Dense amorphous packing of binary hard sphere mixtures with chemical order: The stability of a solute ordered approximant

Recently, Miracle proposed that the intermediate structure in metallic glasses could be usefully characterized as an ordered face centered cubic packing of solute-centered coordination clusters. In this paper we examine the stability of such solute ordered arrangements in binary hard sphere mixtures subject to density maximization through local particle moves.     

On the Statistical Mechanics and Surface Tensions of Binary Mixtures

Within a lattice model describing a binary mixture with fixed concentrations of the species we discuss the relationship between the surface tension of the mixture and the concentrations.     

Correlation between thermodynamic and kinetic fragilities in nonpolymeric glass-forming liquids

A phenomenological relationship between reduced excess heat capacity of supercooled liquid DeltaC(p)(exc)(T(g))DeltaS(m) at the glass transition temperature T(g), fragility index m, and reduced glass transition temperature T(rg)=T(g)T(m), where T(m) is the melting (liquidus) temperature, was derived for fragile nonpolymeric glass-forming liquids under the assumptions that the fragile behavior of these liquids is described by the Vogel-Fulcher-Tammann (VFT) equation; the excess heat capacity of liquid is inversely proportional to the absolute temperature and the VFT temperature T(0) is equal to the Kauzmann temperature T(K). It was found that DeltaC(p)(exc)(T(g))DeltaS(m) is a composite function of m and T(rg), which indicates that the empirical correlation DeltaC(p)(exc)(T(g))DeltaS(m)=0.025m recently identified by Wang et al. [J. Chem Phys. 125, 074505 (2006)] is probably valid only for liquids which have nearly the same values of T(rg).     

The influence of solute distribution on the high nucleation density of Al crystals in amorphous aluminum alloys

An extension of a previous model that describes the role of solute atoms on glass formability leads to the conclusion that solute distribution plays an important role in the formation and stability of amorphous metals. A random distribution of solutes is shown to produce local solute-depleted regions (on the size scale of the mean inter-solute spacing) that provide preferred sites for the formation of crystalline nuclei. The possibility that these solute-depleted regions are responsible for the exceptionally high number density of critical Al nuclei is explored for three Al-Y binary alloys using a computer simulation. Up to 10⁷ Y atoms were placed at random locations in the system, and the number of solute-free regions were counted as a function of the size of these regions. The experimentally observed number density of critical nuclei (∼3 × 10²¹ m⁻³) is reproduced for a critical nucleus about 5 Al atoms in diameter, containing ∼60 Al atoms in an fcc array. Good agreement with previous suggestions of the size of a critical nucleus (about 6 atoms in diameter, containing about 100 atoms) support the conclusion that the current model provides a reasonable physical explanation for the quenched-in features responsible for the exceptionally high nucleation density in some amorphous Al alloys.     

Multipolarities of γ-rays from 92, 94Nb and 94,95,96,97,98Tc

^{92, 94}Nb and ^{94, 96, 98}Tc have been produced by the (p, n) reaction at proton energies on and near the $\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ isobaric analog resonance. ^95,97Tc have been produced by the (p, γ) reaction below the (p, n) threshold. Internal conversion electrons due to the decay of their excited states were detected on-line with a mini-orange spectrometer which is optimized for the energy range 50 to 500 keV. Gamma rays from these nuclei were detected with a thin Ge(Li) detector. Isomeric-delayed internal conversion electrons and γ-rays were observed, using a nanosecond-pulsed beam. The internal conversion coefficients for 55 transitions in these nuclei have been determined and their multipolarities deduced. The multipolarity of the transitions in these nuclei is predominantly M1. Negative parities have been assigned through use of the $\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ isobaric analog resonance enhancements of the population of negative-parity final states. The systematic behavior of the 2^?, 3^? doublet and of the $\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{?}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ multiplet in these nuclei is discussed.     

Icosahedral and dense random cluster packing in metallic glass structures

It has recently been shown that metallic glass structures can be idealized as inter-penetrating solute-centered atomic clusters that are packed with essentially periodic symmetry. The present work applies the same methodology to explore whether experimental observations can be matched by inter-connected solute-centered clusters that are organized in space via dense random cluster packing, Bergman icosahedral cluster packing or Mackay icosahedral cluster packing. Idealized partial pair distribution functions are developed where the symmetry of the solute positions in the structure is derived from the cluster-packing symmetry and the solute concentration, which establishes occupation of inter-cluster sites, especially β structural sites enclosed by an octahedron of solute-centered clusters. While each of the three models matches major features of the measured solute-solute partial pair distribution functions, the arrangement of clusters with Mackay icosahedral ordering provides the best fit. However, this model is not able to match an essential feature in solute-lean glasses and does not provide the same overall agreement as does periodic cluster packing for solute-rich glasses. Strong similarities between the structure factors in the Mackay icosahedral and periodic cluster-packing models, along with expected deviations from the idealized solute positions studied here, are likely to hinder an unambiguous distinction between these two models.     

Glass-formation and crystallization processes in Ag–Y–Cu alloys

Investigation of glass-formation and crystallization processes of several alloys of Ag–Y–Cu system was conducted. The samples were produced by melt spinning and Cu-mold casting. The structure of ribbon samples was examined by X-ray diffractometry and transmission electron microscopy. Phase transformations were studied by differential scanning and isothermal calorimetry and differential thermal analysis. Despite the large difference in atomic radii between the components in the investigated system, even being produced by melt spinning technique at high cooling rate, only Ag₆₁Y₂₉Cu₁₀ alloy with large supercooled liquid region was found to be X-ray amorphous. A principle for obtaining an alloy with high glass forming ability involving difference in atomic radii between the alloy components is considered. Efficient cluster packing model was also tested.     

The influence of efficient atomic packing on the constitution of metallic glasses

Efficient atomic packing is shown to be a fundamental consideration in the formation of metallic glasses. A simple concept of packing efficiency, based on atom packing in the first coordination shell of solute-centred clusters, is proposed and developed. This model leads to the prediction that specific radius ratios, defined as the radius of the solute atom divided by the radius of the solvent atom, are preferred in the constitution of metallic glasses. Analysis of a large number of binary and complex metallic glasses shows that these specific critical radius ratios R* are indeed preferred in known metallic glasses. The predictions of this model extend previous proposals to describe the influence of topology on the formation of metallic glasses. Although this model represents a simple idealization, the strong agreement with published metallic glasses suggests that efficient atomic packing, enabled by solute-centred clusters, forms a fundamental consideration in the constitution of metallic glasses.     

Comparative study of the photochemistry of chloroplast membranes and photosystem II particles

A comparative study of the photoreducing potentials of spinach thylakoid membranes and spinach photosystem II particles has been made. Hexachloroplatinate ions have been used as electron acceptors in a Hill-like assay for oxygen evolution measurements with both thylakoid membranes and photosystem II particles. However, unlike other Hill acceptors, such as ferricyanide, hexachloroplatinate can be fully reduced to metallic platinum that is catalytically active for hydrogen evolution. This is experimentally confirmed in the ability of chloroplast membranes to photoprecipitate platinum and photoproduce molecular hydrogen. Although similar experiments with photosystem II particles resulted in hexachloroplatinate-supported oxygen evolution, hydrogen evolution was not observed. Moreover, photosystem II particles coupled to ferredoxin and hydrogenase resulted in neither hydrogen nor oxygen evolution—a distinct contrast to the results obtained with chloroplast membranes.