Iron redox equilibrium, structure and properties of zinc iron phosphate glasses

Iron redox equilibrium, structure and properties were investigated for the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glasses melted at different temperatures. The structure and valence states of the iron ions in these glasses were investigated using Mössbauer spectroscopy, Raman spectroscopy and differential thermal analysis. Mössbauer spectroscopy indicated that the concentration of Fe²⁺ ions increased in the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glass with increasing melting temperature. The Fe²⁺/(Fe²⁺ + Fe³⁺) ratio increased from 0.18 to 0.38 as the melting temperature increased from 1100 to 1300 °C. The measured isomer shifts showed that both Fe²⁺ and Fe³⁺ ions are in octahedral coordination. It was shown that the dc conductivity strongly depended on Fe²⁺/(Fe²⁺ + Fe³⁺) ratio in glasses. The dc conductivity increases with the increasing Fe²⁺ ion content in these glasses. The conductivity arises from the polaron hopping between Fe²⁺ and Fe³⁺ ions which suggests that the conduction is electronic in nature in zinc iron phosphate glasses.     

Nano-scale structural inhomogeneities of CuI-Cu2MoO4 superionic conducting glass observed by high resolution transmission electron microscopy

Nano-meter sized structural inhomogeneities of (CuI)_0.52-(Cu₂MoO₄)_0.48 superionic conducting glass were investigated by high resolution transmission electron microscopy. The as-quenched sample of CuI-Cu₂MoO₄ is a homogeneous glass, in which the CuI component is finely and uniformly dispersed among the oxyanions of Cu₂MoO₄ glassy matrix. A two-step crystallization, starting at 440 and 495 K, was observed in the glass. After the first step crystallization, precipitating nano-crystalline cubic CuI 2-3 nm in diameter, the electrical conductivity increases by about 50%. On the other hand, the electrical conductivity decreases with the second crystallization event forming crystalline phases of CuI, Cu₂O and others 20-30 nm in diameter.     

Vibrational states of glassy and crystalline orthoterphenyl

Low-frequency vibrations of glassy and crystalline orthoterphenyl are studied by means of neutron scattering. Phonon dispersions are measured along the main axes of a single crystal, and the corresponding longitudinal and transversal sound velocities are obtained. For glassy and polycrystalline samples, a density of vibrational states is determined and cross-checked against other dynamic observables. In the crystal, low-lying zone-boundary modes lead to an excess over the Debye density of states. In the glass, the boson peak is located at even lower frequencies. With increasing temperature, both glass and crystal show anharmonicity. Received 7 December 1999     

Stretched exponential relaxation on the hypercube and the glass transition

We study random walks on the dilute hypercube using an exact enumeration Master equation technique, which is much more efficient than Monte Carlo methods for this problem. For each dilution p the form of the relaxation of the memory function q(t) can be accurately parametrized by a stretched exponential over several orders of magnitude in q(t). As the critical dilution for percolation is approached, the time constant tends to diverge and the stretching exponent drops towards 1/3. As the same pattern of relaxation is observed in a wide class of glass formers, the fractal like morphology of the giant cluster in the dilute hypercube appears to be a good representation of the coarse grained phase space in these systems. For these glass formers the glass transition may be pictured as a percolation transition in phase space. Received 16 June 2000 and Received in final form 13 October 2000     

Forward Raman scattering in GaAs/AlAs superlattices: Study of optical phonon anisotropy

We present the forward Raman scattering study of zone-centre optical phonon anisotropy in short-period GaAs/AlAs superlattices. Experiments were performed on specially prepared superlattice structures having anti-reflection dielectric coatings and removed substrates. The experimental data are compared with the angular dispersion of superlattice optical phonons calculated within the dielectric susceptibility model. We have found a good agreement between the experimental data and the calculations taking into account interface disorder. Received 9 September 1998 and Received in final form 22 October 1998     

