National Institute Of Materials Physics - Romania

Calcium borohydride (Ca(BH4)(2)) is a complex hydride that has been less investigated compared to its lighter counterpart, magnesium borohydride. While offering slightly lower hydrogen storage capacity (11.5 wt% theoretical maximum, 9.6 wt% under actual dehydrogenation conditions), there are many improvement avenues for maximizing the reversible hydrogen storage that have been explored recently, from DFT calculations and polymorph investigations to reactive hydride composites (RHCs) and catalytic and nanosizing effects. The stability of Ca(BH4)(2), the possibility of regeneration from spent products, and the relatively mild dehydrogenation conditions make calcium borohydride an attractive compound for hydrogen storage purposes. The ionic conductivity enhancements brought about by the rich speciation of borohydride anions can extend the use of Ca(BH4)(2) to battery applications, considering the abundance of Ca relative to alkali metal borohydrides typically used for this purpose. The current work aims to review the synthetic strategies, structural considerations of various polymorphs and adducts, and hydrogen storage capacity of composites based on calcium borohydrides and related complex hydrides (mixed anions, mixed cations, additives, catalysts, etc.). Additional applications related to batteries, organic and organometallic chemistry, and catalysis have been briefly described.

Calcium borohydride (Ca(BH4)(2)) is a complex hydride that has been less investigated compared to its lighter counterpart, magnesium borohydride. While offering slightly lower hydrogen storage capacity (11.5 wt% theoretical maximum, 9.6 wt% under actual dehydrogenation conditions), there are many improvement avenues for maximizing the reversible hydrogen storage that have been explored recently, from DFT calculations and polymorph investigations to reactive hydride composites (RHCs) and catalytic and nanosizing effects. The stability of Ca(BH4)(2), the possibility of regeneration from spent products, and the relatively mild dehydrogenation conditions make calcium borohydride an attractive compound for hydrogen storage purposes. The ionic conductivity enhancements brought about by the rich speciation of borohydride anions can extend the use of Ca(BH4)(2) to battery applications, considering the abundance of Ca relative to alkali metal borohydrides typically used for this purpose. The current work aims to review the synthetic strategies, structural considerations of various polymorphs and adducts, and hydrogen storage capacity of composites based on calcium borohydrides and related complex hydrides (mixed anions, mixed cations, additives, catalysts, etc.). Additional applications related to batteries, organic and organometallic chemistry, and catalysis have been briefly described.

Energy production, distribution, and storage remain paramount to a variety of applications that reflect on our daily lives, from renewable energy systems, to electric vehicles and consumer electronics. Hydrogen is the sole element promising high energy, emission-free, and sustainable energy, and metal hydrides in particular have been investigated as promising materials for this purpose. While offering the highest gravimetric and volumetric hydrogen storage capacity of all known materials, metal hydrides are plagued by some serious deficiencies, such as poor kinetics, high activation energies that lead to high operating temperatures, poor recyclability, and/or stability, while environmental considerations related to the treatment of end-of-life fuel disposal are also of concern. A strategy to overcome these limitations is offered by nanotechnology, namely embedding reactive hydride compounds in nanosized supports such as graphene. Graphene is a 2D carbon material featuring unique mechanical, thermal, and electronic properties, which all recommend its use as the support for metal hydrides. With its high surface area, excellent mechanical strength, and thermal conductivity parameters, graphene can serve as the support for simple and complex hydrides as well as RHC (reactive hydride composites), producing nanocomposites with very attractive hydrogen storage properties.

The Cu-Y2O3 and CuCrZr-Y2O3 materials have been devised as thermal barriers in nuclear fusion reactors. It is expected that in the nuclear environments, the materials should be working on extreme conditions of irradiation. In this work the Cu-Y2O3 and CuCrZr-Y2O3 were prepared and then irradiated in order to understand the surface irradiation resistance of the material. The composites were prepared in a glove box and consolidated with spark plasma sintering. The microstructures revealed regions of Y2O3 dispersion and Y2O3 agglomerates both in the Cu matrix and in the CuCrZr. The irradiated samples did not show any surface modification indicating that the materials seem to be irradiation resistant in the present situation. The thermal conductivity values for all the samples measured are lower than pure Cu and higher than pure W, however are higher than those expected, and therefore, the application of these materials as thermal barriers is compromised.

The revolutionary economic potential of micro and nanotechnology is already recognized. Micro and nano-scale technologies that use electrical, magnetic, optical, mechanical, and thermal phenomena separately or in combination are either already in the industrial phase or approaching it. The products of micro and nanotechnology are made of small quantities of material but have high functionality and added value. This paper presents such a product: a system with micro-tweezers for biomedical applications-a micromanipulator with optimized constructive characteristics, including optimal centering, consumption, and minimum size, for handling micro-particles and constructive micro components. The advantage of the proposed structure consists mainly in obtaining a large working area combined with a good working resolution due to the double actuation principle: electromagnetic and piezoelectric.

