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.

A Lagrangian relaxation approach to a coupled lot-sizing and cutting stock problem

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Dielectric relaxation and dc conductivity on the PVOH-CF(3)COONH(4) polymer system

In the present paper, the ionic conductivity and the dielectric relaxation properties on the poly(vinyl alcohol)-CF(3)COONH(4) polymer system have been investigated by means of impedance spectroscopy measurements over wide ranges of frequencies and temperatures. The electrolyte samples were prepared by solution casting technique. The temperature dependence of the sample's conductivity was modeled by Arrhenius and Vogel-Tammann-Fulcher (VTF) equations. The highest conductivity of the electrolyte of 3.41x10 (-aEuro parts per thousand 3) (Omega cm) (-aEuro parts per thousand 1) was obtained at 423 K. For these polymer system two relaxation processes are revealed in the frequency range and temperature interval of the measurements. One is the glass transition relaxation (alpha-relaxation) of the amorphous region at about 353 K and the other is the relaxation associated with the crystalline region at about 423 K. Dielectric relaxation has been studied using the complex electric modulus formalism. It has been observed that the conductivity relaxation in this polymer system is highly non-exponential. From the electric modulus formalism, it is concluded that the electrical relaxation mechanism is independent of temperature for the two relaxation processes, but is dependent on composition.

Relaxation-chaos phenomena in celestial mechanics. I. On wisdom's model for the 3/1 kirkwood gap

Sudden eccentricity increases of asteroidal motion in 3/1 resonance with Jupiter were discovered and explained by J. Wisdom through the occurrence of jumps in the action corresponding to the critical angle (resonant combination of the mean motions). We pursue some aspects of this mechanism, which could be termed relaxation-chaos: that is, an unconventional form of homoclinic behavior arising in perturbed integrable Hamiltonian systems for which the KAM theorem hypothesis do not hold. © 1987.

Anelastic relaxation due to OH pairs in NbZr alloys

In the last 30 years several studies have been made to understand the relaxation mechanisms of the hydrogen atoms present in transition metals and their alloys. In this work, we observed the stress-induced ordering of hydrogen atoms around the interstitial oxygen atoms near the niobium matrix atoms. We studied this relaxation process by measuring the attenuation of longitudinal ultrasonic waves. These measurements were made in Nb1.0%Zr polycrystalline alloys at 10 and 30 MHz, pure and doped with 0.7 and 4.2 at.% hydrogen. The results revealed a thermally activated relaxation structure around 202 K and 235 K for 10 MHz and 30 MHz respectively. This relaxation structure increases with increasing hydrogen concentration. © 1994.

Uniaxial stress relaxation measurement in fluoroindate glasses

Glasses of composition 40InF3-20SrF2-16BaF2-20ZnF 2-2GdF3-2NaF (mol%) have been prepared under controlled atmosphere. The time response of the stresses under the application of a constant strain was determined by microellipsometer technique, performed in ambient atmosphere at T < Tg = 294°C. The glasses show a Newtonian behavior at small stress level. During the relaxation process, very small grooves perpendicular to the applied strain appeared on the glass surface and affected its behavior after a time. The formation of these grooves is associated with the ambient atmosphere. Measurements in dry atmosphere showed that humidity was an important parameter in the relaxation process.

Electric and magnetic properties of polymer electrolyte/carbon black composites

Measurements of 1H Nuclear Magnetic Resonance (NMR) relaxation times, Electron Paramagnetic Resonance (EPR) and AC Impedance Spectroscopy (IS) are reported for composites based on PEO8:LiClO4 and carbon black (CB), prepared by two methods: solvent and fusion processing. Three nuclear relaxation processes were identified for 1H nuclei: (i) belonging to the polymer chains in the amorphous phase, loosely bound to the CB particles, whose dynamics is almost the same as for unfilled polymer, (ii) belonging to the polymer chains which are tightly attached to the CB particles, and (iii) belonging to the crystalline phase in the loose polymer chain. The paramagnetic electronic susceptibility of the composite samples, measured by EPR, was interpreted by assuming a contribution of localized spin states that follow a Curie law, and a Pauli-like contribution of delocalized spins. A significant change of the EPR linewidth was observed at 40 K, which is the temperature where the Curie and Pauli susceptibilities equally contribute to the paramagnetic electronic susceptibility. The electrical properties are very sensitive to the preparation methods of the composites, which conditions the interaction between carbon particle-carbon particle and carbon particle-polymer chain. Classical statistic models to describe the conductivity in these media were not satisfactory. © 1998 Published by Elsevier Science B.V. All rights reserved.

