PVA-SSA-HPA Mixed-Matrix-Membrane Electrolytes for DMFCs

Stabilized forms of heteropolyacids (HPAs), namely phosphomolybdic acid (PMA), phosphotungstic acid (PTA), and silicotungstic acid (STA), are incorporated into poly (vinyl alcohol) (PVA) cross-linked with sulfosuccinic acid (SSA) to form mixed-matrix membranes for application in direct methanol fuel cells (DMFCs). Bridging SSA between PVA molecules not only strengthens the network but also facilitates proton conduction in HPAs. The mixed-matrix membranes are characterized for their mechanical stability, sorption capability, ion-exchange capacity, and wetting in conjunction with their proton conductivity, methanol permeability, and DMFC performance. Methanol-release kinetics is studied ex situ by volume-localized NMR spectroscopy (employing point-resolved spectroscopy'') with the results clearly demonstrating that the incorporation of certain inorganic fillers in PVA-SSA viz., STA and PTA, retards the methanol-release kinetics under osmotic drag compared to Nafion, although PVA-SSA itself exhibits a still lower methanol permeability. The methanol crossover rate for PVA-SSA-HPA-bridged-mixed-matrix membranes decreases dramatically with increasing current density rendering higher DMFC performance in relation to a DMFC using a pristine PVA-SSA membrane. A peak power density of 150 mW/cm(2) at a load current density of 500 mA/cm(2) is achieved for the DMFC using a PVA-SSA-STA-bridged-mixed-matrix-membrane electrolyte. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3465653] All rights reserved.

Microstructure related influence on the electrical properties of pulsed laser ablated (Ba, Sr)TiO3 thin films

The microstructural dependence of electrical properties of (Ba, Sr)TiO3(BST) thin films were studied from the viewpoint of dc and ac electrical properties. The films were grown using a pulsed laser deposition technique in a temperature range of 300 to 600 degrees C, inducing changes in grain size, structure, and morphology. Consequently, two different types of films were realized, of which type I, was polycrystalline, multigrained, while type II was [100] oriented possessing a densely packed fibrous microstructure. Leakage current measurements were done at elevated temperatures to provide evidence of the conduction mechanism present in these films. The results revealed a contribution from both electronic and ionic conduction. In the case of type I films, two trapping levels were identified with energies around 0.5 and 2.73 eV, which possibly originate from oxygen vacancies V-O and Ti3+ centers, respectively. These levels act as shallow and deep traps and are reflected in the current-voltage characteristics of the BST thin films. The activation energy associated with oxygen vacancy motion in this case was obtained as 1.28 eV. On the contrary, type II films showed no evidence of deep trap energy levels, while the identified activation energy associated with shallow traps was obtained as 0.38 eV. The activation energy obtained for oxygen vacancy motion in type II films was around 1.02 eV. The dc measurement results were further elucidated through ac impedance analysis, which revealed a grain boundary dominated response in type I in comparison to type II films where grain response is highlighted. A comparison of the mean relaxation time of the two films revealed three orders of magnitude higher relaxation time in the case of type I films. Due to smaller grain size in type I films the grains were considered to be completely depleted giving rise to only grain boundary response for the bulk of the film. The activation energy obtained from conductivity plots agree very well with that of dc measurements giving values 1.3 and 1.07 eV for type I and type II films, respectively. Since oxygen vacancy transport have been identified as the origin of resistance degradation in BST thin films, type I films with their higher value of activation energy for oxygen ion mobility explains the improvement in breakdown characteristics under constant high dc field stress. The role of microstructure in controlling the rate of degradation is found useful in this instance to enhance the film properties under high electric field stresses. (C) 2000 American Institute of Physics. [S0021-8979(00)00418-7].

Spatially dependent correlation functions in the Anderson model

We report results from a first principles calculation of spatially dependent correlation functions around a magnetic impurity in metals described by the nondegenerate Anderson model. Our computations are based on a combination of perturbative scaling theory and numerical renormalization group methods. Results for the conduction election charge density around the impurity and correlation functions involving the conduction electron and impurity charge and spin densities will be presented. The behavior in various regimes including the mixed valent regime will be explored.

Critical behavior of electrical resistivity in polar + nonpolar binary liquid systems

The behavior of electrical resistivity in the critical region of three polar + nonpolar binary liquid systems CS2 +(CH3CO)2O, C6H12+(CH3CO)2O, and n‐C7H16+(CH3CO)2O is studied. For the mixtures with critical composition, the two phase region shows a conductivity behavior with σ1−σ2∼ (−ϵ)β with β?0.35. In the one phase region dR/dT has a singularity ϵ−b with b?0.35. A possible theory of the impurity conduction is given, which broadly explains these results. The possibility of dR/dT being positive or negative is also discussed.

