Designing a Thermoelectric Copper-Rich Sulfide from a Natural Mineral: Synthetic Germanite Cu22Fe8Ge4S32.

This study shows that the design of copper-rich sulfides by mimicking natural minerals allows a new germanite-type sulfide Cu22Fe8Ge4S32 with promising thermoelectric properties to be synthesized. The Mössbauer spectroscopy and X-ray diffraction analyses provide evidence that the structure of our synthetic compound differs from that of the natural germanite mineral Cu26Fe4Ge4S32 by its much higher Cu+/Cu2+ ratio and different cationic occupancies. The coupled substitution Cu/Fe in the Cu26-xFe4+xGe4S32 series also appears as a promising approach to optimize the thermoelectric properties. The electrical resistivity, which decreases slightly as the temperature increases, shows that these materials exhibit a semiconducting behavior, but are at the border of a metallic state. The magnitudes of the electrical resistivity and Seebeck coefficient increase with x, which suggests that Fe for Cu substitution decreases the hole concentration. The thermal conductivity decreases as the temperature increases leading to a moderately low value of 1.2 W m-1 K-1 and a maximum ZT value of 0.17 at 575 K.

Extended Czjzek model applied to NMR parameter distributions in sodium metaphosphate glass.

The extended Czjzek model (ECM) is applied to the distribution of NMR parameters of a simple glass model (sodium metaphosphate, NaPO3) obtained by molecular dynamics (MD) simulations. Accurate NMR tensors, electric field gradient (EFG) and chemical shift anisotropy (CSA) are calculated from density functional theory (DFT) within the well-established PAW/GIPAW framework. The theoretical results are compared to experimental high-resolution solid-state NMR data and are used to validate the considered structural model. The distributions of the calculated coupling constant C(Q) is proportional to |V(zz)| and the asymmetry parameter η(Q) that characterize the quadrupolar interaction are discussed in terms of structural considerations with the help of a simple point charge model. Finally, the ECM analysis is shown to be relevant for studying the distribution of CSA tensor parameters and gives new insight into the structural characterization of disordered systems by solid-state NMR.

Transformations in oxides induced by high-energy ball-milling.

This paper, by no means exhaustive, focuses on high-energy ball-milling of oxides, on their mechanically induced changes and on the consequences of such changes on their physical and chemical properties. High-energy ball-milling offers a fortunate combination of technical simplicity and of complexity both of physical mechanisms which act during milling and of mechanosynthesized materials. Its basic interest, which stems from the large diversity of routes it offers to prepare oxides either directly or indirectly, is illustrated with various families of oxides. The direct path is to be favoured when as-milled oxides are of interest per se because of their nanocrystalline characteristics, their defects or their modified structures which result from mechanically driven phase transformations. The indirect path consists of a sequence of steps starting with mechanically activated oxides which may be subsequently just annealed or submitted to a combination of thermal treatments, with the possible occurrence of various chemical reactions, to prepare the sought-after materials with potential gains in processing temperatures and times. High energy ball-milling of oxides is more and more currently used to activate powders and to prepare nano-oxides at moderate temperatures. The interest of an activation step is well illustrated by the broad development of doped titania powders, synthesized by heat treatment of pre-ground reactants, for photocatalytic applications or to develop antibacterial materials. Another important class of applications of high-energy ball-milling is the formation of composites. It is exemplified here with the case of oxide-dispersed strengthened alloys whose properties are considerably improved by a dispersion of ultra-stable nanosized oxides whose formation mechanisms were recently described. The basic understanding of the mechanisms by which oxides or oxide mixtures evolve by high-energy ball-milling appears to be less advanced than it is for metallic materials essentially because of the overall complexity of the oxide structures, of their surfaces, of their defects and of their mechanical behavior.

Difference in lipid packing sensitivity of exchangeable apolipoproteins apoA-I and apoA-II: an important determinant for their distinctive role in lipid metabolism.

