X-ray photoelectron spectroscopy of superconducting RuSr2Eu1.5Ce0.5Cu2O10 and nonsuperconducting RuSr2EuCeCu2O10

We report x-ray photoelectron spectroscopic investigation of RuSr2Eu1.5Ce0.5Cu2O10 with ferromagnetic T-C similar to 100 K and a superconducting transition temperature of similar to 30 K compared with RuSr2EuCeCu2O10, which is a ferromagnetic (T-C similar to 150 K) insulator. Our results show that the rare earths, Eu and Ce, are in 3+ and 4+ states, respectively. Comparing the Ru core level spectra from these compounds to those from two Ru reference oxides, we also show that Ru in these ruthenocuprates is always in 5+ state, suggesting that the doped holes in the superconducting compound arising from the substitution of Ce4+ by Eu3+ are primarily in the Cu-O plane, in close analogy to all other doped high-T-C cuprates. Analysis of Cu 2p spectra in terms of a configuration interaction model provides a quantitative description of the gross electronic structures of these ruthenocuprates.

Increasing ionic conductivity of polymer-sodium salt complex by addition of a non-ionic plastic crystal

Ionic conductivity and other physico-chemical properties of a soft matter composite electrolyte comprising of a polymer-sodium salt complex and a non-ionic plastic crystal are discussed here. The electrolyte under discussion comprises of polyethyleneoxide (PEO)-sodium triflate (NaCF3SO3) and succinonitrile (SN). Addition of SN to PEO-NaCF3SO3 resulted in significant enhancement in ionic conductivity. At 50% SN concentration (with respect to weight of polymer), the polymer-plastic composite electrolyte room temperature (= 25 degrees C) ionic conductivity was similar to 1.1 x 10(-4) Omega(-1) cm(-1), approximately 45 times higher than PEO-NaCF3SO3. Observations from ac-impedance spectroscopy along with X-ray diffraction, differential scanning calorimetry and Fourier transform inrared spectroscopy strongly suggest the enhancement in the composite is ionicconductivity due to enhanced ion mobility via decrease in crystallinity of PEO. The free standing composite polymer-plastic electrolytes were more compliable than PEO-NaCF3SO3 thus exhibiting no detrimental effects of succinonitrile addition on the mechanical stability of PEO-NaCF3SO3. We propose that the exploratory PEO-NaCF3SO3-SN system.discussed here will eventually be developed as a prototype electrolyte.for sodium-sulfur batteries capable of operating at ambient and.sub-ambient conditions. (C) 2010 Elsevier B.V. All rights reserved.

Direct observation of low frequency confined acoustic phonons in silver nanoparticles: Terahertz time domain spectroscopy

Terahertz time domain spectroscopy has been used to study low frequency confined acoustic phonons of silver nanoparticles embedded in poly (vinyl alcohol) matrix in the spectral range of 0.1-2.5 THz. The real and imaginary parts of the dielectric function show two bands at 0.60 and 2.12 THz attributed to the spheroidal and toroidal modes of silver nanoparticles, thus demonstrating the usefulness of terahertz time domain spectroscopy as a complementary technique to Raman spectroscopy in characterizing the nanoparticles. (C) 2010 American Institute of Physics. [doi:10.1063/1.3456372]

Mode-dependent dispersion in Raman line shapes: Observation and implications from ultrafast Raman loss spectroscopy

Ultrafast Raman loss spectroscopy (URLS) enables one to obtain the vibrational structural information of molecular systems including fluorescent materials. URLS, a nonlinear process analog to stimulated Raman gain, involves a narrow bandwidth picosecond Raman pump pulse anda femtosecond broadband white light continuum. Under nonresonant condition, the Raman response appears as a negative (loss) signal, whereas, on resonance with the electronic transition the line shape changes from a negative to a positive through a dispersive form. The intensities observed and thus, the Franck-Condon activity (coordinate dependent), are sensitive to the wavelength of the white light corresponding to a particular Raman frequency with respect to the Raman pump pulse wavelength, i.e., there is a mode-dependent response in URLS. (C) 2010 American Institute of Physics.

