999 resultados para mixed ionic–electronic conduction


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Modern concepts for the treatment of myocardial diseases focus on novel cell therapeutic strategies involving stem cell-derived cardiomyocytes (SCMs). However, functional integration of SCMs requires similar electrophysiological properties as primary cardiomyocytes (PCMs) and the ability to establish intercellular connections with host myocytes in order to contribute to the electrical and mechanical activity of the heart. The aim of this project was to investigate the properties of cardiac conduction in a co-culture approach using SCMs and PCMs in cultured cell strands. Murine embryonic SCMs were pooled with fetal ventricular cells and seeded in predefined proportions on microelectrode arrays to form patterned strands of mixed cells. Conduction velocity (CV) was measured during steady state pacing. SCM excitability was estimated from action potentials measured in single cells using the patch clamp technique. Experiments were complemented with computer simulations of conduction using a detailed model of cellular architecture in mixed cell strands. CV was significantly lower in strands composed purely of SCMs (5.5 ± 1.5 cm/s, n = 11) as compared to PCMs (34.9 ± 2.9 cm/s, n = 21) at similar refractoriness (100% SCMs: 122 ± 25 ms, n = 9; 100% PCMs: 139 ± 67 ms, n = 14). In mixed strands combining both cell types, CV was higher than in pure SCMs strands, but always lower than in 100% PCM strands. Computer simulations demonstrated that both intercellular coupling and electrical excitability limit CV. These data provide evidence that in cultures of murine ventricular cardiomyocytes, SCMs cannot restore CV to control levels resulting in slow conduction, which may lead to reentry circuits and arrhythmias.

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A La0.6Sr0.4Co0.2F0.8O3 mixed ionic electronic conducting (MIEC) membrane was used in a dual chamber reactor for the promotion of the catalytic activity of a platinum catalyst for ethylene oxidation. By controlling the oxygen chemical potential difference across the membrane, a driving force for oxygen ions to migrate across the membrane and backspillover onto the catalyst surface is established. The reaction is then promoted by the formation of a double layer of oxide anions on the catalyst surface. Thelectronic conductivity of the membrane material eliminates the need for an external circuit to pump the promoting oxide ion species through the membrane and onto the catalyst surface. This renders this "wireless" system simpler and more amenable for large-scale practical application. Preliminary experiments show that the reaction rate of ethylene oxidation can indeed be promoted by almost one order of magnitude upon exposure to an oxygen atmosphere on the sweep side of the membrane reactor, and thus inducing an oxygen chemical potential difference across the membrane, as compared to the rate under an inert sweep gas. Moreover, the rate does not return to its initial unpromoted value upon cessation of the oxygen flow on the sweep side, but remains permanently promoted. A number of comparisons are drawn between the classical electrochemical promotion that utilises an external circuit and the "wireless" system that utilises chemical potential differences. In addition a 'surface oxygen capture' model is proposed to explain the permanent promotion of the catalyst activity. © 2007 Springer Science+Business Media, LLC.

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The electrochemical promotion of a platinum catalyst for ethylene oxidation on a dual chamber membrane reactor was studied. The catalyst was supported on a La0.6Sr0.4Co0.2Fe0.803 membrane. Due the supporting membrane's electronic conductivity it is possible to promote the reaction by controlling the oxygen chemical potential difference across the membrane. Upon establishment of an oxygen potential difference across the membrane, oxygen species can migrate and spillover onto the catalyst surface, modifying the catalytic activity. Initial experiments showed an overall promotion of approximately one order of magnitude of the reaction rate of ethylene, under an oxygen atmosphere on the sweep side of the membrane reactor, as compared with the rate under an inert sweep gas. The reaction rate can keep its promoted state even after the flow of oxygen on the sweep side was interrupted. This behavior caused further promotion with every experiment cycle. The causes of permanent promotion and on demonstrating controllable promotion of the catalytic activity are presented. This is an abstract of a paper presented at the AIChE Annual Meeting (San Francisco, CA 11/12-17/2006).

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Two solid state galvanic cells:Pt, Ni + Ni2Si04 + Si02/(Y203)Zr02/Ni + + NiO, Pt (1) and Pt, Ni + NizSiOj + Si02/CaF2/Ni + + NiO, Pt (11) have been employed for the determination of the Gibbs' energy of formation of nickel orthosilicate(Ni2Si04) from nickel oxide and quartz. The emf of cell (I) was reversible and reproducible in the temperature range 925 to 1375K whereas emf of cell (11) drifted with time and changed polarity. From the results of cell (I), the Gibbs' energy of formation of nickel silicate is obtained as,2Ni0 (r.s.) + Si02 (quartz) + Ni2Si04 (olivine)Gibbs' energy of formation of the spinel form of Ni2Si04 is obtained by combining the data for olivine obtained in this study with high pressure data on olivine to spinel transition reported in the literature. The complex time dependence of the emf of cell (11) can be rationalised on the basis of formation of calcium silicates from calcium oxide, generally present as an impurity in the calcium fluoride electrolyte, and silica. The emf of cell (11) is shown to be the function of the activity of calcium oxide at the electrolyte/ electrode interface. The results provide strong evidence against the recent suggestion of mixed anionic conduction in calcium fluoride.

