Eutectic modification of Al-Si alloys with rare earth metals

The effects of different concentrations of individual additions of rare earth metals (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) on eutectic modification in Al-10mass%Si has been studied by thermal analysis and optical microscopy. According to the twin-plane re-entrant edge (TPRE) and impurity induced twinning mechanism, rare earth metals with atomic radii of about 1.65 times larger than that of silicon, are possible candidates for eutectic modification. All of the rare earth elements caused a depression of the eutectic growth temperature, but only Eu modified the eutectic silicon to a fibrous morphology. At best, the remaining elements resulted in only a small degree of refinement of the plate-like silicon. The samples were also quenched during the eutectic arrest to examine the eutectic solidification modes. Many of the rare-earth additions significantly altered the eutectic solidification mode from that of the unmodified alloy. It is concluded that the impurity induced twinning model of modification, based on atomic radius alone, is inadequate and other mechanisms are essential for the modification process. Furthermore, modification and the eutectic nucleation and growth modes are controlled independently of each other.

Theory of strongly correlated electron systems. I. Intersite coulomb interaction and the approximation of renormalized fermions in total energy calculations

The diagrammatic strong-coupling perturbation theory (SCPT) for correlated electron systems is developed for intersite Coulomb interaction and for a nonorthogonal basis set. The construction is based on iterations of exact closed equations for many - electron Green functions (GFs) for Hubbard operators in terms of functional derivatives with respect to external sources. The graphs, which do not contain the contributions from the fluctuations of the local population numbers of the ion states, play a special role: a one-to-one correspondence is found between the subset of such graphs for the many - electron GFs and the complete set of Feynman graphs of weak-coupling perturbation theory (WCPT) for single-electron GFs. This fact is used for formulation of the approximation of renormalized Fermions (ARF) in which the many-electron quasi-particles behave analogously to normal Fermions. Then, by analyzing: (a) Sham's equation, which connects the self-energy and the exchange- correlation potential in density functional theory (DFT); and (b) the Galitskii and Migdal expressions for the total energy, written within WCPT and within ARF SCPT, a way we suggest a method to improve the description of the systems with correlated electrons within the local density approximation (LDA) to DFT. The formulation, in terms of renormalized Fermions LIDA (RF LDA), is obtained by introducing the spectral weights of the many electron GFs into the definitions of the charge density, the overlap matrices, effective mixing and hopping matrix elements, into existing electronic structure codes, whereas the weights themselves have to be found from an additional set of equations. Compared with LDA+U and self-interaction correction (SIC) methods, RF LDA has the advantage of taking into account the transfer of spectral weights, and, when formulated in terms of GFs, also allows for consideration of excitations and nonzero temperature. Going beyond the ARF SCPT, as well as RF LIDA, and taking into account the fluctuations of ion population numbers would require writing completely new codes for ab initio calculations. The application of RF LDA for ab initio band structure calculations for rare earth metals is presented in part 11 of this study (this issue). (c) 2005 Wiley Periodicals, Inc.

'Tetol': a stereo-rigid four-strand motif for alkali and alkaline earth metal ion coordination

The tetraalcohol 2,3,5,6-endo,endo,endo,endo-tetrakis(hydroxymethyl]bicyclo[2.2.1]heptane (tetol, 1) has been prepared and crystallises readily as the lithium(I) complex [Li(1)(2)]Cl, forming an oligomeric multi-chain structure in which pairs of alcohols from two crystallographically independent tetol molecules bind lithium ions tetrahedrally. However, formation of monomeric structures in solution is inferred from electrospray mass spectroscopy, which has also shown evidence of exchange of lithium ion in the complexed species by added alkaline earth ions. (C) 2000 Elsevier Science S.A. All rights reserved.

Why H Atom Prefers the On-Top Site and Alkali Metals Favor the Middle Hollow Site on the Basal Plane of Graphite

In this work, the different adsorption properties of H and alkali metal atoms on the basal plane of graphite are studied and compared using a density functional method on the same model chemistry level. The results show that H prefers the on-top site while alkali metals favor the middle hollow site of graphite basal plane due to the unique electronic structures of H, alkali metals, and graphite. H has a higher electronegativity than carbon, preferring to form a covalent bond with C atoms, whereas alkaline metals have lower electronegativity, tending to adsorb on the highest electrostatic potential sites. During adsorption, there are more charges transferred from alkali metal to graphite than from H to graphite.

