Electrical relaxation in proton conductor composites based on (NH4)H2PO4/TiO2

We report on electrical relaxation measurements of (1-x)NH4H2PO4-xTiO(2) (x = 0.1) composites by admittance spectroscopy, in the 40-Hz-5-MHz frequency range and at temperatures between 303 and 563 K. Simultaneous thermal and electrical measurements on the composites identify a stable crystalline phase between 373 and 463 K. The real part of the conductivity, sigma', shows a power-law frequency dependence below 523 K, which is well described by Jonscher's expression sigma' = sigma(0)(1 + (omega/omega(p))(n)), where sigma(0) is the dc conductivity, omega(p)/2 pi = f(p) is a characteristic relaxation frequency, and n is a fractional exponent between 0 and 1. Both sigma(0) and f(p) are thermally activated with nearly the same activation energy in the II region, indicating that the dispersive conductivity originates from the migration of protons. However, activation energies decrease from 0.55 to 0.35 eV and n increases toward 1.0, as the concentration of TiO2 nanoparticles increases, thus, enhancing cooperative correlation among moving ions. The highest dc conductivity is obtained for the composite x = 0.05 concentration, with values above room temperature about three orders of magnitude higher than that of crystalline NH4H2PO4 (ADP), reaching values on the order of 0.1 (Omega cm)(-1) above 543 K.

Nanoscale effects and polaronic relaxation in CaCu3Ti 4O12 compounds

In the present communication, by using dielectric spectroscopy measurement, the correlations between Nanosized Barrier Layer Capacitance (NBLC) (Bueno et al. (2009) [7]) and the high frequency polaronic near-Debye dipolar relaxation found in CaCu3Ti4O12 compounds was discussed. The polaronic process was confirmed to be closely associated with the ultrahigh dielectric features of CaCu3Ti4O12 materials and its concomitant dielectric loss. Herein, the shift in relaxation frequency as a function of temperature was used for calculating the activation energy for hopping electronic conduction. The value obtained was 33 meV, an energy whose magnitude is compatible and confirmed the hypothesis of polaronic features for this high frequency dipolar relaxation process. Furthermore, it is shown that the nanosized barrier inferred from the NBLC model has a polaronic feature with dielectric permittivity exiting orthogonally to dielectric loss, a phenomenological pattern that contradicts the normally observed behavior for traditional dielectrics but explain the dielectric and conductivity feature of CaCu3Ti4O12 compounds. © 2010 Elsevier Ltd. All rights reserved.

Rietveld refinement, microstructure, conductivity and impedance properties of Ba[Zr0.25Ti0.75]O-3 ceramic

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

Análise das interações moleculares em blendas sintéticas tipo biodiesel/diesel por espectroscopia dielétrica e vibracional de absorção na região do infravermelho

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Análise da interação intermolecular em blendas biocombustíveis/petrodiesel do sistema biodiesel-diesel-álcool etílico via propriedades de excesso, espectroscopia de infravermelho e impedância

Pós-graduação em Química - IBILCE

Anelastic relaxation due to hydrogen in Ti-35Nb-7Zr-5Ta alloy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Anelastic Relaxation Measurements in Nb-46wt%Ti Alloys with Interstitial Solutes in Solid Solution

Anelastic relaxation measurements were performed in a Nb-46wt%Ti alloy, in the temperature range of 300 to 700 K, using a torsion pendulum operating at an oscillating frequency near 2.0 Hz. The samples were measured in different conditions: cold worked, annealed in ultra-high vacuum and doped with several quantities of nitrogen. The relaxation spectra obtained were resolved into their component peaks, corresponding to the different kinds of interaction of the interstitial solutes with the metallic matrix. The relaxation parameters of each process were calculated using Debye's elementary peaks.

