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.

On-line determination of Sb(III) and total Sb using baker's yeast immobilized on polyurethane foam and hydride generation inductively coupled plasma optical emission spectrometry

The yeast Saccharomyces cerevisiae was immobilized in cubes of polyurethane foam and the ability of this immobilized material to separate Sb(III) and Sb(V) was investigated. A method based on sequential determination of total Sb (after on-line reduction of Sb(V) to Sb(III) with thiourea) and Sb(Ill) (after on-line solid-liquid phase extraction) by hydride generation inductively coupled plasma optical emission spectrometry is proposed. A flow system assembled with solenoid valves was used to manage all stages of the process. The effects of pH, sample loading and elution flow rates on solid-liquid phase extraction of Sb(III) were evaluated. Also, the parameters related to online pre-reduction (reaction coil and flow rates) were optimized. Detection limits of 0.8 and 0.15 mu g L-1 were obtained for total Sb and Sb (III), respectively. The proposed method was applied to the analysis of river water and effluent samples. The results obtained for the determination of total Sb were in agreement with expected values, including the river water Standard Reference Material 1640 certified by the National Institute of Standards and Technology (NIST). Recoveries of Sb(III) and Sb(V) in spiked samples were between 81 19 and I I I 15% when 120 s of sample loading were used. (c) 2006 Elsevier B.V. All rights reserved.

Speciation analysis of Sn(II) and Sn(IV) using baker's yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a substrate to selectively retain Sn(II) and Sn(IV) has been investigated. Several factors affecting the retention of the analytes by yeast, such as pH, amount of biomass, temperature and time of contact were evaluated. Based on this study, a method for determination of Sn(II) and Sn(IV) combining inductively coupled plasma optical emission spectrometry (ICP OES) and solid phase extraction using Saccharomyces cerevisiae is proposed. The procedure consists of the selective retention of Sn(IV) by yeast at pH = 2.0 while Sn(II) remains in solution. Determination of tin in the solid phase was easily carried out by submitting a slurry of the yeast (0.5 g/40 mL) directly to ICP OES. The precision of the extraction procedure was characterized by an RSD lower than 4%. The detection limits of tin (3 sigma) in the solid phase and the liquid phase were 1.1 and 0.7 mu g L-1, respectively. The proposed approach was evaluated for determination of Sn(II) and Sn(IV) in spiked river water and real samples of industrial waste water (untreated and treated). For all samples, recoveries of spiked Sn(II) and Sn(IV) were between 85 and 112%.

Determination of Cd(II) and Cd-metallothioneins in biological extracts using baker's yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a sorbent material to separate Cd(II) and Cd-metallothionein complex (Cd-MT) has been explored. Solid-liquid phase extractions were carried out in batch mode and the main parameters of the process (pH, temperature, time of incubation, amount of biomass and analyte) were evaluated. Under optimized conditions, the yeast quantitatively retain (94 +/- 5%) the Cd(II) while 97 +/- 2% of the Cd-MT remain in the supernatant. on base of the findings of this study, a simple method is proposed to determine Cd(II) and Cd-MT in cytosols extracted from mouse kidney and crab hepatopancreas. Inductively coupled plasma optical emission spectrometry was used to quantify the analytes in solid and liquid phase. Determination of Cd in the solid phase was carried out by introducing a slurry of the yeast (0.0625 g/10 mL) directly to the inductively coupled plasma optical emission spectrometer. Mixed standards solutions, which also have been submitted to the extraction procedure, were used to quantify the analytes in the samples. Thus, matrix effects due to nebulization of the slurry were overcame. Limits of detection (3 sigma) for Cd(II) and Cd-MT were 1.5 and 1.2 mu g L-1, respectively. Relative standard deviations of signals were 4.2% for measurements in the slurry of solid phase and 2.1% for measurements in the liquid phase. Recoveries of the analytes in cytosol samples were between 76 and 114%. The concentrations of Cd(II) (2.4 +/- 0.5 mu g L-1) and Cd-MT (3.0 +/- 0.5 mu g L-1) found by using the proposed approach were close to those found by tangential-flow ultrafiltration technique (2.6 +/- 0.7 mu g L-1 for Cd(II) and 3.7 +/- 1.7 mu g L-1 for Cd-MT).

