103 research outputs found
Atomic structure and vibrational properties of icosahedral BC boron carbide
The atomic structure of icosahedral BC boron carbide is determined by
comparing existing infra-red absorption and Raman diffusion measurements with
the predictions of accurate {\it ab initio} lattice-dynamical calculations
performed for different structural models. This allows us to unambiguously
determine the location of the carbon atom within the boron icosahedron, a task
presently beyond X-ray and neutron diffraction ability. By examining the inter-
and intra-icosahedral contributions to the stiffness we show that, contrary to
recent conjectures, intra-icosahedral bonds are harder.Comment: 9 pages including 3 figures, accepted in Physical Review Letter
Pressure-induced metallization in solid boron
Different phases of solid boron under high pressure are studied by first
principles calculations. The -B structure is found to be stable
up to 270 GPa. Its semiconductor band gap (1.72 eV) decreases continuously to
zero around 160 GPa, where the material transforms to a weak metal. The
metallicity, as measured by the density of states at the Fermi level, enhances
as the pressure is further increased. The pressure-induced metallization can be
attributed to the enhanced boron-boron interactions that cause bands overlap.
These results are consist with the recently observed metallization and the
associated superconductivity of bulk boron under high pressure (M.I.Eremets et
al, Science{\bf 293}, 272(2001)).Comment: 14 pages, 5 figure
Ionic high-pressure form of elemental boron
Boron is an element of fascinating chemical complexity. Controversies have
shrouded this element since its discovery was announced in 1808: the new
'element' turned out to be a compound containing less than 60-70 percent of
boron, and it was not until 1909 that 99-percent pure boron was obtained. And
although we now know of at least 16 polymorphs, the stable phase of boron is
not yet experimentally established even at ambient conditions. Boron's
complexities arise from frustration: situated between metals and insulators in
the periodic table, boron has only three valence electrons, which would favour
metallicity, but they are sufficiently localized that insulating states emerge.
However, this subtle balance between metallic and insulating states is easily
shifted by pressure, temperature and impurities. Here we report the results of
high-pressure experiments and ab initio evolutionary crystal structure
predictions that explore the structural stability of boron under pressure and,
strikingly, reveal a partially ionic high-pressure boron phase. This new phase
is stable between 19 and 89 GPa, can be quenched to ambient conditions, and has
a hitherto unknown structure (space group Pnnm, 28 atoms in the unit cell)
consisting of icosahedral B12 clusters and B2 pairs in a NaCl-type arrangement.
We find that the ionicity of the phase affects its electronic bandgap, infrared
adsorption and dielectric constants, and that it arises from the different
electronic properties of the B2 pairs and B12 clusters and the resultant charge
transfer between them.Comment: Published in Nature 453, 863-867 (2009
The high-pressure phase of boron, {\gamma}-B28: disputes and conclusions of 5 years after discovery
{\gamma}-B28 is a recently established high-pressure phase of boron. Its
structure consists of icosahedral B12 clusters and B2 dumbbells in a NaCl-type
arrangement (B2){\delta}+(B12){\delta}- and displays a significant charge
transfer {\delta}~0.5- 0.6. The discovery of this phase proved essential for
the understanding and construction of the phase diagram of boron. {\gamma}-B28
was first experimentally obtained as a pure boron allotrope in early 2004 and
its structure was discovered in 2006. This paper reviews recent results and in
particular deals with the contentious issues related to the equation of state,
hardness, putative isostructural phase transformation at ~40 GPa, and debates
on the nature of chemical bonding in this phase. Our analysis confirms that (a)
calculations based on density functional theory give an accurate description of
its equation of state, (b) the reported isostructural phase transformation in
{\gamma}-B28 is an artifact rather than a fact, (c) the best estimate of
hardness of this phase is 50 GPa, (d) chemical bonding in this phase has a
significant degree of ionicity. Apart from presenting an overview of previous
results within a consistent view grounded in experiment, thermodynamics and
quantum mechanics, we present new results on Bader charges in {\gamma}-B28
using different levels of quantum-mechanical theory (GGA, exact exchange, and
HSE06 hybrid functional), and show that the earlier conclusion about
significant degree of partial ionicity in this phase is very robust
Study of multi-carbide B4C-SiC/(Al, Si) reaction infiltrated composites by SEM with EBSD
In the definition of conceptual developments and design of new materials with singular or unique properties, characterisation takes a key role in clarifying the relationships of composition, properties and processing that define the new material. B4C has a rare combination of properties that makes it suitable for a wide range of applications in engineering: high refractoriness, thermal stability, high hardness and abrasion resistance coupled to low density. However, the low self-diffusion coefficient of B4C limits full densification by sintering. A way to overturn this constraint is by using an alloy, for example Al-Si, forming composites with B4C. Multi-carbide B4C-SiC/(Al, Si) composites were produced by the reactive melt infiltration technique at 1200 - 1350 degrees C with up to 1 hour of isothermal temperature holds. Pressed preforms made from C-containing B4C were spontaneously infiltrated with Al-Si alloys of composition varying from 25 to 50 wt% Si. The present study involves the characterisation of the microstructure and crystalline phases in the alloys and in the composites by X-ray diffraction and SEM/EDS with EBSD. Electron backscatter diffraction is used in detail to look for segregation and spatial distribution of Si and Al containing phases during solidification of the metallic infiltrate inside the channels of the ceramic matrix when the composite cools down to the eutectic temperature (577 degrees C). It complements elemental maps of the SEM/EDS. The production of a flat surface by polishing is intrinsically difficult and the problems inherent to the preparation of EBSD qualified finishing in polished samples of such type of composites are further discussed
- …