Dielectric relaxation of vegetable-based polyurethane

Vegetable-based polyurethane (PU) was prepared in the thin film form by spin coating. This polymer is synthesised from castor oil, which can be extracted from the seeds of a native plant in Brazil called mamona. This polymer is biocompatible and is being used as material for artificial bone. The PU was characterised by dielectric spectroscopy in a wide range of frequency (10(-5) Hz to 10(5) Hz) and by thermally stimulated discharge current (TSDC) measurements. The glass transition temperature (T-g=39degreesC) was determined and using the initial rise method the activation energy was found to be 1.58 eV. (C) 2003 Kluwer Academic Publishers.

Stress induced ordering due to interstitial elements in Nb and Ta by frequency analysis

It is well known that the interstitial elements present in solid solution in metals interact with the matrix by a relaxation process known as stress induced ordering. Traditionally this relaxation process is observed in the internal friction measurements. It is a common practice that researchers present the results of the frequency together with internal friction without giving any analysis. In this work we apply an expression which relates the variation of frequency with temperature and analyse the experimental results cited in the literature of the relaxation process due to the stress induced ordering of oxygen and nitrogen present in niobium and tantalum.

Optical spectroscopy and frequency upconversion properties of Tm3+ doped tungstate fluorophosphate glasses

Tungstate fluorophosphate glasses of good optical quality were synthesized by fusion of the components and casting under air atmosphere. The absorption spectra from near-infrared to visible were obtained and the Judd-Ofelt parameters determined from the absorption bands. Transition probabilities, excited state lifetimes and transition branching ratios, were, determined from the measurements. Pumping with a 354.7 nm beam from a pulsed laser. resulted in emission at 450 nm. due to transition D-1(2)-->F-3(4) in Tm3+ ions and a broadband emission centered at approximate to 550 nm attributed to the glass matrix. When pumping at 650 nm, two emission bands at 450 nm (D-1(2)-->F-3(4)) and at 790 nm (H-3(4)-->H-3(6)) were observed. Excitation spectra were also obtained in order to understand the origin of both emissions. Theoretical and experimental lifetimes were determined and,the results were explained in terms of multiphonon relaxation. (C) 2003 American Institute of Physics.

Mechanical and electrical driving field induced high-frequency dielectric anomalies in ferroelectric systems

Polycrystalline or single-crystal ferroelectric materials present dielectric dispersion in the frequency range 100 MHz-1 GHz that has been attributed to a dispersive ( relaxation-like) mechanism as well as a resonant mechanism. Particularly in 'normal' ferroelectric materials, a dielectric response that is indistinguishable from dispersion or a resonance has been reported. Nevertheless, the reported results are not conclusive enough to distinguish each mechanism clearly. A detailed study of the dielectric dispersion phenomenon has been carried out in PbTiO3-based ferroelectric ceramics, with the composition Pb1-xLaxTiO3 (x = 0.15), over a wide range of temperatures and frequencies, including microwave frequencies. The dielectric response of La-modified lead titanate ferroelectric ceramics, in 'virgin' and poled states, has been investigated in the temperature and frequency ranges 300-450 K and 1 kHz-2 GHz, respectively. The results revealed that the frequency dependence of the dielectric anomalies, depending on the measuring direction with respect to the orientation of the macroscopic polarization, may be described as a general mechanism related to an 'over-damped' resonant process. Applying either a uniaxial stress along the measurement field direction or a poling electric field parallel and/or perpendicular to the measuring direction, a resonant response of the real and imaginary components of the dielectric constant is observed, in contrast to the dispersion behavior obtained in the absence of the stress, for the 'virgin' samples. Both results, resonance and/or dispersion, can be explained by considering a common mechanism involving a resonant response (damped and/or over-damped) which is strongly affected by a ferroelastic-ferroelectric coupling, contributing to the low-field dielectric constant.

Internal friction and frequency measurements in molybdenum containing oxygen and nitrogen

We have measured internal friction and frequency as a function of temperature in molybdenum containing oxygen and nitrogen in solid solution. These measurements were performed by a torsion pendulum operating in the temperature range of 300 K to 700 K with oscillation frequency about 1.0 Hz. The results showed the complex relaxation process identifying the stress induced ordering of oxygen and nitrogen atom around the molybdenum atoms of the metallic matrix.