Relaxation effects on the negatively charged Mg impurity in zincblende GaN

The electronic structure of Mg impurity in zincblende (c-)GaN is investigated by using the ab initio full potential linear-augmented plane-wave method and the local density-functional approximation. Full geometry optimization calculations, including nearest and next-nearest neighbor displacements, are performed for the impurity in the neutral and negatively charged states. A value of 190 ± 10 meV was obtained for the Franck-Condon shift to the thermal energy, which is in good agreement with that observed in recent low temperature photoluminescence and Hall-effect measurements. We conclude that the nearest and next-nearest neighbors of the Mg impurity replacing Ga in C-GaN undergo outward relaxations which play an important role in the determination of the center acceptor energies.

Light-induced electric dipole relaxation in synthetic and natural alexandrite

We present results of thermally stimulated depolarization current (TSDC) measurements in synthetic and natural alexandrite, which show TSDC bands related to the presence of electric dipoles in both types of samples. Synthetic material shows a wide TSDC band with a peak at 179 K, which can be fitted by two distinct relaxing dipole distributions. For natural alexandrite the TSDC band has a maximum around 195 K and can be fitted by three different distributions. Both samples present one of the calculated curves with a peak about 179 K, with activation energy of 0.57 eV and constant relaxation time of 1 × 10-14 sec. Photo-induced TSDC shows that TSDC bands can also be generated by simultaneous application of light and an electric field at 77 K.

Effects of thermal treatment on phase transitions and on the mechanical relaxation in poly(vinylidene fluoride)

This work reports on the effects from thermal treatment in poly(vinylidene fluoride), PVDF, obtained with differential scanning calorimetry (DSC) and dynamic thermal analysis (DMA) measurements. It is shown that in successive DMA measurements performed with one sample the α relaxation peak almost disappears while the γ′ peak appears. The α relaxation peak, at ∼100°C in DMA measurements, is attributed to the preferential orientation of chains in the amorphous phase while the γ′ relaxation peak, at ∼50°C, is related to the thermal treatment to which the sample was submitted.

Conformational basis for the biological activity of TOAC-labeled angiotensin II and bradykinin: Electron paramagnetic resonance, circular dichroism, and fluorescence studies

N-Terminally and internally labeled analogues of the hormones angiotensin (AII, DRVYIHPF) and bradykinin (BK, RPPGFSPFR) were synthesized containing the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4- carboxylic acid (TOAC). TOAC replaced Asp 1 (TOAC 1-AII) and Val 3 (TOAC 3-AII) in AII and was inserted prior to Arg 1 (TOAC 0-BK) and replacing Pro 3 (TOAC 3-BK) in BK. The peptide conformational properties were examined as a function of trifluoroethanol (TFE) content and pH. Electron paramagnetic resonance spectra were sensitive to both variables and showed that internally labeled analogues yielded rotational correlation times (TC) considerably larger than N-terminally labeled ones, evincing the greater freedom of motion of the N-terminus. In TFE, τ C increased due to viscosity effects. Calculation of τ Cpeptide/τ CTOAC ratios indicated that the peptides acquired more folded conformations. Circular dichroism spectra showed that, except for TOAC 1-AII in TFE, the N-terminally labeled analogues displayed a conformational behavior similar to that of the parent peptides. In contrast, under all conditions, the TOAC 3 derivatives acquired more restricted conformations. Fluorescence spectra of All and its derivatives were especially sensitive to the ionization of Tyr 4. Fluorescence quenching by the nitroxide moiety was much more pronounced for TOAC 3-AII The conformational behavior of the TOAC derivatives bears excellent correlation with their biological activity, since, while the N-terminally labeled peptides were partially active, their internally labeled counterparts were inactive [Nakaie, C. R., et al., Peptides 2002, 23, 65-70]. The data demonstrate that insertion of TOAC in the middle of the peptide chain induces conformational restrictions that lead to loss of backbone flexibility, not allowing the peptides to acquire their receptor-bound conformation. © 2004 Wiley Periodicals, Inc.

