Slow, Steady-State Transport with "Loading" and Bulk Reactions: the Mixed Ionic Conductor La2_2CuO4+δ_{4+\delta}

We consider slow, steady transport for the normal state of the superconductor La$_2$CuO$_{4+\delta}$ in a one-dimensional geometry, with surface fluxes sufficiently general to permit oxygen to be driven into the sample (``loaded'') either by electrochemical means or by high oxygen partial pressure. We include the bulk reaction O$\to$O$^{2-}+2h$, where neutral atoms ($a$) go into ions ($i$) and holes ($h$). For slow, steady transport, the transport equations simplify because the bulk reaction rate density $r$ and the bulk loading rates $\partial_t n$ then are uniform in space and time. All three fluxes $j$ must be specified at each surface, which for a uniform current density $J$ corresponds to five independent fluxes. These fluxes generate two types of static modes at each surface and a bulk response with a voltage profile that varies quadratically in space, characterized by $J$ and the total oxygen flux $j_O$ (neutral plus ion) at each surface. One type of surface mode is associated with electrical screening; the other type is associated both with diffusion and drift, and with chemical reaction (the {\it diffusion-reaction mode}). The diffusion-reaction mode is accompanied by changes in the chemical potentials $\mu$, and by reactions and fluxes, but it neither carries current (J=0) nor loads the system chemically ($j_O=0$). Generation of the diffusion-reaction mode may explain the phenomenon of ``turbulence in the voltage'' often observed near the electrodes of other mixed ionic electronic conductors (MIECs).Comment: 11 pages, 1 figur

Silica containing composite anion exchange membranes by sol–gel synthesis: a short review

This short review summarizes the literature on composite anion exchange membranes (AEM) containing an organo-silica network formed by sol-gel chemistry. The article covers AEM for diffusion dialysis (DD), for electrochemical energy technologies including fuel cells and redox flow batteries, and for electrodialysis. By applying a vast variety of organically modified silica compounds (ORMOSIL), many composite AEM reported in the last 15 years are based on poly (vinylalcohol) (PVA) or poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) used as polymer matrix. The most stringent requirements are high permselectivity and water flux for DD membranes, while high ionic conductivity is essential for electrochemical applications. Furthermore, the alkaline stability of AEM for fuel cell applications remains a challenging problem that is not yet solved. Possible future topics of investigation on composite AEM containing an organo-silica network are also discussed

Stability of proton exchange membranes in phosphate buffer for enzymatic fuel cell application: hydration, conductivity and mechanical properties

Proton-conducting ionomers are widespread materials for application in electrochemical energy storage devices. However, their properties depend strongly on operating conditions. In bio-fuel cells with a separator membrane, the swelling behavior as well as the conductivity need to be optimized with regard to the use of buffer solutions for the stability of the enzyme catalyst. This work presents a study of the hydrolytic stability, conductivity and mechanical behavior of different proton exchange membranes based on sulfonated poly(ether ether ketone) (SPEEK) and sulfonated poly(phenyl sulfone) (SPPSU) ionomers in phosphate buffer solution. The results show that the membrane stability can be adapted by changing the casting solvent (DMSO, water or ethanol) and procedures, including a crosslinking heat treatment, or by blending the two ionomers. A comparison with Nafion(TM) shows the different behavior of this ionomer versus SPEEK membranes

Oscillator Strengths for B-X, C-X, and E-X Transitions in Carbon Monoxide

Band oscillator strengths for electronic transitions in CO were obtained at the Synchrotron Radiation Center of the University of Wisconsin-Madison. Our focus was on transitions that are observed in interstellar spectra with the Far Ultraviolet Spectroscopic Explorer; these transitions are also important in studies of selective isotope photodissociation where fractionation among isotopomers can occur. Absorption from the ground state (X ^1Sigma^+ v'' = 0) to A ^1Pi (v'= 5), B ^1Sigma^+ (v' = 0, 1), C ^1Sigma^+ (v' = 0, 1), and E ^1Pi (v' = 0) was measured. Fits to the A - X (5, 0) band, whose oscillator strength is well known, yielded the necessary column density and excitation temperature. These parameters were used in a least-squares fit of the observed profiles for the transitions of interest to extract their band oscillator strengths. Our oscillator strengths are in excellent agreement with results from recent experiments using a variety of techniques. This agreement provides the basis for a self-consistent set of f-values at far ultraviolet wavelengths for studies of interstellar (and stellar) CO.Comment: 22 pages, 3 figures, ApJS (in press

What is the Total Deuterium Abundance in the Local Galactic Disk?

Analyses of spectra obtained with the Far Ultraviolet Spectroscopic Explorer (FUSE) satellite, together with spectra from the Copernicus and IMAPS instruments, reveal an unexplained very wide range in the observed deuterium/hydrogen (D/H) ratios for interstellar gas in the Galactic disk beyond the Local Bubble. We argue that spatial variations in the depletion of deuterium onto dust grains can explain these local variations in the observed gas-phase D/H ratios. We present a variable deuterium depletion model that naturally explains the constant measured values of D/H inside the Local Bubble, the wide range of gas-phase D/H ratios observed in the intermediate regime (log N(H I} = 19.2-20.7), and the low gas-phase D/H ratios observed at larger hydrogen column densities. We consider empirical tests of the deuterium depletion hypothesis: (i) correlations of gas-phase D/H ratios with depletions of the refractory metals iron and silicon, and (ii) correlation with the molecular hydrogen rotational temperature. Both of these tests are consistent with deuterium depletion from the gas phase in cold, not recently shocked, regions of the ISM, and high gas-phase D/H ratios in gas that has been shocked or otherwise heated recently. We argue that the most representative value for the total (gas plus dust) D/H ratio within 1 kpc of the Sun is >=23.1 +/- 2.4 (1 sigma) parts per million (ppm). This ratio constrains Galactic chemical evolution models to have a very small deuterium astration factor, the ratio of primordial to total (D/H) ratio in the local region of the Galactic disk, which we estimate to be f_d <= 1.19 +/-0.16 (1 sigma) or <= 1.12 +/- 0.14 (1 sigma) depending on the adopted light element nuclear reaction rates.Comment: 19 pages, 9 figure

Josephson array of mesoscopic objects. Modulation of system properties through the chemical potential

The phase diagram of a two-dimensional Josephson array of mesoscopic objects is examined. Quantum fluctuations in both the modulus and phase of the superconducting order parameter are taken into account within a lattice boson Hubbard model. Modulating the average occupation number $n_0$ of the sites in the system leads to changes in the state of the array, and the character of these changes depends significantly on the region of the phase diagram being examined. In the region where there are large quantum fluctuations in the phase of the superconducting order parameter, variation of the chemical potential causes oscillations with alternating superconducting (superfluid) and normal states of the array. On the other hand, in the region where the bosons interact weakly, the properties of the system depend monotonically on $n_0$. Lowering the temperature and increasing the particle interaction force lead to a reduction in the width of the region of variation in $n_0$ within which the system properties depend weakly on the average occupation number. The phase diagram of the array is obtained by mapping this quantum system onto a classical two-dimensional XY model with a renormalized Josephson coupling constant and is consistent with our quantum Path-Integral Monte Carlo calculations.Comment: 12 pages, 8 Postscript figure