Solids, Volume 5, Issue 3 (September 2024) – 8 articles

Composite materials such as molybdenum carbides, nitrides, oxides, and mixed anionic compounds like Mo(C,N,O)_x embedded in carbonaceous matrix exhibit promising potential as anode materials for lithium batteries, with a preference for fine-grained morphologies. In this study, we present a novel synthetic approach involving an inorganic–organic hybrid precursor precipitated from aqueous solutions of ammonium heptamolybdate and one of two organic species: 1,8-diaminonaphthalene (1,8-DAN) or hexamethylenediamine (HMD). The precipitation reaction can be carried out in a beaker and in a continuous process using a microjet reactor. This enables the synthesis of precursor material on the gram scale within minutes. The pyrolysis of these precursors yields mixtures of Mo(C,N,O)_x, MoO₂, Mo₂C, Mo₂N, and Mo, with the choice of organic compound significantly influencing the resulting phases and the excess carbon content in the pyrolyzed product. Notably, the pyrolysis process maintains the size and morphology of the micro- to nanometer-sized starting materials. Full article

This study explores the feasibility of using Cu/AZO thin films as low-emissivity materials with antibacterial properties, fabricated using the linear sputtering method. The linear sputtering technique deposits thin films onto continuous substrates, offering high throughput, uniform coatings, and precise control over film properties. In this research, Cu/AZO thin films underwent either vacuum annealing or hydrogen plasma annealing treatments. The Cu layer imparts antibacterial properties, while the AZO layer primarily provides thermal insulation. Experimental results show that annealing treatments enhance both photoelectric performance and antibacterial capability. Annealed Cu/AZO films exhibit lower resistivity and emissivity. Among the samples, those subjected to vacuum annealing at 400 °C are most suitable for low-emissivity applications, with an average visible light transmittance of 60%, an emissivity of 0.16, and an antibacterial activity value of 8.8. The Cu/AZO films proposed in this study effectively combine antibacterial and thermal insulation properties, making them relevant for the field of green materials. Full article

Spinel-type InGaMgO₄ with a = 8.56615(3) Å was prepared by treating layered YbFe₂O₄-type InGaMgO₄ at 6 GPa and 1473 K. DFT calculation and Rietveld analysis of synchrotron X-ray powder diffraction data revealed the inverse spinel structure with In³⁺:Ga³⁺/Mg²⁺ = 0.726:0.274 in the tetrahedral site and 0.137:0.863 in the octahedral site. InGaMgO₄ spinel is an insulator with an experimental band gap of 2.80 eV, and the attempt at hole doping by post-annealing in a reducing atmosphere to introduce an oxygen defect was unsuccessful. This is the first report of the bulk synthesis of AB₂O₄ compounds with both YbFe₂O₄ and spinel polymorphs. Full article

The atomistic structure and point-defect thermodynamics of the model $\Sigma 5\left(310\right)\left[001\right]$ grain boundary in CeO₂ were explored with atomistic simulations. An interface with a double-diamond-shaped structural repeat unit was found to have the lowest energy. Segregation energies were calculated for oxygen vacancies, electron polarons, gadolinium and scandium acceptor cations, and tantalum donor cations. These energies deviate strongly from their bulk values over the same length scale, thus indicating a structural grain-boundary width of approximately 1.5 nm. However, an analysis revealed no unambiguous correlation between segregation energies and local structural descriptors, such as interatomic distance or coordination number. From the segregation energies, the grain-boundary space-charge potential in Gouy–Chapman and restricted-equilibrium regimes was calculated as a function of temperature for dilute solutions of (i) oxygen vacancies and acceptor cations and (ii) electron polarons and donor cations. For the latter, the space-charge potential is predicted to change from negative to positive in the restricted-equilibrium regime. For the former, the calculation of the space-charge potential from atomistic segregation energies is shown to require the inclusion of the segregation energies for acceptor cations. Nevertheless, the space-charge potential in the restricted-equilibrium regime can be described well with an empirical model employing a single effective oxygen-vacancy segregation energy. Full article