Exchangeable apolipoproteins A-I and A-II play distinct roles in reverse cholesterol transport. ApoA-I interacts with phospholipids and cholesterol of the cell membrane to make high density lipoprotein particles whereas apolipoprotein A-II interacts with high density lipoprotein particles to release apolipoprotein A-I. The two proteins show a high activity at the aqueous solution/lipid interface and are characterized by a high content of amphipathic α-helices built upon repetition of the same structural motif. We set out to investigate to what extent the number of α-helix repeats of this structural motif modulates the affinity of the protein for lipids and the sensitivity to lipid packing. To this aim we have compared the insertion of apolipoproteins A-I and A-II in phospholipid monolayers formed on a Langmuir trough in conditions where lipid packing, surface pressure and charge were controlled. We also used atomic force microscopy to obtain high resolution topographic images of the surface at a resolution of several nanometers and performed statistical image analysis to calculate the spatial distribution and geometrical shape of apolipoproteins A-I and A-II clusters. Our data indicate that apolipoprotein A-I is sensitive to packing of zwitterionic lipids but insensitive to the packing of negatively charged lipids. Interestingly, apolipoprotein A-II proved to be insensitive to the packing of zwitterionic lipids. The different sensitivity to lipid packing provides clues as to why apolipoprotein A-II barely forms nascent high density lipoprotein particles while apolipoprotein A-I promotes their formation. We conclude that the different interfacial behaviors of apolipoprotein A-I and apolipoprotein A-II in lipidic monolayers are important determinants of their distinctive roles in lipid metabolism.

An extension of the Czjzek model for the distributions of electric field gradients in disordered solids and an application to NMR spectra of 71Ga in chalcogenide glasses.

First, the basis and the characteristics of the Czjzek model for the distribution of electric field gradient (EFG) tensor in disordered solids, some of which are still unnoticed, are depicted. That model results from the statistical invariance by rotation of the structure of the considered disordered solid and from the applicability of a central limit theorem to the EFG tensor. These two conditions, which are physically realistic for a wealth of disordered solids, simplify tremendously the derivation of the EFG distribution but at the cost of a complete loss of structural information about the investigated solid. Next, we describe a simple extension of it which is intended to mimic a well-defined local environment, with given values of the asymmetry parameter and of the principal component Vzz of the EFG tensor, perturbed by the disorder of more remote atoms. The effect of disorder is rendered by a Gaussian (Czjzek) noise with an adjustable weight relative to Vzz. The number of free parameters is limited to three, as compared to a sole scale factor for the Czjzek model. Its characteristics are described as a function of the given asymmetry parameter and of the strength of the noise. The aim is to lead to a practical tool which may help to retrieve, as far as possible, the information about the local environment perturbed by disorder from hyperfine measurements and notably from NMR spectra of quadrupolar nuclei. As an example, that extension is applied to some static NMR spectra of 71Ga in covalent glasses. Calculated static 71Ga NMR lineshapes are shown as a function of the parameters of the extended model.

Measurement of granular entropy.

Recently, Dean and Lefèvre [Phys. Rev. Lett. 90, 198301 (2003)] developed a method for testing the statistical mechanical theory of granular packings proposed by Edwards and co-workers [Physica A 157, 1080 (1989); Phys. Rev. E 58, 4758 (1998)]. The method relies on the prediction that the ratio of two overlapping volume histograms should be exponential in volume. We extend the method by showing that one can also calculate the entropy of the packing and also that the method can yield false positive results when the histograms are Gaussians with nearly identical variances. We then apply the method to simulations and experiments of granular compaction. The distribution of global volumes (the volume of the entire packing) is nearly Gaussian and it is difficult to conclude if the theory is valid. On the other hand, the distribution of Voronoï volumes clearly obeys the theoretical prediction.

Preferred sizes and ordering in surface nanobubble populations.

Two types of homogeneous surface nanobubble populations, created by different means, are analyzed statistically on both their sizes and spatial positions. In the first type (created by droplet deposition, case A) the bubble size R is found to be distributed according to a generalized gamma law with a preferred radius R*=20 nm. The radial distribution function shows a preferred spacing at approximately 5.5R*. These characteristics do not show up in comparable Monte Carlo simulated configurations of random packings of hard disks with the same size distribution and the same density, suggesting a structuring effect in the nanobubble formation process. The nanobubble size distribution of the second population type (created by ethanol-water exchange, case B) is a mixture of two clearly separated distributions, hence, with two preferred radii. The local ordering is less significant, due to the looser packing of the nanobubbles.