An active/reactive predispatch model incorporating ramp rate constraints solved by dual decomposition/lagrangian relaxation

The Predispatch model (PD) calculates a short-term generation policy for power systems. In this work a PD model is proposed that improves two modeling aspects generally neglected in the literature: voltage/reactive power constraints and ramp rate constraints for generating units. Reactive power constraints turn the PD into a non-linear problem and the ramp rate constraints couple the problem dynamically in time domain. The solution of the PD is turned into a harder task when such constraints are introduced. The dual decomposition/ lagrangian relaxation technique is used in the solution approach for handing dynamic constraints. As a result the PD is decomposed into a series of independent Optimal Power Flow (FPO) sub problems, in which the reactive power is represented in detail. The solution of the independent FPO is coordinated by means of Lagrange multipliers, so that dynamic constraints are iteratively satisfied. Comparisons between dispatch policies calculated with and without the representation of ramp rate constraints are performed, using the IEEE 30 bus test system. The results point-out the importance of representing such constraints in the generation dispatch policy. © 2004 IEEE.

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd3+, Mn2+ and Cu2+ heat treated at different temperatures, ranging from the glass transition temperature (Tg) to the crystallization temperature (Tc), are investigated by electron paramagnetic resonance (EPR) and 19F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu2+ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba2ZnF6, which correspond to Cu2+ in a tetragonal compressed F- octahedron and to Cu2+ on interstitial sites with a square-planar F- co-ordination. The EPR spectra of the Mn2+ doped glasses exhibit a sextet structure due to the Mn2+ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn2+ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn2+ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn2+ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd3+ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd3+ ions in environment close to cubic symmetry. The 19F NMR spin-lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above Tc. For the glass samples (doped or undoped) the 19F magnetization recoveries were found to be adjusted by an exponential function and the spin-lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above Tc, the 19F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu2+, Mn2+, Gd3+ EPR spectra and NMR relaxation, are always observed for the samples annealed above Tc. © 2006 Elsevier B.V. All rights reserved.

Anelastic relaxation due to interstitial solutes diffusion in Nb and Nb-1 wt% Zr

Metals and alloys containing solute atoms dissolved interstitially often show anelastic behavior due to a process know as stress-induced ordering. The application of mechanical spectroscopy measurements to diffusion studies in body-centered cubic metals has been extensively used in the last decades. However the kind of preferential occupation of interstitial solutes in body-centered cubic metals is still controversial. The anelastic properties of the Nb and Nb-1 wt% Zr polycrystalline alloys were determined by internal friction and oscillation frequency measurements using a torsion pendulum inverted performed between 300K and 650K, operating in a frequency oscillation in the hertz bandwidth. The interstitial diffusion coefficients of oxygen and nitrogen in Nb and Nb-1 wt% Zr samples were determined at two distinct conditions: (a) for low concentration of oxygen and (b) for high concentration of oxygen.

Strain relaxation and stress-driven interdiffusion in InAsInGaAsInP nanowires

The authors have investigated strain relaxation in InAsInGaAsInP nanowires (NW's). Transmission electron microscopy images show an additional stress field attributed to compositional modulation in the ternary layer, which disrupts NW formation and drives Ga interdiffusion into InAs, according to grazing incidence x-Ray diffraction under anomalous scattering conditions. The strain profile along the NW, however, is not significantly affected when interdiffusion is considered. Results show that the InAs NW energetic stability is preserved with the introduction of ternary buffer layer in the structure. © 2007 American Institute of Physics.