Akimotoite, ilmenite-type MgSiO₃ high-pressure polymorph can be stable in the lower-mantle transition zone along average mantle and subducting slab geotherms. Significant amounts of Al₂O₃ can be incorporated into the structure, having the pyrope (Mg₃Al₂Si₃O₁₂) composition. Previous studies have investigated the effect of Al₂O₃ on its crystal structure at nearly endmember compositions. In this study, we synthesized high-quality ilmenite-type Mg₃Al₂Si₃O₁₂ phase at 27 GPa and 1073 K by means of a Kawai-type multi-anvil press and refined the crystal structure at ambient conditions using a synchrotron X-ray diffraction data via the Rietveld method to examine the effect of Al₂O₃. The unit-cell lattice parameters were determined to be a = 4.7553(7) Å, c = 13.310(2) Å, and V = 260.66(6) ų, with Z = 6 (hexagonal, R$\overline{3}$). The volume of the present phase was placed on the akimotoite-corundum endmember join. However, the refined structure showed a strong nonlinear behavior of the a- and c-axes, which can be explained by Al incorporation into the MgO₆ and SiO₆ octahedral sites, which are distinctly different each other. Ilmenite-type Mg₃Al₂Si₃O₁₂ phase may be found in shocked meteorites and can be a good indicator for shock conditions at relatively low temperatures of 1027–1127 K. Full article

Governments worldwide are actively committed to achieving their carbon emission reduction targets, and one avenue under exploration is harnessing the potential of hydrogen. Blending hydrogen with natural gas is emerging as a promising strategy to reduce carbon emissions, as it burns cleanly without emitting carbon dioxide. This blending could significantly contribute to emissions reduction in both residential and commercial settings. However, a critical challenge associated with this approach is the potential for Hydrogen Embrittlement (HE), a phenomenon wherein the mechanical properties of pipe steels degrade due to the infiltration of hydrogen atoms into the metal lattice structure. This can result in sudden and sever failures when the steel is subjected to mechanical stress. To effectively implement hydrogen-natural gas blending, it is imperative to gain a comprehensive understanding of how hydrogen affects the integrity of pipe steel. This necessitates the development of robust experimental methodologies capable of monitoring the presence and impact of hydrogen within the microstructures of steel. Key techniques employed for this assessment include microscopic observation, hydrogen permeation tests, and tensile and fatigue testing. In this study, samples from two distinct types of pipeline steels used in the natural gas distribution network underwent rigorous examination. The findings from this research indicate that charged samples exhibit a discernible decline in fatigue and tensile properties. This deterioration is attributed to embrittlement and reduced ductility stemming from the infiltration of hydrogen into the steel matrix. The extent of degradation in fatigue properties is correlated not only to the hydrogen content but also to the hydrogen permeability and diffusion rate influenced by steel’s microstructural features, with higher charging current densities indicating a more significant presence of hydrogen in the natural gas pipeline blend. Full article

The atomic structures of Zn and Na borophosphate glasses were studied using X-ray and neutron scattering techniques. Peaks assigned to the B−O, P−O, and O−O distances confirm that only BO₄ units co-exist with the PO₄ tetrahedra. The Zn−O and Na−O coordination numbers are found to be a little larger than four. The narrowest peaks of the Zn−O first-neighbor distances exist for the glasses along a line connecting the Zn(PO₃)₂ and BPO₄ compositions (50 mol% P₂O₅), which is explained by networks of ZnO₄, BO₄, and PO₄ tetrahedra with twofold coordinated oxygens. The calculated amounts of available oxygen support this interpretation. Broadened peaks occur for glasses with lower P₂O₅ contents, which is consistent with the presence of threefold coordinated oxygens. The two distinct P−O peak components of the Zn and Na borophosphate glasses differ in their relative abundances. This is interpreted as follows: Na⁺ cations coordinate oxygens in some P−O−B bridges, which is something not seen for the Zn²⁺ ions. Full article

Solid-state drug delivery systems for the drug substances transport are of great importance nowadays. In the present work, the non-covalent interactions between taxifolin (Tax) and graphene as well as nitrogenated (N-doped) graphenes were systematically studied by using a wide set of theoretical techniques. Symmetry-adapted perturbation theory (SAPT0) calculations confirmed more favorable adsorption of Tax on N-doped graphenes compared to pristine graphene. It was established that dispersion interactions play the main role in the attractive interactions (>60%), whereas electrostatic and induction forces contribute only moderately to the attraction (~25% and 7–8%, respectively). Independent gradient model (IGM) analysis visually demonstrated the existence of dispersion interactions and hydrogen bonding in the studied Tax complexes. Ab initio molecular dynamics calculations indicated stability of these complexes at different temperatures. Our results show that N-doped graphenes with the enhanced interaction energy (E_int) toward Tax are promising candidates for the technical realization of the targeted drug delivery systems. Full article