutrient toward the monitoring measurements. These results demonstrate that the volume of nutrient in this solid substrate-based growth media can be assessed using a ceramic sensor to measure the imaginary admittance. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Improvement of the dielectric and ferroelectric properties in superlattice structure of Pb(Zr,Ti)O-3 thin films grown by a chemical solution route

Making heterolayered perovskite materials constitutes an approach for the creation of better dielectric and ferroelectric properties. In the experiment reported here, heterolayered PZT40/PZT60 films were grown on Pt/Ti/SiO2/Si (100) by a chemical solution deposition. The dielectric constant of the heterolayered thin film was significantly enhanced compared with that of pure PZT40 and PZT60 thin films. A dielectric constant of 701 at 100 kHz was observed for a stacking periodicity of six layers having a total thickness of 150 nm. The heterolayered film exhibited greater remanent polarization than PZT60 and PZT40 films. The values of remanent polarization were 7.9, 18.5, and 31 muC/cm(2), respectively, for pure PZT60, PZT40, and heterolayered thin films, suggesting that the superior dielectric and ferroelectric properties of the heterolayered thin film resulted from a cooperative interaction between the ferroelectric phases made from alternating tetragonal and rhombohedral phases of PZT, simulating the morphotropic phase boundary of this system. (C) 2004 American Institute of Physics.

Investigation of phase transition in ferroelectric Pb0.70Sr0.30TiO3 thin films

We have carried out dielectric and Raman spectroscopy studies at the 298-623 K temperature range in polycrystalline Pb0.70Sr0.30TiO3 thin films grown by a soft chemical method. The diffuse phase-transition behavior of the thin films was observed by means of the dielectric constant versus temperature curves, which show a broad peak. Such behavior was confirmed later by Raman spectroscopy measurements up to 823 K, indicating that a diffuselike phase transition takes place at around 548-573 K. The damping factor of the E(1TO) soft mode was calculated using the damped simple harmonic oscillator model. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of a breakdown of the microscopic local cubic symmetry by chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands at some temperature interval above the ferroelectric-paraelectric phase-transition temperature suggested a diffuse nature of the phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in this thin film. (C) 2004 American Institute of Physics.

Absence of relaxor-like ferroelectric phase transition in (Pb,Sr)TiO3 thin films

We have performed dielectric and micro-Raman spectroscopy measurements in the 298 - 673 K temperature range in polycrystalline Pb0.50Sr0.50TiO3 thin films prepared by a soft chemical method. The phase transition have been investigated by dielectric measurements at various frequencies during the heating cycle. It was found that the temperature corresponding to the peak value of the dielectric constant is frequency-independent, indicating a non-relaxor ferroelectric behavior. However, the dielectric constant versus temperature curves associated with the ferroelectric to paraelectric phase transition showed a broad maximum peak at around 433 K. The observed behavior is explained in terms of a diffuse phase transition. The obtained Raman spectra indicate the presence of a local symmetry disorder, due to a higher strontium concentration in the host lattice. The monitoring of some modes, conducted in the Pb0.50Sr0.50TiO3 thin films, showed that the ferroelectric tetragonal phase undergoes a transition to the paraelectric cubic phase at around 423 K. However, the Raman activity did not disappear, as would be expected from a transition to the cubic paraelectric phase. The strong Raman spectrum observed for this cubic phase is indicative that a diffuse-type phase transition is taking place. This behavior is attributed to distortions of the perovskite structure, allowing the persistence of low-symmetry phase features in cubic phase high above the transition temperature. This result is in contrast to the forbidden first-order Raman spectrum, which would be expected from a cubic paraelectric phase, such as the one observed at high temperature in pure PbTiO3 perovskite.