Electrical conduction mechanism and phase transition studies using dielectric properties and Raman spectroscopy in ferroelectric Pb0.76Ca0.24TiO3 thin films

We have studied the phase transition behavior of Pb0.76Ca0.24TiO3 thin films using Raman scattering and dielectric measurement techniques. We also have studied the leakage current conduction mechanism as a function of temperature for these thin films on platinized silicon substrates. A Pb0.76Ca0.24TiO3 thin film was prepared using a soft chemical process, called the polymeric precursor method. The results showed that the dependence of the dielectric constant upon the frequency does not reveal any relaxor behavior. However, a diffuse character-type phase transition was observed upon transformation from a cubic paraelectric phase to a tetragonal ferroelectric phase. The temperature dependency of Raman scattering spectra was investigated through the ferroelectric phase transition. The soft mode showed a marked dependence on temperature and its disappearance at about 598 K. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive above the phase transition temperature. The origin of these modes must be interpreted in terms of a local breakdown of cubic symmetry by some kind of disorder. The lack of a well-defined transition temperature suggested a diffuse-type phase transition. This result corroborate the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in the thin film. The leakage current density of the PCT24 thin film was studied at elevated temperatures, and the data were well fitted by the Schottky emission model. The Schottky barrier height of the PCT24 thin film was estimated to be 1.49 eV. (C) 2003 American Institute of Physics.

A Raman and dielectric study of a diffuse phase transition in (Pb1-xCax)TiO3 thin films

Dielectric and Raman scattering experiments were performed on polycrystalline Pb1-xCaxTiO3 thin films (x=0.10, 0.20, 0.30, and 0.40) as a function of temperature. The results showed no shift in the dielectric constant (K) maxima, a broadening with frequency, and a linear dependence of the transition temperature on increasing Ca2+ content. on the other hand, a diffuse-type phase transition was observed upon transforming from the cubic paraelectric to the tetragonal ferroelectric phase in all thin films. The temperature dependence of Raman scattering spectra was investigated through the ferroelectric phase transition. The temperature dependence of the phonon frequencies was used to characterize the phase transitions. Raman modes persisted 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 local cubic symmetry due to chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands in some temperature interval above the FE-PE phase transition temperature suggested a diffuse-type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films.

An alternative modal representation of a symmetrical nontransposed three-phase transmission line

The objective of this letter is to propose an alternative modal representation of a nontransposed three-phase transmission line with a vertical symmetry plane by using two transformation matrices. Initially, Clarke's matrix is used to separate the line into components a, 0, and zero. Because a and zero components are not exact modes, they can be considered as being a two-phase line that will be decomposed in its exact modes by using a 2 x 2 modal transformation matrix. This letter will describe the characteristics of the two-phase line before mentioned. This modal representation is applied to decouple a nontransposed three-phase transmission line with a vertical symmetry plane whose nominal voltage is 440 kV.

Modal representation of three-phase lines applying two transformation matrices: Evaluation of its eigenvectors

The objective of this paper is to show an alternative representation in time domain of a non-transposed three-phase transmission line decomposed in its exact modes by using two transformation matrices. The first matrix is Clarke's matrix that is real, frequency independent, easily represented in computational transient programs (EMTP) and separates the line into Quasi-modes alpha, beta and zero. After that, Quasi-modes a and zero are decomposed into their exact modes by using a modal transformation matrix whose elements can be synthesized in time domain through standard curve-fitting techniques. The main advantage of this alternative representation is to reduce the processing time because a frequency dependent modal transformation matrix of a three-phase line has nine elements to be represented in time domain while a modal transformation matrix of a two-phase line has only four elements. This paper shows modal decomposition process and eigenvectors of a nontransposed three-phase line with a vertical symmetry plane whose nominal voltage is 440 kV and line length is 500 km.

Reconstruction of deformed defects in field theory from deformed zero modes and applications

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

On-line redox speciation analysis of antimony using L-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Time Domain Analyses for Three-phase Lines with Corrected Modal Transformation Matrix

The results presented in this paper are based on a research about the application of approximated transformation matrices for electromagnetic transient analyses and simulations in transmission lines. Initially, it has developed the application of a single real transformation matrix for a double three-phase transmission lines, because the symmetry of the distribution of the phase conductors and the ground wires. After this, the same type of transformation matrix has applied for symmetrical single three-phase transmission lines. Analyzing asymmetrical single three-phase lines, it has used three different line configurations. For these transmission line types, the errors between the eigenvalues and the approximated results, called quasi modes, have been considered negligible. on the other hand, the quasi mode eigenvalue matrix for each case was not a diagonal one. and the relative values of the off-diagonal elements of the approximated quasi mode matrix are not negligible, mainly for the low frequencies. Based on this problem, a correction procedure has been applied for minimizing the mentioned relative values. For the correction procedure application, symmetrical and asymmetrical single three-phase transmission line samples have been used. Checking the correction procedure results, analyses and simulations have been carried out in mode and time domain. In this paper, the last results of mentioned research are presented and they related to the time domain simulations.

