Configurational order-disorder induced metal-nonmetal transition in B13_{13}C2_{2} studied with first-principles superatom-special quasirandom structure method

Due to a large discrepancy between theory and experiment, the electronic character of crystalline boron carbide B$_{13}$C$_{2}$ has been a controversial topic in the field of icosahedral boron-rich solids. We demonstrate that this discrepancy is removed when configurational disorder is accurately considered in the theoretical calculations. We find that while ordered ground state B$_{13}$C$_{2}$ is metallic, configurationally disordered B$_{13}$C$_{2}$, modeled with a superatom-special quasirandom structure method, goes through a metal to non-metal transition as the degree of disorder is increased with increasing temperature. Specifically, one of the chain-end carbon atoms in the CBC chains substitutes a neighboring equatorial boron atom in a B$_{12}$ icosahedron bonded to it, giving rise to a B$_{11}$C$^{e}$(BBC) unit. The atomic configuration of the substitutionally disordered B$_{13}$C$_{2}$ thus tends to be dominated by a mixture between B$_{12}$(CBC) and B$_{11}$C$^{e}$(BBC). Due to splitting of valence states in B$_{11}$C$^{e}$(BBC), the electron deficiency in B$_{12}$(CBC) is gradually compensated

A 10B-based neutron detector with stacked Multiwire Proportional Counters and macrostructured cathodes

We present the results of the measurements of the detection efficiency for a 4.7 \r{A} neutron beam incident upon a detector incorporating a stack of up to five MultiWire Proportional Counters (MWPC) with Boron-coated cathodes. The cathodes were made of Aluminum and had a surface exhibiting millimeter-deep V-shaped grooves of 45{\deg}, upon which the thin Boron film was deposited by DC magnetron sputtering. The incident neutrons interacting with the converter layer deposited on the sidewalls of the grooves have a higher capture probability, owing to the larger effective absorption film thickness. This leads to a higher overall detection efficiency for the grooved cathode when compared to a cathode with a flat surface. Both the experimental results and the predictions of the GEANT4 model suggests that a 5-counter detector stack with coated grooved cathodes has the same efficiency as a 7-counter stack with flat cathodes. The reduction in the number of counters in the stack without altering the detection efficiency will prove highly beneficial for large-area position-sensitive detectors for neutron scattering applications, for which the cost-effective manufacturing of the detector and associated readout electronics is an important objective. The proposed detector concept could be a technological option for one of the new chopper spectrometers and other instruments planned to be built at the future European Spallation Source in Sweden. These results with macrostructured cathodes generally apply not just to MWPCs but to other gaseous detectors as well.Comment: 14 pages, 9 figure

Surface Morphology of Unused and Used HydromerR-Coated Intravenous Catheters

HydromerR-coated polyurethane (Erythroflex)R catheters, unused, or intravenously inserted for 2-20 days, were studied by scanning electron microscopy (SEM). Both unfixed and fixed (2% glutar-aldehyde in phosphate buffer), and air-or critical-point dried (CPD) specimens were investigated. The catheter segments were sputter-coated with approx. 20 nm gold and studied at an accelerating voltage of 20 kV. The specimens were examined for surface depositions, thickness and structure of the HydromerR layers, and occurrence of adhering and embedded bacteria. The outer HydromerR layer showed, in the un-used specimens, scratches and fissures, as well as adhering foreign bodies. In used specimens, the layer was swollen, with cracks (like dried earth ), and, occasionally , amorphous substances and coccoid bacteria were seen adhering. Damage to the layer, or even its total disappearance was also noted in some specimens. The inner (luminal) HydromerR layer was, in unused specimens, clean and slightly wavy. In used catheters, it was thicker, possibly swollen, with small, isolated or agglomerated protrusions, like a lunar landscape . Adhering platelets and amorphous substances were also occasionally seen. The results suggest that the HydromerR is a fragile material in both its dry and wet forms. Thus, the HydromerR-coated catheters should neither be stored in flexible packs, nor inserted by the Seldinger technique. The findings do not support the belief that the HydromerR-coating can prevent either thrombus formation, or intraluminal occlusion of the in-situ catheters