Terahertz Spectroscopy of Single-Walled Carbon Nanotubes in a Polymer Film: Observation of Low-Frequency Phonons

We investigate the dielectric response of single-walled carbon nanotubes dispersed in poly(vinyl alcohol) matrix by using terahertz time domain spectroscopy. Frequency-dependent real and imaginary parts of the complex dielectric function are measured experimentally in the terahertz regime. The low-frequency phonons of carbon nanotubes, though predicted theoretically, are directly observed for the first time at frequencies 0.26, 0.60, and 0.85 THz. Further, a broad resonance is observed at 1.15 THz associated with the longitudinal acoustic mode of vibration of straight-chain segments of the long polymeric molecules in the film. The latter is observed at 1.24 THz for a pristine polymer film and has been used to derive the size of crystalline lamellae in the film.

Nature of Pb in superconducting cuprates containing lead: A Pb L3 x‐ray absorption near‐edge spectroscopy study

X‐ray absorption near‐edge spectroscopy studies show that Pb in superconducting Tl0.5Pb0.5CaSr2Cu2O7+δ is essentially in the 4+ state while it is in the 2+ state in Pb2Sr2Ca1−xLnxCu3O8+δ.

Novel phase-transition behavior in an aqueous electrolyte solution

We have investigated the near-critical behavior of the susceptibility of a ternary liquid mixture of 3-methylpyridine. water, and sodium bromide as a function of the salt concentration. The susceptibility was determined from light-scattering measurements performed at a scattering angle of 90 degrees in the one-phase region near the locus of lower consolute points. A sharp crossover from asymptotic Ising behavior to mean-field behavior has been observed at concentrations ranging from 8 to 16.5 mass% NaBr. The range of asymptotic Ising behavior shrinks with increasing salt concentration and vanishes at a NaBr concentration of about 17 mass%. where complete mean-field-like behavior of the susceptibility is observed. A simultaneous pronounced increase in the background scattering at concentrations above 15 mass%, as well as a dip in the critical locus at 17 mass % NaBr, suggests that this phenomenon can be interpreted as mean-field tricritical behavior associated with the formation of a microheterogeneous phase due to clustering of the molecules and ions. An analogy with tri critical behavior observed in polymer solutions as well as the possibility of a charge-density-wave phase is also discussed. In addition, we, have observed a third soap-like phase an the liquid-liquid interface in several binary and ternary liquid mixtures.

Electronic structure of high-Tc Ba0.6K0.4BiO3 by x-ray photoelectron spectroscopy

We have investigated the electronic structure of Ba1-xKxBiO3 (0spectroscopy. The Bi(4f) core levels show a normal valency of +3 as in Bi2O3 and we find no evidence for the disproportionation of Bi4+ to Bi3+ and Bi5+. Instead, we find that BaBiO3 has mixed valent O2- and O1- ions. As the potassium doping is increased, the binding energy of the O2- ions in the O(1s) photoelectron spectra steadily decreases from 529.7 to 528.8 eV. The effect of lowering the O(1s) binding energy is to raise the O(2p) band towards EF and at the superconducting composition a finite density of O(2p) states is observed near EF. Similarly, the Ba(5p) binding energies decrease with potassium doping, indicating increased metallicity. The behavior of the O(1s), Ba(5p), and the valence band resembles that of all the cuprate superconductors and we conclude that in all these oxide superconductors, a hole in the (filled) O(2p) band is the carrier responsible for superconductivity, which predicts hole conduction in the Ba-K-Bi-O and Ba-Pb-Bi-O systems.

Angle-resolved photoemission spectroscopy of the insulating NaxWO3: Anderson localization, polaron formation, and remnant Fermi surface

The electronic structure of the insulating sodium tungsten bronze, Na0.025WO3, is investigated by high-resolution angle-resolved photoemission spectroscopy. We find that near-E-F states are localized due to the strong disorder arising from random distribution of Na+ ions in the WO3 lattice, which makes the system insulating. The temperature dependence of photoemission spectra provides direct evidence for polaron formation. The remnant Fermi surface of the insulator is found to be the replica of the real Fermi surface in the metallic system

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.