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Directionally solidified zirconia-based eutectic (DSE) fibres were obtained using the laser floating zone (LFZ) method. Two systems were investigated: zirconia-barium zirconate and zirconia-mullite. The purpose was to take advantage of zirconia properties, particularly as an ionic conductor and a mechanical rein-forcement phase. The influence of processing conditions in the structural and microstructural characteristics and their consequences on the electrical and mechanical behaviour were the focus of this thesis. The novel zirconia-barium zirconate eutectic materials were developed in order to combine oxygen ionic conduction through zirconia with protonic conduction from barium zirconate, promoting mixed ionic conduction behaviour. The mi-crostructure of the fibres comprises two alternated regions: bands having coarser zirconia-rich microstructure; and inter-band regions changing from a homogeneous coupled eutectic, at the lowest pulling rate, to columnar colony microstructure, for the faster grown fibres. The bands inter-distance increases with the growth rate and, at 300 mm/h, zirconia dendrites develop enclosed in a fine-interpenetrated network of 50 vol.% ZrO2-50 vol.% BaZrO3. Both phases display contiguity without interphase boundaries, according to impedance spec-troscopy data. Yttria-rich compositions were considered in order to promote the yttrium incorporation in both phases, as revealed by Raman spectroscopy and corroborated by the elemental chemical analysis in energy dispersive spectros-copy. This is a mandatory condition to attain simultaneous contribution to the mixed ionic conduction. Such results are supported by impedance spectrosco-py measurements, which clearly disclose an increase of total ionic conduction for lower temperatures in wet/reduction atmospheres (activation energies of 35 kJ/mol in N2+H2 and 48 kJ/mol in air, in the range of 320-500 ºC) compared to the dry/oxidizing conditions (attaining values close to 90 kJ/mol, above 500 ºC). At high temperatures, the proton incorporation into the barium zirconate is un-favourable, so oxygen ion conduction through zirconia prevails, in dry and oxi-dizing environments, reaching a maximum of 1.3x10-2 S/cm in dry air, at ~1000 ºC. The ionic conduction of zirconia was alternatively combined with another high temperature oxygen ion conductor, as mullite, in order to obtain a broad elec-trolytic domain. The growth rate has a huge influence in the amount of phases and microstructure of the directionally solidified zirconia-mullite fibres. Their microstructure changes from planar coupled eutectic to dendritic eutectic mor-phology, when the growth rate rises from 1 to 500 mm/h, along with an incre-ment of tetragonal zirconia content. Furthermore, high growth rates lead to the development of Al-Si-Y glassy phase, and thus less mullite amount, which is found to considerably reduce the total ionic conduction of as-grown fibres. The reduction of the glassy phase content after annealing (10h; 1400 ºC) promotes an increase of the total ionic conduction (≥0.01 S/cm at 1370 °C), raising the mullite and tetragonal zirconia contents and leading to microstructural differ-ences, namely the distribution and size of the zirconia constituent. This has important consequences in conductivity by improving the percolation pathways. A notable increase in hardness is observed from 11.3 GPa for the 10 mm/h pulled fibre to 21.2 GPa for the fibre grown at 500 mm/h. The ultra-fine eutectic morphology of the 500 mm/h fibres results in a maximum value of 534 MPa for room temperature bending strength, which decreases to about one-fourth of this value at high temperature testing (1400 ºC) due to the soft nature of the glassy-matrix.

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Mixed ionic and electronic conduction in Zr02-based solid electrolytes was studied.The effect of impurities and second-phase particles on the mixed conduction parameter, P,, was measured for different types of ZrOZ electrolytes. The performance of solid-state sensors incorporating ZrOZ electrolytes is sometimes limited by electronic conduction in ZrOZ, especially at temperatures >I800 K. Methods for eliminating or minimizing errors in measured emf due to electronically driven transport of oxygen anions are discussed. Examples include probes for monitoring oxygen content in liquid steel as well as the newly developed sulfur sensor based on a ZrOz(Ca0) + CaS electrolyte. The use of mixed conducting ZrOZ as a semipermeable membrane or chemically selective sieve for oxygen at high temperatures is discussed. Oxygen transport from liquid iron to CO + C& gas mixtures through a ZrOZ membrane driven by a chemical potential gradient, in the absence of electrical leads or imposed potentials, was experimentally observed.

