Evolution of structural and electronic properties standardized description in rhenium disulfide at the bulk-monolayer transition.

The structural and electronic properties of ReS2 different forms - three-dimensional bulk and two-dimensional monolayer - were studied within density functional theory and pseudopotentials. A method for standardizing the description of bulk unit cells and "artificial" slab unit cells for DFT research has been proposed. The preference of this method for studying zone dispersion has been shown. The influence of the vacuum layer thickness on specified special high-symmetry points is discussed. Electron band dispersion in both classical 3D Brillouin zones and transition to 2D Brillouin zones in the proposed two-dimensional approach using the Niggli form of the unit cell was compared. The proposed two-dimensional approach is preferable for low-symmetry layered crystals such as ReS2. It was established that the bulk ReS2 is a direct gap semiconductor (band gap of 1.20 eV), with the direct transition lying in the X point of the first Brillouin zone, and it is in good agreement with published experimental data. The reduction in material dimension from bulk to monolayer was conducted with an increasing band gap up to 1.45 eV, with a moving direct transition towards the Brillouin zone center. The monolayer of ReS2 is a direct-gap semiconductor in a wide range of temperatures, excluding only a narrow range at low temperatures, where it comes as a quasi-direct gap semiconductor. The transition, situated directly in the Γ-point, lies 3.3 meV below the first direct transition located near this point. The electronic density of states of ReS2 in the bulk and monolayer cases of ReS2 were analyzed. The molecular orbitals were built for both types of ReS2 structures as well as the electron difference density maps. For all types of ReS2 structures, an analysis of populations according to Mulliken and Voronoi was carried out. All calculated data is discussed in the context of weak quantum confinement in the 2D case.

Investigation of the structure and dielectric properties of doped barium titanates.

This work examined the influence of zirconium concentration on barium titanate (BZT) BaZrxTi1-xO3, with (x = 0, 0.15, 0.50, 0.75, and 1), produced by the tartrate precursor technique. The Fourier transform infrared (FTIR) spectra support the X-ray diffraction (XRD) results regarding formation of the perovskite structure. Grain size grows with Zr concentration, suggesting that the presence of Zr ions enlarges the grains. The transmission electron microscopy (TEM) images demonstrated that, due to their nano size, nanocrystallites are agglomerated in most images with irregular morphologies and average particle sizes from 20.75 nm to 63.75 nm. Increasing Zr content diminished the piezoelectric coefficient (d33) and the grain size. The value of d33 decreases by increasing Zr content, and there is an inverse relationship between grain size and d33. The remnant polarization of BZT increases with increasing Zr4+ content, which may be suitable for permanent memory device applications.

Growing crystals and studying structure and electronic properties of Cu2ZnGe(SÑ Se1-x)4 compositions.

Single crystals of Cu2ZnGeSe4 and Cu2ZnGeS4 solid solutions were developed and successfully obtained using the chemical vapor transfer method, with iodine acting as a transporter. The structure, compositional dependences of lattice parameters, pycnometric and X-ray densities and microhardness were determined. The chemical composition determined by the X-ray microanalysis satisfactorily corresponds to the nominal one with a tolerance of ±5 %. The XRD analysis showed that all the obtained compounds and their solid solutions have unit cell described by tetragonal symmetry. The attice parameters were found to be а = 5.342 ± 0.005 Å, с = 10.51 ± 0.01 Å for the Сu2ZnGeS4 compound and а = 5.607 ± 0.005 Å, с = 11.04 ± 0.01 Å for the Cu2ZnGeSe4, respectively. Structural studies confirmed the validity of the Vegard's law in relation to the obtained samples. The pycnometric densities of ∼4.28 g/cm3 for the Cu2ZnGeS4 and ∼5.46 g/cm3 for the Cu2ZnGeSe4 were found to be slightly less than their X-ray densities of ∼4.32 g/cm3 and ∼5.52 g/cm3, respectively. The maximum microhardness of ∼398 kg/mm2 for these solid solutions corresponds to x = 0.60. The melt point of the solid solutions increases from ∼1180 °C for the Сu2ZnGeSe4 up to ∼1400 °C for the Сu2ZnGeS4. Based on X-ray fluorescence analysis and DTA data, the phase diagram of the Cu2ZnGeSe4-Cu2ZnGeS4 system was constructed. Analysis of the obtained diagram indicates its first type according to Rozbom's classification.

