Magnetomechanical effects in textured polycrystalline Tb76Dy24

Uniaxial stress-strain measurements were performed on polycrystalline Tb76Dy24 alloys which exhibit "giant magnetostriction" at cryogenic temperatures. The Young's moduli were reduced by up to a factor of five at 77 K, in comparison to their values at 300 K. We attribute this reduction to a mechanical compliance from domain rotation. Large mechanical hysteresis is also found in nominally elastic stress-strain curves measured below the Curie temperature. Hysteretic curves from 0 to 25 MPa demonstrate up to 19% dissipation of the applied mechanical energy. The anisotropy of thermal expansion was also measured and used as a parameter for the degree of crystallographic texture. This anisotropy was correlated to bulk magnetostriction and to mechanical hysteresis

Nanocrystalline and Thin Film Germanium Electrodes with High Lithium Capacity and High Rate Capabilities

Germanium nanocrystals (12 nm mean diam) and amorphous thin films (60-250 nm thick) were prepared as anodes for lithium secondary cells. Amorphous thin film electrodes prepared on planar nickel substrates showed stable capacities of 1700 mAh/g over 60 cycles. Germanium nanocrystals showed reversible gravimetric capacities of up to 1400 mAh/g with 60% capacity retention after 50 cycles. Both electrodes were found to be crystalline in the fully lithiated state. The enhanced capacity, rate capability (1000C), and cycle life of nanophase germanium over bulk crystalline germanium is attributed to the high surface area and short diffusion lengths of the active material and the absence of defects in nanophase materials

Highly Reversible Lithium Storage in Nanostructured Silicon

Anode materials of nanostructured silicon have been prepared by physical vapor deposition and characterized using electrochemical methods. The electrodes were prepared in thin-film form as nanocrystalline particles (12 nm mean diameter) and as continuous amorphous thin films (100 nm thick). The nanocrystalline silicon exhibited specific capacities of around 1100 mAh/g with a 50% capacity retention after 50 cycles. The amorphous thin-film electrodes exhibited initial capacities of 3500 mAh/g with a stable capacity of 2000 mAh/g over 50 cycles. We suggest that the nanoscale dimensions of the silicon circumvents conventional mechanisms of mechanical deterioration, permitting good cycle life

Magnetostriction of single crystal and polycrystalline Tb0.60Dy0.40 at cryogenic temperatures

At cryogenic temperatures, single crystals of TbDy alloys exhibit giant magnetostrictions of nearly 9000 ppm, making these materials promising for engineering service in cryogenic actuators, valves, and positioners. The preparation of single crystals is difficult and costly. Preliminary results on the magnetostriction of textured polycrystalline materials are presented here. For instance, polycrystalline Tb0.60Dy0.40, plane-rolled (one direction of applied stress) to induce crystallographic texture, has shown magnetostrictions at 77 K of 3000 ppm for an applied field of 4.5 kOe and an applied load of 23 MPa, or 48% that of a single crystal under similar conditions. Comparisons are presented between the magnetostrictive response of plane- and form-rolled (two orthogonal directions of applied stress) polycrystalline Tb0.60Dy0.40 at 10 and 77 K. It is reported that at 10 K plane-rolled Tb0.60Dy0.40 exhibits 1600 ppm magnetostriction at an applied field of 4.4 kOe with a minimal applied load of 0.28 MPa. An observed restoration of the initial unstrained state may be a useful feature of polycrystalline materials for engineering service. Finally it is reported that thermal expansion measurements provide a measure of crystallographic texture for comparison with the magnetostriction

Structure and Thermodynamics of the Mixed Alkali Alanates

The thermodynamics and structural properties of the hexahydride alanates (M2M'AlH6) with the elpasolite structure have been investigated. A series of mixed alkali alanates (Na2LiAlH6, K2LiAlH6 and K2NaAlH6) were synthesized and found to reversibly absorb and desorb hydrogen without the need for a catalyst. Pressure-composition isotherms were measured to investigate the thermodynamics of the absorption and desorption reactions with hydrogen. Isotherms for catalyzed (4 mol% TiCl3) and uncatalyzed Na2LiAlH6 exhibited an increase in kinetics, but no change in the bulk thermodynamics with the addition of a dopant. A structural analysis using synchrotron x-ray diffraction showed that these compounds favor the Fm-3m space group with the smaller ion (M') occupying an octahedral site. These results demonstrate that appropriate cation substitutions can be used to stabilize or destabilize the material and may provide an avenue to improving the unfavorable thermodynamics of a number of materials with promising gravimetric hydrogen densities.Comment: 6 pages, 7 figures,3 tables, submitted to PR

X-ray absorption study of Ti-activated sodium aluminum hydride

Ti K-edge x-ray absorption near edge spectroscopy (XANES) was used to explore the Ti valence and coordination in Ti-activated sodium alanate. An empirical relationship was established between the Ti valence and the Ti K-edge onset based on a set of standards. This relationship was used to estimate oxidation states of the titanium catalyst in 2 mol% and 4 mol% Ti-doped NaAlH4. These results demonstrate that the formal titanium valence is zero in doped sodium alanate and nearly invariant during hydrogen cycling. A qualitative comparison of the edge fine structure suggests that the Ti is present on the surface in the form of amorphous TiAl3.Comment: 3 pages, 4 figures, submitted to Appl. Phys. Let

Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Comparison

Knowledge of the relative stabilities of alane (AlH3) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for thirty-eight alane complexes with NH3-nRn (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine, and obtaining upper limits of delta G for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. Based on this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system.Comment: Accepted by the Journal of Physical Chemistry

The Forgotten Side of Partisanship: Negative Party Identification in Four Anglo-American Democracies

Early studies of electoral behavior proposed that party identification could be negative as well as positive. Over time, though, the concept became mostly understood as a positive construct. The few studies that took negative identification into account tended to portray it as a marginal factor that went “hand-in-hand” with positive preferences. Recent scholarship in psychology reaffirms, however, that negative evaluations are not simply the bipolar opposite of positive ones. This article considers negative party identification from this standpoint, and evaluates its impact in recent national elections in Australia, Canada, New Zealand, and the United States. Our findings highlight the autonomous power of negative partisanship. They indicate as well that ideology has an influence on both positive and negative partisan identification

The pleasures and perils of inheritance

Facing death, reflecting on one’s legacies (material and ethical, personal and political) and the legal and interpersonal attempts to resolve or prevent inheritance conflicts, all bring to the fore constructions of memory and identity, intergenerational relations, and the complexities of doing and undoing family and kinship. Consequently, drawing attention to inheritance, keeping sight of it, and bringing it into play is a useful piece of the puzzle of ageing across a range of disciplines and this article provides an overview of some of the key themes in this emerging field