Determination of furosemide in pharmaceutical formulations by diffuse reflectance spectroscopy

In this report an analytical method to determine furosemide by using diffuse reflectance spectroscopy is presented. This study shows that this technique can give quantitative results using spot test analysis, particularly in the case of pharmaceuticals containing furosemide. The color spot test could be obtained by reaction between furosemide with p-dimethylaminocinnamaldehyde, in acid medium. This reaction produced a stable complex on filter paper after heating to 80degreesC for 5 min. All reflectance measurements were carried out at 585 nm and the linear range was from 7.56 x 10(-3) to 6.05 x 10(-2) mol l(-1), with a correlation coefficient of 0.999. The limit of detection was estimated to be 2.49 x 10(-3) mol l(-1) (R.S.D. = 1.7%) and the effect of common excipients on the reflectance measurements was evaluated. The method was applied to determine furosemide in commercial brands of pharmaceuticals. The results obtained by the proposed method were favorably compared with those of the official method, showing for the first time ever that quantitative spot test analysis by diffuse reflectance could be successfully used to determine furosemide in tablets. (C) 2004 Elsevier B.V. All rights reserved.

Phase transition in poly(vinylidene fluoride) investigated with micro-Raman spectroscopy

The phase transition from the non-polar a-phase to the polar beta-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous because it is a nondestructive technique. Films of alpha-PVDF were subjected to stretching under controlled rates at 80 degrees C, while the transition to P-PVDF was monitored by the decrease in the Raman band at 794 cm(-1) characteristic of the a-phase, along with the concomitant increase in the 839 cm-1 band characteristic of the P-phase. The alpha ->beta transition in our PVDF samples could be achieved even for the sample stretched to twice (2 X -stretched) the initial length and it did not depend on the stretching rate in the range between 2.0 and 7.0 mm/min. These conclusions were corroborated by differential scanning calorimetry (DSC) and X-ray diffraction experiments for PVDF samples processed under the same conditions as in the Raman scattering measurements. Poling with negative corona discharge was found to affect the a-PVDF morphology, improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, i.e., X-ray diffraction and infrared spectroscopy.

Use of impedance spectroscopy in the study of the effect of Cr concentration on the electrical properties of SnO2-based ceramics

This paper reports a study of influence of Cr concentration on the electrical properties and microstructure of SnO2-based powders doped with Mn and Nb, prepared by an organic route (Pechini method). All the samples were compacted into discs and sintered at 1300 degrees C for 3h, resulting in ceramics with relative density varying between 78% and 98%. The powders were characterized by X-ray diffraction analysis. Impedance spectroscopy characterization indicated that the conductivity decreases as Cr concentration increases, probably due to Cr segregation at grain boundaries, which reduces grain size, increasing the number of resistive boundaries.

Characterization of humic acids from a Brazilian Oxisol under different tillage systems by EPR, C-13 NMR, FTIR and fluorescence spectroscopy

The importance of soil organic matter functions is well known, but structural information, chemical composition and changes induced by anthropogenic factors such as tillage practices are still being researched. In the present paper were characterized Brazilian humic acids (HAs) from an Oxisol under different treatments: conventional tillage/maize-bare fallow (CT1); conventional tillage/maize rotation with soybean-bare fallow (CT2)-, no-till/maize-bare fallow (NT1); no-till/maize rotation with soybean-bare fallow (NT2); no-till/maize-cajanus (NT3) and no cultivated soil under natural vegetation (NC). Soil HA samples were analyzed by electron paramagnetic resonance (EPR), solid-state C-13 nuclear magnetic resonance (C-13 NMR), Fourier transform intra-red (FTIR) and UV-Vis fluorescence spectroscopies and elemental analysis (CHNS). The FTIR spectra of the HAs were similar for all treatments. The level of semiquinone-type free radical determined from the EPR spectra was lower for treatments no-till/maize-cajanus (NT3) and noncultivated soil (1.74 X 10(17) and 1.02 x 10(17) spins g(-1) HA, respectively), compared with 2.3 X 10(17) spins g(-1) HA for other soils under cultivation. The percentage of aromatic carbons determined by C-13 NMR also decreases for noncultivated soil to 24%, being around 30% for samples of the other treatments. The solid-state C-13 NMR and EPR spectroscopies showed small differences in chemical composition of the HA from soils where incorporation of vegetal residues was higher, showing that organic matter (OM) formed in this cases is less aromatic. The fluorescence intensities were in agreement with the percentage of aromatic carbons, determined by NMR (r = 0.97 P < 0.01) and with semiquinone content, determined by EPR (r = 0.97 P < 0.01). No important effect due to tillage system was observed in these areas after 5 years of cultivation. Probably, the studied Oxisol has a high clay content that offers protection to the clay-Fe-OM complex against strong structural alterations. (C) 2003 Elsevier B.V. All rights reserved.

