Voronoi polyhedra analysis of MD simulated silicate glasses

The relationship between the volume and the surface of Voronoi polyhedra (VP) appeared to be an effective tool for the characterization of the structure of MD simulated silicate glasses. This feature was demonstrated on the series of binary potassium-silicate glasses with the alkali content ranging from 5 to 20 mol%. Moreover, the temperature dependence of the slope of the above dependence, when expressed for various types of central atoms (Si, O and K in our case) was studied. Each type of central atom is characterised by its own iron line linearly relating the volume of VP to its properly powered surface, so that new geometrical constrains to the VP was found.     

Temperature Dependence of the Magnetic Hyperfine Field at 140Ce on Gd Sites in GdAg Compound

Perturbed gamma–gamma angular correlation technique was used to measure the magnetic hyperfine field at Gd sites in the intermetallic compound GdAg using the ¹⁴⁰La→¹⁴⁰Ce nuclear probe. A major and well-defined magnetic interaction is observed at ¹⁴⁰Ce substituting Gd sites in GdAg below 130 K, corresponding to a ferromagnetic ordering of Gd moments. The temperature dependence of magnetic hyperfine field, however, shows a sharp deviation from an expected Brillouin-like behavior for temperatures below 75 K. This additional magnetic interaction is believed to result from the polarization of Ce spin moments induced by the magnetic field from Gd atoms.     

Enthalpy recovery, creep and creep-recovery measurements during physical aging of amorphous selenium

The physical aging behavior of amorphous selenium has been investigated using differential scanning calorimetry and conventional and interrupted creep experiments. As a result of physical aging, enthalpy decreases and the creep and recovery curves shift to longer times. The times required to reach equilibrium for enthalpy recovery and creep appear to have different temperature dependences resulting in enthalpy reaching equilibrium before creep at aging temperatures a few degrees below the nominal glass temperature. In the nominal glass transformation range, however, the times required to reach equilibrium are approximately the same. A general picture of aging behavior has emerged from our data on selenium coupled with past work on polyetherimide and polystyrene.     

On the quality of plate reverberation

Metallic plates are used in recording studios to create artificial reverberation. In this paper, the flexural vibrations of such plates are analysed in order to better understand the influence of geometry and materials on the quality of plate reverberation. A comparison is made with acoustic reverberation, both in the time and frequency domain. This comparison is supported by objective criteria such as modal density and density of reflections. From a physical point of view, the internal and external damping mechanisms are examined in detail since they determine the frequency dependence of the reverberation time. Theoretical results are validated through comparison with experiments performed on an EMT140 reverberation plate. The underlying model is aimed at developing numerical simulations of plates (virtual reverberators) allowing a large variety of reverberations based on variations of geometry and materials as input parameters.     

Free energy profiles of Al and La cation distribution in silica and soda silicate glasses

The factors that control the distribution of Al³⁺ and La³⁺ cations in silica and soda silicate glasses is examined by using molecular dynamics (MD) simulations. In particular, the response of the glass network to the presence of metal oxide is probed using a liquid state theory that treats the glass network as a solvent and the metal cation as a solute. MD simulations are used to obtain the mean solvent-solute and solute-solute force. The trajectory used to determine the free energy is analyzed to determine the stable configurations of a cation pair. Details of determining the potential of mean force for an Al cation pair in silica and silicate glass is presented. A comparison of these results with those previously calculated for a La cation pair in the same glass systems is given. The results reveal that there are differences in how the network accommodates the two different size cations. It is found that for the potential used here, based on the Vessal potential, the network wraps itself around the larger La cation forming a solvent shell, whereas, the smaller Al cation is incorporated into the network backbone. In silica and soda silicate glasses, La ion pairs cluster to form La-O-La linkages. In contrast, the glasses favor a separated state of the Al ion pair.     