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Numerical modeling is used to explain the origin of the large ON/OFF ratios, ultralow leakage, and high ON-current densities exhibited by back-end-of-the-line-friendly access devices based on copper-containing mixed-ionic-electronic-conduction (MIEC) materials. Hall effect measurements confirm that the electronic current is hole dominated; a commercial semiconductor modeling tool is adapted to model MIEC. Motion of large populations of copper ions and vacancies leads to exponential increases in hole current, with a turn-ON voltage that depends on material bandgap. Device simulations match experimental observations as a function of temperature, electrode aspect ratio, thickness, and device diameter.

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Mn1−xZnxFe2O4 nanoparticles (x = 0 to 1) were synthesized by the wet chemical co-precipitation technique. X-ray diffraction and transmission electron microscopy and high resolution transmission electron microscopy were effectively utilized to investigate the different structural parameters. The ac conductivity of nanosized Mn1−xZnxFe2O4 were investigated as a function of frequency, temperature and composition. The frequency dependence of ac conductivity is analysed by the power law σ(ω)ac = Bωn which is typical for charge transport by hopping or tunnelling processes. The temperature dependence of frequency exponent n was investigated to understand the conduction mechanism in different compositions. The conduction mechanisms are mainly based on polaron hopping conduction

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The temperature and frequency dependence of dielectric permittivity and dielectric loss of nanosized Mn1-xZnxFe2O4 (for x = 0, 0.2, 0.4, 0.6, 0.8, 1) were investigated. The impact of zinc substitution on the dielectric properties of the mixed ferrite is elucidated. Strong dielectric dispersion and broad relaxation were exhibited by Mn1-xZnxFe2O4. The variation of dielectric relaxation time with temperature suggests the involvement of multiple relaxation processes. Cole-Cole plots were employed as an effective tool for studying the observed phenomenon. The activation energies were calculated from relaxation peaks and Cole-Cole plots and found to be consistent with each other and indicative of a polaron conduction.

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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.

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The temperature variation in the insulation around an electronic component, mounted on a horizontal circuit board is studied numerically. The flow is assumed to be laminar and fully developed. The effect of mixed convection and two different types of insulation are considered. The mass, momentum and energy conservation equations in the fluid and conduction equation in the insulation are solved using the SIMPLER algorithm. Computations are carried out for liquid Freon and water, for different conductivity ratios, and different Rayleigh numbers. It is demonstrated that the temperature variation within the insulation becomes important when the thermal conductivity of the insulation is less than ten times the thermal conductivity of the cooling medium.

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The present work is a numerical study of heat transfer characteristics from the bottom tip of a cylinder spinning about a vertical axis in an infinitely saturated porous medium. The problem is axisymmetric. The non-dimensionalized governing equations are solved using the SIMPLER algorithm on a staggered grid. The influence of rotational Reynolds numbers and Darcy numbers on the heat transfer for a Grashof number of 104 and Prandtl number of 7.0 is studied. It is found that for very high Darcy numbers, over a wide range of rotational Reynolds numbers, the heat transfer takes place mainly due to conduction. The convective heat transfer takes place for lower Darcy numbers and for higher rotational Reynolds numbers. Moreover, there is a rapid increase in the overall Nusselt number below a certain Darcy number with increase in the rotational Reynolds numbers. The effect of the Darcy number and the rotational Reynolds number on the heat transfer and fluid flow in the porous medium is depicted in the form of streamline and isotherm plots. The variation of the overall Nusselt number with respect to the Darcy number for various rotational Reynolds numbers is plotted. The variation of the local Nusselt number with respect to the radial coordinate at the heated tip of the vertical cylinder is plotted for various Darcy and rotational Reynolds numbers.

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thermal conduction, and acoustic wave propagation are included. This

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It has been found that the catalytic activity and selectivity of a metal film deposited on a solid electrolyte could be enhanced dramatically and in a reversible way by applying an electrical current or potential between the metal catalyst and the counter electrode (also deposited on the electrolyte). This phenomenon is know as NEMCA [S. Bebelis, C.G. Vayenas, Journal of Catalysis, 118 (1989) 125-146.] or electrochemical promotion (EP) [J. Prichard, Nature, 343 (1990) 592.] of catalysis. Yttria-doped barium zirconate, BaZr0.9Y0.1O3 - α (BZY), a known proton conductor, has been used in this study. It has been reported that proton conducting perovskites can, under the appropriate conditions, act also as oxide ion conductors. In mixed conducting systems the mechanism of conduction depends upon the gas atmosphere that to which the material is exposed. Therefore, the use of a mixed ionic (oxide ion and proton) conducting membrane as a support for a platinum catalyst may facilitate the tuning of the promotional behaviour of the catalyst by allowing the control of the conduction mechanism of the electrolyte. The conductivity of BZY under different atmospheres was measured and the presence of oxide ion conduction under the appropriate conditions was confirmed. Moreover, kinetic experiments on ethylene oxidation corroborated the findings from the conductivity measurements showing that the use of a mixed ionic conductor allows for the tuning of the reaction rate. © 2006 Elsevier B.V. All rights reserved.