Optical absorption and photoluminescence studies on heavily doped (Ga,Mn)Sb crystals

Ga1-xMnxSb crystals are grown with different Mn doping concentrations by the horizontal Bridgman method (x = 0 - 0.04). Optical absorption and photoluminescence studies are carried out in the temperature range 3-300 K. Optical absorption studies reveal that the inter-valence band transition from the spin-orbit split-off band to the light/heavy hole bands is dominant over the fundamental valence band to conduction band absorption. In higher doped crystals, the fundamental absorption peak is merged with the inter-valence band transition and could not be resolved. Photoluminescence measurements in heavily doped crystals reveal the band gap narrowing and band filling effects due to the Fermi level shifting into the valence band.

An excitonic mechanism for high-temperature. Superconductivity in YBa2Cu3O7

We propose an excitonic mechanism for high temperature superconductivity in YBa2Cu3O7. We feel that in this material, nature has provided a very elegant system, closely simulated by the model proposed by Allender, Bray and Bardeen1 using Ginzburg's ideas.2 In this system the excitonic layer and the conduction electron layers are indeed atomic planes making contacts on atomic level, an ideal version of the situation envisaged by Allender et al. Further, since these layers are physically separated, the question of screening of charges is avoided.

High-temperature dielectric response in pulsed laser deposited Bi1.5Zn1.0Nb1.5O7 thin films

Cubic pyrochlore Bi1.5Zn1.0Nb1.5O7 thin films were deposited by pulsed laser ablation on Pt(200)/SiO2/Si at 500, 550, 600, and 650 degrees C. The thin films with (222) preferred orientation were found to grow at 650 degrees C with better crystallinity which was established by the lowest full-width half maxima of similar to 0.38. The dielectric response of the thin films grown at 650 degrees C have been characterized within a temperature range of 270-650 K and a frequency window of 0.1-100 kHz. The dielectric dispersion in the thin films shows a Maxwell-Wagner type relaxation with two different kinds of response confirmed by temperature dependent Nyquist plots. The ac conduction of the films showed a varied behavior in two different frequency regions. The power law exponent values of more than 1 at high frequency are explained by a jump-relaxation-model. The possibility of grain boundary related large polaronic hopping, due to two different power law exponents and transformation of double to single response in Nyquist plots at high temperature, has been excluded. The ``attempt jump frequency'' obtained from temperature dependent tangent loss and real part of dielectric constants, has been found to lie in the range of their lattice vibronic frequencies (10(12)-10(13) Hz). The activation energy arising from a large polaronic hopping due to trapped charge at low frequency region has been calculated from the ac conduction behavior. The range of activation energies (0.26-0.59. eV) suggests that the polaronic hopping at low frequency is mostly due to oxygen vacancies. (C) 2010 American Institute of Physics. doi:10.106311.3457335]

A theory on the migration of an extraneous electron across hydrogen bonds in polypeptides

The migrating electrons in biological systems normally are extraneous and taking this into account the electron delocalisation across the hydrogen bonds in proteins is re-examined. It is seen that an extraneous electron can travel rapidly via the low-lying virtual orbitals of the hydrogen-bonded π-electronic structure of peptide units in proteins. The frequency of electron transfer decreases slowly with an increase in the path length. However, the coupling of electron and protonic motions enhances this frequency. Transfer of electrons across the hydrogen bonds in accordance with the double-exchange mechanism does not appear to be possible. This theory offers a possibility for an extraneous electron to transfer within protein structures.

Electrical switching in benzidine-DDQ under pressure

The effect of pressure on non-ohmic conduction and electrical switching in the charge transfer complex benzidine-DDQ has been studied up to a pressure of 7·66 GPa at a temperature of 300K. Pulsed I-V measurements reveal heating contribution to non-ohmicity and switching. At high electric fields (∼ 3 × 103 V/cm), the sample switches from high resistance OFF state of several kiloohms to low resistance ON state of several ohms. Temperature dependence of conductivity of ON state show semiconducting behaviour with very low activation energy.

Complex Permittivity Characteristics of Epoxy Nanocomposites at Low Frequencies

The complex permittivity characteristics of epoxy nanocomposite systems were examined and an attempt has been made to understand the underlying physics governing some of the unique macroscopic dielectric behaviors. The experimental investigations were performed using two different nanocomposite systems with low filler concentrations over the frequency range of 10(-2)-400 Hz, but for some cases, the data has been reported upto 10(6) Hz for a better understanding of the behaviors. Results demonstrate that nanocomposites do possess unique permittivity behaviors as compared to those already known for unfilled polymer and microcomposite systems. The nanocomposite real permittivity and tan delta values are found to be lower than that of unfilled epoxy. In addition, results show that interfacial polarization and charge carrier mobilities are suppressed in epoxy nanocomposite systems. The complex permittivity spectra coupled with the ac conductivity characteristics with respect to frequency was found to be sufficient to identify several of the nanocomposite characteristics like the reduction in permittivity values, reduction in the interfacial polarization mechanisms and the electrical conduction behaviors. Analysis of the results are also performed using electric modulus formalisms and it has been seen that the nanocomposite dielectric behaviors at low frequencies can also be explained clearly using this formalism.