Structure, composition, and transport properties of Mg2-xAgx(Si0.3Sn0.7)1-yGay (x = {0, 0.021, y = {0, 0.02, 0.04, 0.061) solid solutions produced by melting followed by spark plasma sintering are investigated. The preparation method is adjusted to control sample stoichiometry and phase composition. Doping with two types of dopants at different sites, while employing synthesis methods which generate a small amount of secondary phase, is an uncommon approach in this materials, expected to enhance their thermoelectric performance. An enhanced carrier concentration but diminished mobility is observed in the samples with higher amounts of dopant, which leads to the highest values of the power factor, for Mg1.98Ag0.02Si0.27Sn0.67Ga0.06 in a narrow temperature range (575-675 K) around the peak value, of 9.10-4 Wm-1 K-2 at 625 K. The two types of dopants have opposing effects on the thermal conductivity, with Ag promoting strong phonon scattering and decreasing its values while Ga increases them because of its en-hanced carrier concentration. The rather high thermal conductivity values of the double doped compounds produce low values of the ZT without exceeding 0.29 at 627 K for Mg1.98Ag0.02Si0.3Sn0.7 sample.(c) 2023 Elsevier B.V. All rights reserved.

The phosphate KCoCr-(PO4)(2) and iron-substitutedvariants KCoCr1-x Fe x (PO4)(2) (x =0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route,while a high substitution level of Fe was achieved. Their structureswere refined using powder X-ray diffraction and indexed in a monoclinicsystem with a P2(1)/n spacegroup. A 3D framework with six-sided tunnels parallel to the [101]direction was formed in which the K atoms are located. Mo''ssbauerspectroscopy confirms the exclusive presence of octahedral paramagneticFe(3+) ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopyconfirmed the presence of paramagnetic Cr3+ ions. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present higher ionic activity. Relative to the electrochemicalactivity of K, these materials could be good candidates for positiveand/or negative electrode materials for energy storage applications. The synthesized phosphate KCoCr-(PO4)(2) and Fe-substituted variants KCoCr1-x Fe x (PO4)(2) (x = 0.25, 0.5, and 0.75) present a 3D frameworkwith six-sided tunnels in which the K atoms are located. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present improved ionic activity, making these materials goodcandidates for positive and/or negative electrode materials for energystorage applications.

The phosphate KCoCr-(PO4)(2) and iron-substitutedvariants KCoCr1-x Fe x (PO4)(2) (x =0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route,while a high substitution level of Fe was achieved. Their structureswere refined using powder X-ray diffraction and indexed in a monoclinicsystem with a P2(1)/n spacegroup. A 3D framework with six-sided tunnels parallel to the [101]direction was formed in which the K atoms are located. Mo''ssbauerspectroscopy confirms the exclusive presence of octahedral paramagneticFe(3+) ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopyconfirmed the presence of paramagnetic Cr3+ ions. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present higher ionic activity. Relative to the electrochemicalactivity of K, these materials could be good candidates for positiveand/or negative electrode materials for energy storage applications. The synthesized phosphate KCoCr-(PO4)(2) and Fe-substituted variants KCoCr1-x Fe x (PO4)(2) (x = 0.25, 0.5, and 0.75) present a 3D frameworkwith six-sided tunnels in which the K atoms are located. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present improved ionic activity, making these materials goodcandidates for positive and/or negative electrode materials for energystorage applications.

High density (99.5%) ceramic composite composed of titanium boride and boron carbide (70/30 vol%) was obtained by spark plasma sintering and was tested by 3-point bending test in Ar atmosphere at 1800 degrees C. Bending strength was high, around 1.1 GPa. The strength-strain curve presents a peculiar shape composed of three regions where elastic and plastic deformations are active with a different weight. Based on transmission electron microscopy observations we propose a process of mechanical energy absorption driven by shear stress in the boron carbide crystals: stacking faults with (1-11) and (011) stacking planes and twins with (1-11) twinning plane rearrange into nano-twins with (10-1) twinning planes, orthogonal but equivalent to the initial ones. This rearrangement mechanism provides in the first instance a plastic signature, but further contributes strengthening.

High density (99.5%) ceramic composite composed of titanium boride and boron carbide (70/30 vol%) was obtained by spark plasma sintering and was tested by 3-point bending test in Ar atmosphere at 1800 degrees C. Bending strength was high, around 1.1 GPa. The strength-strain curve presents a peculiar shape composed of three regions where elastic and plastic deformations are active with a different weight. Based on transmission electron microscopy observations we propose a process of mechanical energy absorption driven by shear stress in the boron carbide crystals: stacking faults with (1-11) and (011) stacking planes and twins with (1-11) twinning plane rearrange into nano-twins with (10-1) twinning planes, orthogonal but equivalent to the initial ones. This rearrangement mechanism provides in the first instance a plastic signature, but further contributes strengthening.