Atomic structure and vibrational properties of icosahedral B4_4C boron carbide

The atomic structure of icosahedral B$_4$C 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

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

Fast single piece identification with a 3D scanning LIBS for aluminium cast and wrought alloys recycling

In industrial recycling processes secondary metals need to be separated by material grades before they can be further processed. The identification and separation into different material classes lead to higher value-added industrial feedstock and prevent downgrading processes. Secondary raw materials can be used more efficiently resulting in an increased use of waste products in resource-intensive production processes. Laser-induced breakdown spectroscopy (LIBS) offers a contact free, multi-elemental and fast method for the inline quantitative analysis of single objects in moving particle streams. The LIBS method presented in this paper is based on a 3D object detection combined with a scanning LIBS setup. The optical system consists of a pulsed Nd:YAG laser running at 40 Hz, delivering a 200 mJ double pulse for plasma generation. A high performance three axis galvo-scanner guides the laser beam onto single pieces moving at 3 m s-1 through a measuring volume of 600 × 60 0 × 100 mm3 with a precision of ±1.5 mm. Twenty channels of a high resolution Paschen-Runge spectrometer are simultaneously processed within a few microseconds enabling multi-elemental analysis of different aluminium (Al) alloys. A dimensionless figure of merit is introduced for the evaluation of the analytical performance. Sorting measurements of Al post-consumer scrap charges, consisting of wrought and cast alloys were carried out. After discarding 20% of the data as outliers low and high silicon alloyed Al pieces were identified with a correctness of >96%. In a second sorting scenario the analytical discrimination of 8 different Al alloys of production scrap, requiring high analytical precision, is investigated. A mean identification correctness of wrought Al alloys >95% is demonstrated successfully for the first time