Steady incompressible flow of cohesionless granular materials through a wedge-shaped hopper: Frictional 14kinetic solution to the smooth wall, radial gravity problem

Hybrid frictional-kinetic equations are used to predict the velocity, grain temperature, and stress fields in hoppers. A suitable choice of dimensionless variables permits the pseudo-thermal energy balance to be decoupled from the momentum balance. These balances contain a small parameter, which is analogous to a reciprocal Reynolds number. Hence an approximate semi-analytical solution is constructed using perturbation methods. The energy balance is solved using the method of matched asymptotic expansions. The effect of heat conduction is confined to a very thin boundary layer near the exit, where it causes a marginal change in the temperature. Outside this layer, the temperature T increases rapidly as the radial coordinate r decreases. In particular, the conduction-free energy balance yields an asymptotic solution, valid for small values of r, of the form T proportional r-4. There is a corresponding increase in the kinetic stresses, which attain their maximum values at the hopper exit. The momentum balance is solved by a regular perturbation method. The contribution of the kinetic stresses is important only in a small region near the exit, where the frictional stresses tend to zero. Therefore, the discharge rate is only about 2.3% lower than the frictional value, for typical parameter values. As in the frictional case, the discharge rate for deep hoppers is found to be independent of the head of material.

The contribution of polarons, bipolarons and intersite tunneling to low temperature conductivity in doped polypyrrole

The conductivity of highly doped polypyrrole is less than that of intermediately doped samples, by two orders of magnitude, at 4.2 K. This may be due to more number of bipolarons in highly doped samples. Bipolarons require four times more activation energy than single polarons to hop by thermally induced virtual transitions to intermediate dissociated polaron states than by the nondissociated process. The conduction process in these polyconjugated systems involve ionization from deep trapped states, having a View the MathML source dependence, hopping from localised states, having View the MathML source dependence, and intersite tunnel percolation, having T−1 dependence. The interplay of these factors leads to a better fit by View the MathML source. The mechanism for this exponential behaviour need not be same as that of Motts variable range hopping. Conduction by percolation is possible, if an infinite cluster of chains can be connected by impurity centers created by dopant ions. The tendency for the saturation of conductivity at very low temperatures is due to the possibility of intersite tunnel percolation is disordered polaronic systems.

A model for antiferromagnetic to superconductor transition

A model system capable of exhibiting both superconductivity of conduction electrons and “antiferromagnetic” order of site localised electrons is studied. Coexistence of both types of order seems a possibility and the model predicts a re-entrant behaviour of the transition temperature.

Varistor property of n‐BaTiO3 based current limiters

Highly stable varistor (voltage-limiting) property is observed for ceramics based on donor doped (Ba1-xSrx)Ti1-yZryO3 (x < 0.35, y < 0.05), when the ambient temperature (T(a)) is above the Curie point (T(c)). If T(a) < T(c), the same ceramics showed stable current-limiting behavior. The leakage current and the breakdown voltage as well as the nonlinearity coefficient (alpha = 30-50) could be varied with the T(c)-shifting components, the grain boundary layer modifiers and the post-sintering annealing. Analyses of the current-voltage relations show that grain boundary layer conduction at T(a) < T(c) corresponds to tunneling across asymmetric barriers formed under steady-state joule heating. At T(a) > T(c), trap-related conduction gives way to tunneling across symmetric barriers as the field strength increases.

Dielectric relaxation in bismuth layer-structured BaBi4Ti4O15 ferroelectric ceramics

The dielectric properties of BaBi4Ti4O15 ceramics were investigated as a function of frequency (10(2)-10(6) Hz) at various temperatures (30 degrees C-470 degrees C), covering the phase transition temperature. Two different conduction mechanisms were obtained by fitting the complex impedance data to Cole-Cole equation. The grain and grain boundary resistivities were found to follow the Arrhenius law associated with activation energies: E-g similar to 1.12 eV below T-m and E-g similar to 0.70 eV above T-m for the grain conduction; and E-gb similar to 0.93 eV below T-m and E-gb similar to 0.71 eV above T-m for the grain boundary conduction. Relaxation times extracted using imaginary part of complex impedance Z `'(omega) and modulus M `'(omega) were also found to follow the Arrhenius law and showed an anomaly around the phase transition temperature. The frequency dependence of conductivity was interpreted in terms of the jump relaxation model and was fitted to the double power law. (C) 2010 Elsevier B. V. All rights reserved.