Effects of promoters on catalytic activity and carbon deposition of Ni/gamma-Al2O3 catalysts in CO2 reforming of CH4

Catalytic reforming of methane with carbon dioxide was studied in a fixed-bed reactor using unpromoted and promoted Ni/gamma-Al2O3 catalysts. The effects of promoters, such as alkali metal oxide (Na2O), alkaline-earth metal oxides (MgO, CaO) and rare-earth metal oxides (La2O3, CeO2), on the catalytic activity and stability in terms of coking resistance and coke reactivity were systematically examined. CaO-, La2O3- and CeO2-promoted Ni/gamma-Al2O3 catalysts exhibited higher stability whereas MgO- and Na2O-promoted catalysts demonstrated lower activity and significant deactivation. Metal-oxide promoters (Na2O, MgO, La2O3, and CeO2) suppressed the carbon deposition, primarily due to the enhanced basicities of the supports and highly reactive carbon species formed during the reaction. In contrast, CaO increased the carbon deposition; however, it promoted the carbon reactivity. (C) 2000 Society of Chemical Industry.

Ionic selectivity of native ATP-activated (P2X) receptor channels in dissociated neurones from rat parasympathetic ganglia

1. The relative permeability of the native P2X receptor channel to monovalent and divalent inorganic and organic cations was determined from reversal potential measurements of ATP-evoked currents in parasympathetic neurones dissociated from rat submandibular ganglia using the dialysed whole-cell patch clamp technique. 2. The P2X receptor-channel exhibited weak selectivity among the alkali metals with a selectivity sequence of Na+ > Li+ > Cs+ > Rb+ > K+, and permeability ratios relative to Cs+ (P-X/P-Cs) ranging from 1. 11 to 0.86. 3. The selectivity for the divalent alkaline earth cations was also weak with the sequence Ca2+ > Sr2+ > Ba2+ > Mn2+ > Mg2+. ATP-evoked currents were strongly inhibited when the extracellular divalent cation concentration was increased. 4, The calculated permeability ratios of different ammonium cations are higher than those of the alkali metal cations. The permeability sequence obtained for the saturated organic cations is inversely correlated with the size of the cation. The unsaturated organic cations have a higher permeability than that predicted by molecular size. 5. Acidification to pH 6.2 increased the ATP-induced current amplitude twofold, whereas alkalization to 8.2 and 9.2 markedly reduced current amplitude. Cell dialysis with either anti-P2X(2) and/or anti-P2X(4) but not anti-P2X(1) antibodies attenuated the ATP-evoked current amplitude. Taken together, these data are consistent with homomeric and/or heteromeric P2X(2) and P2X(4) receptor subtypes expressed in rat submandibular neurones. 6. The permeability ratios for the series of monovalent organic cations, with the exception of unsaturated cations, were approximately related to the ionic size. The relative permeabilities of the monovalent inoganic and organic cations tested are similar to those reported previously for cloned rat P2X2 receptors expressed in mammalian cells.

The igneous charnockite—high-K alkali-calcic I-type granite—incipient charnockite association in Trivandrum Block, southern India

The Pan-African (640 Ma) Chengannoor granite intrudes the NW margin of the Neoproterozoic high-grade metamorphic terrain of the Trivandrum Block (TB), southern India, and is spatially associated with the Cardamom hills igneous charnockite massif (CM). Geochemical features characterize the Chengannoor granite as high-K alkali-calcic I-type granite. Within the constraints imposed by the high temperature, anhydrous, K-rich nature of the magmas, comparison with recent experimental studies on various granitold source compositions, and trace- and rare-earth-element modelling, the distinctive features of the Chengannoor granite reflect a source rock of igneous charnockitic nature. A petrogenetic model is proposed whereby there was a period of basaltic underplating; the partial melting of this basaltic lower crust formed the CM charnockites. The Chengannoor granite was produced by the partial melting of the charnoenderbites from the CM, with subsequent fractionation dominated by feldspars. In a regional context, the Chengannoor I-type granite is considered as a possible heat source for the near-UHT nature of metamorphism in the northern part of the TB. This is different from previous studies, which favoured CM charnockite as the major heat source. The Occurrence of incipient charnockites (both large scale as well as small scale) adjacent to the granite as well as pegmatites (which contain CO2, CO2-H2O, F and other volatiles), suggests that the fluids expelled from the alkaline magma upon solidification generated incipient charnockites through fluid-induced lowering of water activity. Thus the granite and associated alkaline pegmatites acted as conduits for the transfer of heat and volatiles in the Achankovil Shear Zone area, causing pervasive as well as patchy charnockite formation. The transport Of CO2 by felsic melts through the southern Indian middle crust is suggested to be part of a crustal-scale fluid system that linked mantle heat and CO2 input with upward migration of crustally derived felsic melts and incipient charnockite formation, resulting in an igneous charnockite - I-type granite - incipient charnockite association.