Oxidative dissolution of chalcopyrite by Acidithiobacillus ferrooxidans analyzed by electrochemical impedance spectroscopy and atomic force microscopy

The microbiological leaching of chalcopyrite (CuFeS2) is of great interest because of its potential application to many CuFeS2-rich ore materials. However, the efficiency of the microbiological process is very limited because this mineral is one of the most refractory to bacterial attack. Knowledge of bacterial role during chalcopyrite oxidation is very important in order to improve the efficiency of bioleaching operation. The oxidative dissolution of a massive chalcopyrite electrode by Acidithiobacillus ferrooxidans was evaluated by electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM). A massive chalcopyrite electrode was utilized in a Tait-type electrochemical cell in acid medium for different immersion times in the presence or absence of bacterium. The differences observed in the impedance diagrams were correlated with the adhesion process of bacteria on the mineral surface. (C) 2004 Elsevier B.V. All rights reserved.

Microstructure and dielectric properties of (Ba,Sr)TiO3 thin film produced by the polymeric precursor method

BaxSr1-xTiO3 (x = 0.6) (BST) thin films were successfully prepared on a Pt(111)/TiO2/SiO2/Si(100) substrate by spin coating, using the polymeric precursor method. BST films with a perovskite single phase were obtained after heat treatment at 700 degrees C. The multilayer BST thin films had a granular structure will a grain size of approximately 60 nm. A 480-nm-thick film was obtained by carrying out five cycles of the spin-coating/heating process. Scanning electron microscopy and atomic force microscopy analyses showed that the thin films had a smooth, dense, crack-free surface with low surface roughness (3.6 nm). At room temperature and at a frequency of 100 kHz, the dielectric constant and the dissipation factor were, respectively, 748 and 0.042. The high dielectric constant value was due to the high microstructural quality and chemical homogeneity of the thin films obtained by the polymeric precursor method.

Ferroelectric and optical properties of Ba0.8Sr0.2TiO3 thin film

Barium strontium titanate (Ba0.8Sr0.2TiO3) thin films have been prepared on Pt/Ti/SiO2/Si substrates using a soft solution processing. X-ray diffraction and also micro-Raman spectroscopy showed that the Ba0.8Sr0.2TiO3 thin films exhibited a tetragonal structure at room temperature. The presence of Raman active modes was clearly shown at the 299 and 725 cm(-1) peaks. The tetragonal-to-cubic phase transition in the Ba0.8Sr0.2TiO3 thin films is broadened, and suppressed at about 35 degreesC, with a maximum dielectric constant of 948 (100 kHz). Electrical measurements for the prepared Ba0.8Sr0.2TiO3 thin films showed a remnant polarization (P-r) of 6.5 muC/cm(2), a coercive field (E-c) of 41 kV/cm, and good insulating properties. The dispersion of the refractive index is interpreted in terms of a single electronic oscillator at 6.97 eV. The direct band gap energy (E-g) and the refractive index (n) are estimated to be 3.3 eV and n = 2.27-2.10, respectively. (C) 2002 American Institute of Physics.

High dielectric constant of SrTiO3 thin films prepared by chemical process

SrTiO3 thin films were prepared by the polymeric precursor method and deposited by spin-coating onto Pt/Ti/SiO2/Si(100) substrates. The spin-coated films heat treated at 700 degrees C were crack-free, dense, and homogeneous. Microstructural and morphological evaluations were followed by grazing incident X-ray, scanning electron microscopy and atomic force microscopy. Dielectric studies indicated a dielectric constant of about 475, which is higher than that of ceramic SrTiO3, and a factor dissipation of about 0.050 at 100 kHz. SrTiO3 thin films were found to have paraelectric properties with C-V characteristics. (C) 2000 Kluwer Academic Publishers.