Study of phase transition in (Pb,Ba)TiO(3) thin films

Dielectric and Raman scattering experiments were performed on polycrystalline Pb(1-x)Ba(x)TiO(3) thin films (x=0.40 and 0.60) as a function of temperature. The dielectric study on single phase compositions revealed that a diffuse-type phase transition occurred upon transformation of the cubic paraelectric to the tetragonal ferroelectric phase in all thin films, which showed a broadening of the dielectric peak. Diffusivity was found to increase with increasing barium contents in the composition range under study. In addition, the temperature dependence of Raman scattering spectra was investigated through the ferroelectric phase transition. The temperature dependence of the phonon frequencies was used to characterize the phase transitions. Raman modes persisted above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted as a breakdown of the local cubic symmetry by chemical disorder. The lack of a well-defined transition temperature and the presence of broadbands in some temperature intervals above the paraferroelectric phase transition temperature suggest a diffuse-type phase transition. (C) 2008 American Institute of Physics.

Non-transposed three-phase line analyses with a single real transformation matrix

In transmission line transient analyses, a single real transformation matrix can obtain exact modes when the analyzed line is transposed. For non-transposed lines, the results are not exact. In this paper, non-symmetrical and non transposed three-phase line samples are analyzed with a single real transformation matrix application (Clarke's matrix). Some interesting characteristics of this matrix application are: single, real, frequency independent, line parameter independent, identical for voltage and current determination. With Clarke's matrix use, mathematical simplifications are obtained and the developed model can be applied directly in programs based on time domain. This model works without convolution procedures to deal with phase-mode transformation. In EMTP programs, Clarke's matrix can be represented by ideal transformers and the frequency dependent line parameters can be represented by modified-circuits. With these representations, the electrical values at any line point can be accessed for phase domain or mode domain using the Clarke matrix or its inverse matrix. For symmetrical and non-transposed lines, the model originates quite small errors. In addition, the application of the proposed model to the non-symmetrical and non-transposed three phase transmission lines is investigated. ©2005 IEEE.

Modal representation of three-phase lines applying two transformation matrices: Evaluation of its eigenvectors

The objective of this paper is to show an alternative representation in time domain of a non-transposed three-phase transmission line decomposed in its exact modes by using two transformation matrices. The first matrix is Clarke's matrix that is real, frequency independent, easily represented in computational transient programs (EMTP) and separates the line into Quasi-modes α, β and zero. After that, Quasi-modes a and zero are decomposed into their exact modes by using a modal transformation matrix whose elements can be synthesized in time domain through standard curve-fitting techniques. The main advantage of this alternative representation is to reduce the processing time because a frequency dependent modal transformation matrix of a three-phase line has nine elements to be represented in time domain while a modal transformation matrix of a two-phase line has only four elements. This paper shows modal decomposition process and eigenvectors of a non-transposed three-phase line with a vertical symmetry plane whose nominal voltage is 440 kV and line length is 500 km. ©2006 IEEE.

Correction procedure applied to a single real transformation matrix -Untransposed three-phase transmission line cases

Clarke's matrix has been used as an eigenvector matrix for transposed three-phase transmission lines and it can be applied as a phase-mode transformation matrix for transposed cases. Considering untransposed three-phase transmission lines, Clarke's matrix is not an exact eigenvector matrix. In this case, the errors related to the diagonal elements of the Z and Y matrices can be considered negligible, if these diagonal elements are compared to the exact elements in domain mode. The mentioned comparisons are performed based on the error and frequency scan analyses. From these analyses and considering untransposed asymmetrical three-phase transmission lines, a correction procedure is determined searching for better results from the Clarke's matrix use as a phase-mode transformation matrix. Using the Clarke's matrix, the relative errors of the eigenvalue matrix elements can be considered negligible and the relative values of the off-diagonal elements are significant. Applying the corrected transformation matrices, the relative values of the off-diagonal elements are decreased. The comparisons among the results of these analyses show that the homopolar mode is more sensitive to the frequency influence than the two other modes related to three-phase lines. © 2006 IEEE.