Energy-transfer frequency upconversion in neodymium-sensitized praseodymium-doped PbGeO3-PbF2-CdF2 glass excited at 810 nm

Visible frequency upconversion emission through resonant energy-transfer involving neodymium and praseodymium ions in PbGeO3-PbF2-CdF2 glass excited by a semiconductor laser at 8 10 nm is investigated. Luminescence emission centered around 485, 530, 610, and 645 nm, which correspond to the P-3(0) -> H-3(4), P-3(1) + I-1(6) -> H-3(5), P-3(0) -> H-3(6) and P-1(0) -> F-3(2) transitions of praseodymium ions, respectively, are observed. The upconversion excitation of the Pr3+ ions excited-state emitting levels was accomplished by means of an ion-pair interaction involving ground-state absorption, multiphonon relaxation, and excited-state absorption of pump photons at 8 10 nm by the Nd3+ (I-4(9/2) -> H-2(9/2), F-4(5/2); F-4(3/2) -> P-2(1/2)) and direct energy-transfer to Pr3+ ((4)G(11/2) + K-2(11/2), H-3(4) -> I-4(9/2), P-3(1) + I-1(6)). The dependence of the upconversion emission intensity upon the excitation power, and neodymium concentration are also examined. (c) 2004 Elsevier B.V. All rights reserved.

Nuclear magnetic relaxation of F-19 in fluoride glasses

Temperature and frequency dependence of the F-19 nuclear spin relaxation of the fluoroindate glass, 40InF(3)-20ZnF(2)- 20SrF(2)-2GaF(3)-2NaF-16BaF(2) and the fluorozirconate glass, 50ZrF(4)-20BaF(2)-21LiF-5LaF(3)-4AlF(3); are reported. Measurements were undertaken on pure and Gd3+ doped samples, in the temperature range of 185-1000 K, covering the region below and above the glass transition temperature, T-g. The temperature and frequency dependence of the spin-lattice relaxation rate, T-1(-1), measured in the glassy state at temperature <300 K, is less than the observed dependence at higher temperatures. At temperatures >T-g, the fluorine mobility increases, leading to a more efficient spins lattice relaxation process. Activation energies, for F- motion, are 0.8 eV for the fluoroindate glass and 1 eV for the fluorozirconate glass. The addition of Gd3+ paramagnetic impurities;at 0.1-wt%, does not alter the temperature and frequency dependence of T-1(-1), but increases its magnitude more than one order of magnitude. At temperatures <400 K, the spin-spin relaxation time, T-2(-1), measured for all samples, is determined by the rigid-lattice nuclear dipole-dipole coupling, and it is temperature independent within the accuracy of the measurements. Results obtained for the pure glass, at temperatures >400 K, show that T-2(-1) decreases monotonically as the temperature increases. This decrease is explained as a consequence of the motional narrowing effect caused by the onset of the diffusive motion of the F- ions, with an activation energy around 0.8 eV. For the doped samples, the hyperfine interaction with the paramagnetic impurities is most effective in the relaxation of the nuclear spin, causing an increase in the T(2)(-1)s observed at temperatures >600 K. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Anelastic relaxation processes due oxygen in Nb-3.1 at.% Ti alloys

In the last 50 years several studies have been made to understand the relaxation mechanisms of the heavy interstitial atoms present in transition metals and their alloys. Internal friction measurements have been carried out in a Nb-Ti alloy containing 3.1 at.% of Ti produced by the Materials Department of Chemical Engineering Faculty of Lorena (Brazil), with several quantities of oxygen in solid solution using a torsion pendulum. These measurements have been performed by a torsion pendulum in the temperature range from 300 to 700 K with an oscillation frequency between 0.5 and 10 Hz. The experimental results show complex internal friction spectra that have been resolved, into a series of Debye peaks corresponding to different interactions. For each relaxation process it was possible to obtain the height and temperature of the peak, the activation energy and the relaxation time of the process. (C) 2003 Elsevier B.V. All rights reserved.