A unified cluster expansion method applied to the configurational thermodynamics of cubic TiAlN

We study the thermodynamics of cubic Ti1-xAlxN using a unified cluster expansion approach for the alloy problem. The purely configurational part of the alloy Hamiltonian is expanded in terms of concentration and volume dependent effective cluster interactions. By separate expansions of the chemical fixed-lattice, and local lattice relaxation terms of the ordering energies, we demonstrate how the screened generalized perturbation method can be fruitfully combined with a concentration dependent Connolly-Williams cluster expansion method. Utilising the obtained Hamiltonian in Monte Carlo simulations we access the free energy of Ti1-xAlxN alloys and construct the isostructural phase diagram. The results show surprising similarities with the previously obtained mean-field results: The metastable c-TiAlN is subject to coherent spinodal decomposition over a larger part of the concentration range, e.g. from x >= 0.33 at 2000 K.Comment: 21 pages, 7 figure

Gene duplication of the zebrafish kit ligand and partitioning of melanocyte development functions to kit ligand a

The retention of particular genes after the whole genome duplication in zebrafish has given insights into how genes may evolve through partitioning of ancestral functions. We examine the partitioning of expression patterns and functions of two zebrafish kit ligands, kit ligand a (kitla) and kit ligand b (kitlb), and discuss their possible coevolution with the duplicated zebrafish kit receptors (kita and kitb). In situ hybridizations show that kitla mRNA is expressed in the trunk adjacent to the notochord in the middle of each somite during stages of melanocyte migration and later expressed in the skin, when the receptor is required for melanocyte survival. kitla is also expressed in other regions complementary to kita receptor expression, including the pineal gland, tail bud, and ear. In contrast, kitlb mRNA is expressed in brain ventricles, ear, and cardinal vein plexus, in regions generally not complementary to either zebrafish kit receptor ortholog. However, like kitla, kitlb is expressed in the skin during stages consistent with melanocyte survival. Thus, it appears that kita and kitla have maintained congruent expression patterns, while kitb and kitlb have evolved divergent expression patterns. We demonstrate the interaction of kita and kitla by morpholino knockdown analysis. kitla morphants, but not kitlb morphants, phenocopy the null allele of kita, with defects for both melanocyte migration and survival. Furthermore, kitla morpholino, but not kitlb morpholino, interacts genetically with a sensitized allele of kita, confirming that kitla is the functional ligand to kita. Last, we examine kitla overexpression in embryos, which results in hyperpigmentation caused by an increase in the number and size of melanocytes. This hyperpigmentation is dependent on kita function. We conclude that following genome duplication, kita and kitla have maintained their receptor-ligand relationship, coevolved complementary expression patterns, and that functional analysis reveals that most or all of the kita receptor's function in the embryo are promoted by its interaction with kitla. © 2007 Hultman et al

Adaptive hard and tough mechanical response in single-crystal B1 VNx ceramics via control of anion vacancies

High hardness and toughness are generally considered mutually exclusive properties for single-crystal ceramics. Combining experiments and ab initio molecular dynamics (AIMD) atomistic simulations at room temperature, we demonstrate that both the hardness and toughness of single-crystal NaCl-structure VNx/MgO(001) thin films are simultaneously enhanced through the incorporation of anion vacancies. Nanoindentation results show that VN0.8, here considered as representative understoichiometric VNx system, is ~20% harder, as well as more resistant to fracture than stoichiometric VN samples. AIMD modeling of VN and VN0.8 supercells subjected to [001] and [110] elongation reveal that the tensile strengths of the two materials are similar. Nevertheless, while the stoichiometric VN phase systematically cleaves in a brittle manner at tensile yield points, the understoichiometric compound activates transformation-toughening mechanisms that dissipate accumulated stresses. AIMD simulations also show that VN0.8 exhibits an initially greater resistance to both {110} and {111} shear deformation than VN. However, for progressively increasing shear strains, the VN0.8 mechanical behavior gradually evolves from harder to more ductile than VN. The transition is mediated by anion vacancies, which facilitate {110} and {111} lattice slip by reducing activation shear stresses by as much as 35%. Electronic-structure analyses show that the two-regime hard/tough mechanical response of VN0.8 primarily stems from its intrinsic ability to transfer d electrons between 2nd-neighbor and 4th-neighbor (i.e., across vacancy sites) V-V metallic states. Our work offers a route for electronic-structure design of hard materials in which a plastic mechanical response is triggered with loading