Impact of electron irradiation on particle track etching response in polyallyl diglycol carbonate (PADC)

In the present work, attempts have been made to investigate the modification in particle track etching response of polyallyl diglycol carbonate (PADC) due to impact of 2 MeV electrons. PADC samples pre-irradiated to 1, 10, 20, 40, 60, 80 and 100 Mrad doses of 2 MeV electrons were further exposed to 140 MeV²⁸ Si beam and dose-dependent track registration properties of PADC have been studied. Etch-rate values of the PADC irradiated to 100 Mrad dose electron was found to increase by nearly 4 times that of pristine PADC. The electron irradiation has promoted chain scissioning in PADC, thereby converting the polymer into an easily etchable polymer. Moreover, the etching response and the detection efficiency were found to improve by electron irradiation. Scanning electron microscopy of etched samples further revealed the surface damage in these irradiated PADCs.     

Photochemistry of 5.6-epoxy-1,3-dienes : Influence of a 7-hydroxy substituent

Triplet sensitization of the 7-hydroxy-5,6-epoxy-1,3-diene 10 causes cleavage of the C(5),0 epoxide bond followed by the formation of the three isomers 11–13 or induces scission of the C(6), C(7) bond followed by the formation of the aldehyde 14 and the bicyclo[3.2.0]heptanols 15 and 16. However, irradiation of the corresponding acetate 18 gives only C(5),0 epoxide bond scission (18 → f) followed by the cyclization process f → 19, the 1,2-Me shifts f → 20, 21 and the γ-H abstraction f → g leading to the cyclopropane formation g → 22.     

The nature of phase separation in binary oxide melts and glasses. I. Silicate systems

An exhaustive review of compositional and thermal extents of miscibility gaps in 41 binary silicate systems permits identification of three groups of cations exhibiting different immiscibility behaviours. The first group comprises network-modifier cations with an ionic radius larger than about 87.2 pm. They have coordination numbers equal to, or higher than, 5 and their miscibility gap size increases linearly with increasing ionic potential. The second group involves cations with an ionic radius larger than 26 pm and smaller than about 87.2 pm (in octahedral coordination). They have at least two coordination numbers: the first one is always 4 and the other 5 (or more). For this reason they are called amphoteric. Their miscibility gap sizes do not increase linearly with an increase of the ionic potential, but follow curves. The third group includes cations with variable crystal field stabilization energies. They are characterized by larger miscibility gap sizes than expected when they are compared with cations with similar ionic radii despite the fact that some of them (e.g. Cr³⁺) may behave as an amphoteric element because their ionic radii in octahedral coordination are smaller than about 87.2 pm. The origin of phase separation in binary silicate systems is due to coulombic repulsions between poorly screened cations bounded by bridging oxygen strongly polarized towards the silicon, and by non-bridging oxygen.     

New insights on the thermodynamic barrier for nucleation in glasses: The case of lithium disilicate

An analysis is performed of the temperature dependence of the thermodynamic barrier to nucleation, W*(T), calculated from a fit of lithium disilicate glass data to the classical theory of nucleation. It is shown that, in order to obtain a satisfactory agreement between experimental and theoretical determinations of W*(T), lower values must be assigned to both the thermodynamic driving force and the surface energy as compared with the corresponding macroscopic values. This finding is consistent with theoretical considerations taking into account the effect that, in general, both the bulk and surface properties of the critical nuclei differ considerably from the respective properties of the newly evolving macroscopic phases. In addition, an anomalous increase of W*(T) with decreasing temperature is found near the glass transition interval. This increase is interpreted as a result of the effect of elastic strain on the thermodynamic driving force. The values of elastic strain energy estimated from the low temperature behavior of W*(T) are congruent with those calculated using the elastic constants of glass and crystal.     

Giant Spherical Cluster with I‐C140 Fullerene Topology

We report on an effective cluster expansion of CuBr‐linked aggregates by the increase of the steric bulk of the Cp^R ligand in the pentatopic molecules [Cp^RFe(η⁵‐P₅)]. Using [Cp^BIGFe(η⁵‐P₅)] (Cp^BIG=C₅(4‐nBuC₆H₄)₅), the novel multishell aggregate [{Cp^BIGFe(η^{5:2:1:1:1:1:1}‐P₅)}₁₂(CuBr)₉₂] is obtained. It shows topological analogy to the theoretically predicted I‐C₁₄₀ fullerene molecule. The spherical cluster was comprehensively characterized by various methods in solution and in the solid state.