Provenance of long-travelled dust determined with ultra-trace-element composition: A pilot study with samples from New Zealand glaciers

We report high-precision inductively coupled plasma mass spectrometric (ICP-MS) compositional data for 39 trace elements in a variety of dust deposits, trapped sediments and surface samples from New Zealand and Australia. Dusts collected from the surface of alpine glaciers in the Southern Alps, New Zealand, believed to have undergone long-distance atmospheric transport from Australia, are recognizable on account of their overabundances of Pb and Cu with respect to typical upper crustal values. Long-travelled dust from Australia therefore scavenges these and other metals (e.g. Zn, Sb and Cd) from the atmosphere during transport and deposition. Hence, due to anthropogenic pollution, long-travelled Australian dusts can be recognized by elevated metal contents. The relative abundance of 25 other elements that are not affected by atmospheric pollution, mineral sorting (Zr and Hf) and weathering/solubility (alkali and earth alkali elements) reflects the geochemistry of the dust source sediment. As a result, we are able to establish the provenance of dust using ultra-trace-element chemistry at regional scale. Comparison of long-travelled dust chemistry with potential Australian sources shows that fits of variable quality are obtained. We propose that the best fitting potential source chemistry most likely represents the major dust source area. A binary mixing model is used to demonstrate that admixture of small quantities of local dust provides an even better fitting dust chemistry for the long-travelled dusts. Copyright (c) 2005 John Wiley & Sons, Ltd.

Trace metals in Antarctic ecosystems: Results from the Larsemann Hills, East Antarctica

Sediments, mosses and algae, collected from lake catchments of the Larsemann Hills, East Antarctica, were analysed to establish baseline levels of trace metals (Ag, As, Cd, Co, Cr, Cu, Ni, Sb, Pb, Se, V and Zn), and to quantify the extent of trace metal pollution in the area. Both impacted and non-impacted sites were included in the study. Four different leaching solutions (1 M MgCl2, 1 M CH3COONH4, 1 M NH4NO3, and 0.3 N HCl) were tested on the fine fraction (< 63 mu m) of the sediments to extract the mobile fraction of trace metals derived from human impact and from weathering of basement lithologies. Results of these tests indicate that dilute HCl partly dissolves primary minerals present in the sediment, thus leading to an overestimate of the mobile trace metal fraction. Concentrations of trace metals released using the other 3 procedures indicate negligible levels of anthropogenic contribution to the trace metal budget. Data derived from this study and a thorough characterisation of the site allowed the authors to define natural baseline levels of trace metals in sediments, mosses and algae, and their spatial variability across the area. The results show that, with a few notable exceptions, human activities at the research stations have contributed negligible levels (lower than natural variability) of trace metals to the Larsemann Hills ecosystem. This study further demonstrates that anthropogenic sources of trace metals can be correctly identified and quantified only if natural baselines, their variability, and processes controlling the mobility of trace metals in the ecosystem, have been fully characterised. (c) 2006 Elsevier Ltd. All rights reserved.

Aerodynamic Drag Reduction for Satellites in Low Earth Orbit

Stalker (AIAA Paper 87-0403) has suggested that, by ejecting molecules directly upstream from the entire face of a satellite, it is possible to reduce the drag on a satellite in low-Earth orbit and hence maintain orbit with a total fuel mass (for forward ejection and conventional reaction rockets) less than the typical mass requirements of conventional rockets. An analytical analysis is presented here, as well as Monte Carlo simulations. These indicate that to reduce the overall drag on the satellite significantly, collisions between the freestream and ejected molecules must occur at least two satellite diameters upstream. This can be achieved if the molecules are ejected far upstream from the satellite’s surface through a sting that projects forward from the satellite. Using some estimates of what would be feasible sting arrangements, we find that the drag on the satellite can be reduced to such an extent that the satellite’s orbit can be maintained with a total fuel mass of less than 60% of that required for reaction rockets alone. Upstream ejection is effective in reducing the drag for freestream Knudsen numbers less than approximately 250, but not otherwise.

Distribution of major, minor, and trace metals in lake environments of Antarctica

The concentrations of major, minor and trace metals were measured in water samples collected from five shallow Antarctic lakes (Carezza, Edmonson Point (No 14 and 15a), Inexpressible Island and Tarn Flat) found in Terra Nova Bay (northern Victoria Land, Antarctica) during the Italian Expeditions of 1993-2001. The total concentrations of a large suite of elements (Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Gd, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, Pb, Pr, Rb, Sc, Si, Sr, Ta, Ti, U, V, Y, W, Zn and Zr) were determined using spectroscopic techniques (ICP-AES, GF-AAS and ICP-MS). The results are similar to those obtained for the freshwater lakes of the Larsemann Hills, East Antarctica, and for the McMurdo Dry Valleys. Principal Component Analysis (PCA) and Cluster Analysis (CA) were performed to identify groups of samples with similar characteristics and to find correlations between the variables. The variability observed within the water samples is closely connected to the sea spray input; hence, it is primarily a consequence of geographical and meteorological factors, such as distance from the ocean and time of year. The trace element levels, in particular those of heavy metals, are very low, suggesting an origin from natural sources rather than from anthropogenic contamination.