2H NMR in nearly stoichiometric yttrium dideuteride

²H NMR spectra and spin-lattice relaxation rates, R₁ are measured as functions of temperature (4.2-310 K) for YD_1.99 and YD_1.99+0.04. In YD_1.99 the measured temperature dependence of R₁ is explained by the interaction of deuteron spins with conduction electrons and the value s^-1 K^-1 is obtained for the inverse Korringa product . Most of the spectral features in the “rigid” lattice regime are described by the dipolar interaction. No evidence of the deuterium self-diffusion was observed in the measured temperature range. The low-temperature spectra in YD_1.99+0.04 consisted of two components: a central line and a doublet characteristic for the quadrupole interaction. The central line corresponds to zero electric field gradients (EFG) at the sites of the deuterons which have a surrounding with cubic symmetry like in YD_1.99. The doublet indicates a non-zero EFG which can be explained in terms of the presence of short-range ordered domains of the hypothetical YD_2.25 stoichiometry. Other possible interpretations of the spectra are also discussed. In the vicinity of 250 K both spectra and R₁ reflect the onset of the rapid motion of deuterium atoms. The linear dependence of R₁ at low temperatures yields s^-1 K^-1. Received 8 September 1998     

A magnetic resonance study on the structure of amorphous networks in the Si–B–N(–C) system

The amorphous networks Si₃B₃N₇ and ‘SiBN₃C' are studied by solid-state nuclear magnetic resonance (NMR), continuous-wave and pulse electron paramagnetic resonance (EPR), and by one- and two-dimensional electron nuclear double resonance spectroscopy. In both compounds, boron is found to be coordinated exclusively by nitrogen with close to trigonal planar geometry and close to equal bond lengths. Silicon is four-coordinated by nitrogen with the coordination tetrahedra being distorted to accommodate the coordination preferences of boron. REDOR measurements demonstrate that boron resides in the second coordination sphere of silicon. Carbon incorporation into the Si–B–N network does not lead to any observable changes in NMR parameters including the average dipolar coupling between ¹¹B nuclei which depends on the average distance of the boron atoms. Only spin–lattice relaxation of the nuclei is accelerated due to the generation of paramagnetic centers. The unpaired electrons appear to be delocalized over several carbon atoms and exhibit significant hyperfine couplings to boron, silicon, nitrogen, and some residual protons. In contrast to electron spectroscopic imaging experiments, the magnetic resonance results suggest formation of carbon clusters.     

Transparent conducting molybdenum-doped zinc oxide films deposited by RF magnetron sputtering

A new transparent conducting oxide (TCO) film with low resistivity and high transmittance in the visible range, molybdenum-doped zinc oxide (MZO), was successfully prepared by RF magnetron sputtering method on glass substrates at room temperature. The structural, electrical, and optical properties as a function of film thickness were investigated. All the samples have a preferred orientation with the (0 0 2) planes parallel to the substrates. The resistivity initially decreases and then shows an increase with the increase of the film thickness. When the thickness is 400 nm, the film has its best crystallinity and lowest resistivity 9.2 × 10⁻⁴ Ω cm with a Hall mobility of 30 cm² V⁻¹ s⁻¹ and a carrier concentration of 2.3 × 10²⁰ cm⁻³. The average transmittance in the visible range exceeds 84% for all thickness films.     

Coupling between aging and convective motion in a colloidal glass of Laponite

We study thermal convection in a colloidal glass of Laponite in formation. Low concentration preparation are submitted to destabilizing vertical temperature gradient, and present a gradual transition from a turbulent convective state to a steady conductive state as their viscosity increases. The time spent under convection is found to depend strongly on sample concentration, decreasing exponentially with mass fraction of colloidal particles. Moreover, at fixed concentration, it also depends slightly on the pattern selected by the Rayleigh Bénard instability: more rolls maintain the convection state longer. This behavior can be interpreted with recent theoretical approaches of soft glassy material rheology.     

Electron impact ionization of SiCl<Subscript>2</Subscript> and SiCl

We measured absolute partial cross sections for the formation of all singly charged positive ions produced by electron impact on SiCl₂ and SiCl from threshold to 200 eV using the fast-neutral-beam technique. Some of the cross section curves exhibit an unusual energy dependence with a pronounced low-energy maximum at an energy around 30 eV, which may be indicative of the presence of indirect ionization channels. Dissociative ionization channels are dominant for both species. The experimentally determined total single ionization cross sections for both species agree very well with calculated cross sections using the Deutsch-M?rk (DM) formalism. A brief summary of the ionization cross sections determined for all four SiCl_x (x=1–4) species is given highlighting similarities and differences.