Effects of surface vibrations on interlayer mass-transport: ab initio molecular dynamics investigation of Ti adatom descent pathways and rates from TiN/TiN(001) islands

We carry out density-functional ab initio molecular dynamics (AIMD) simulations of Ti adatom (Tiad) migration on, and descent from, TiN -faceted epitaxial islands on TiN(001) at temperatures T ranging from 1200 to 2400 K. Adatom-descent energy-barriers determined via ab initio nudged-elastic-band calculations at 0 Kelvin suggest that Ti interlayer transport on TiN(001) occurs essentially exclusively via direct hopping onto a lower layer. However, AIMD simulations reveal comparable rates for Tiad descent via direct-hopping vs. push-out/exchange with a Ti island edge atom for T >= 1500 K. We demonstrate that the effect is due to surface vibrations, which yield considerably lower activation energies at finite temperatures by significantly modifying the adatom push/out-exchange reaction pathway.Comment: 13 Figure

Zero-bias anomalies of point contact resistance due to adiabatic electron renormalization of dynamical defects

We study effect of the adiabatic electron renormalization on the parameters of the dynamical defects in the ballistic metallic point contact. The upper energy states of the ``dressed'' defect are shown to give a smaller contribution to a resistance of the contact than the lower energy ones. This holds both for the "classical" renormalization related to defect coupling with average local electron density and for the "mesoscopic" renormalization caused by the mesoscopic fluctuations of electronic density the dynamical defects are coupled with. In the case of mesoscopic renormalization one may treat the dynamical defect as coupled with Friedel oscillations originated by the other defects, both static and mobile. Such coupling lifts the energy degeneracy of the states of the dynamical defects giving different mesoscopic contribution to resistance, and provides a new model for the fluctuator as for the object originated by the electronic mesoscopic disorder rather than by the structural one. The correlation between the defect energy and the defect contribution to the resistance leads to zero-temperature and zero-bias anomalies of the point contact resistance. A comparison of these anomalies with those predicted by the Two Channel Kondo Model (TCKM) is made. It is shown, that although the proposed model is based on a completely different from TCKM physical background, it leads to a zero-bias anomalies of the point contact resistance, which are qualitatively similar to TCKM predictions.Comment: 6 pages, to be published in Phys. Rev.

Counting matrices over finite fields with support on skew Young diagrams and complements of Rothe diagrams

We consider the problem of finding the number of matrices over a finite field with a certain rank and with support that avoids a subset of the entries. These matrices are a q-analogue of permutations with restricted positions (i.e., rook placements). For general sets of entries these numbers of matrices are not polynomials in q (Stembridge 98); however, when the set of entries is a Young diagram, the numbers, up to a power of q-1, are polynomials with nonnegative coefficients (Haglund 98). In this paper, we give a number of conditions under which these numbers are polynomials in q, or even polynomials with nonnegative integer coefficients. We extend Haglund's result to complements of skew Young diagrams, and we apply this result to the case when the set of entries is the Rothe diagram of a permutation. In particular, we give a necessary and sufficient condition on the permutation for its Rothe diagram to be the complement of a skew Young diagram up to rearrangement of rows and columns. We end by giving conjectures connecting invertible matrices whose support avoids a Rothe diagram and Poincar\'e polynomials of the strong Bruhat order.Comment: 24 pages, 9 figures, 1 tabl