Heavy alloy based on tungsten and bismuth: fabrication, crystal structure, morphology, and shielding efficiency against gamma-radiation.

W-Bi2O3 composites were fabricated using the hot isostatic pressing technique for the first time. The duration of the samples sintering was 3 minutes under conditions of high pressure and temperature. The study of microstructural features and chemical composition of sintered samples was carried out using scanning electron microscopy and energy-dispersive X-ray spectroscopy, respectively. The effect of temperature on the quality of the obtained W-Bi2O3 composites is determined. The densest samples were obtained at a pressure of 5 GPa and temperatures of 25 °C and 500 °C, the densities of which were 18.10 and 17.85 g cm-3, respectively. It is presented that high temperature exposure during sintering adversely affects both the composite density and microstructure due to the redox reaction accompanied by the reduction of Bi and the oxidation of W. The results of the W-Bi2O3 structure study using X-ray diffraction analysis showed that all samples included the main bulk-centered cubic W phase. The presence of the WO2 phase is noted only when the sintering temperature is increased up to 850 °C, which is confirmed by the appearance of diffraction peaks that correspond to 111 and 22-2 crystallographic planes. The shielding efficiency of the W-Bi2O3 composite against gamma radiation using the Phy-X/PSD software was evaluated. A Co60 isotope with an energy of 0.826-2.506 MeV was used as a source of gamma radiation. The calculation results were compared with those for Pb and Bi. Key shielding parameters such as the linear attenuation coefficient, half-value layer, tenth-value layer, mean free path, and effective atomic number are determined. The calculation results revealed that the W-Bi2O3 composite surpasses Pb and Bi in its shielding properties, which makes it promising for use as a prospective material for radiation shielding applications.

Preparation, phase stability, and magnetization behavior of high entropy hexaferrites.

The polycrystalline SrFe12O19 samples deeply substituted up to at.67% by Al3+, Ga3+, In3+, Co3+, and Cr3+ cations with a high configurational mixing entropy were prepared by solid-phase synthesis. Phase purity and unit cell parameters were obtained from XRD and analyzed versus the average ionic radius of the iron sublattice. The crystallite size varied around ∼4.5 µm. A comprehensive study of the magnetization was realized in various fields and temperatures. The saturation magnetization was calculated using the Law of Approach to Saturation. The accompanying magnetic parameters were determined. The magnetic crystallographic anisotropy coefficient and the anisotropy field were calculated. All investigated magnetization curves turned out to be nonmonotonic. The magnetic ordering and freezing temperatures were extracted from the ZFC and FC curves. The average size of magnetic clusters varied around ∼350 nm. The high values of the configurational mixing entropy and the phenomenon of magnetic dilution were taken into account.

Nanostructured TiAlCuN and TiAlCuCN coatings for spacecraft: effects of reactive magnetron deposition regimes and compositions.

Spacecraft are exposed to a number of factors in the outer space: irradiation by electron flows, high-energy ions, solar electromagnetic radiation, plasma irradiation, and a stream of meteorite particles. All these factors initiate various physical and chemical processes in spacecraft materials, which can eventually lead to failure. To ensure reliable operation of spacecraft, it is necessary to use protective coatings and special radiation-resistant materials. TiAlCuN and TiAlCuCN coatings were formed by reactive magnetron sputtering on different substrates: single-crystal silicon and Titanium Grade 2 wafers. Nitrogen was used as a reactive gas to form nitride coatings and acetylene was used to form carbonitride coatings. The elemental composition was studied by energy-dispersive X-ray (EDX) spectroscopy. The structural-phase state of the coatings was examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Mechanical properties, such as hardness and Young modulus, were investigated by nanoindentation using a CSM Instruments Nanohardness Tester NHT2. The influence of deposition parameters, such as Ti and Al contents, the degree of reactivity α, and carbonitride formation on the structure and their mechanical properties were considered. It was detected that Cu addition to the coatings has effects on crystallite and growth column size refinement in comparison with the TiAlN and TiAlCN analogues due to its segregation along crystalline boundaries, and thus, imparts better mechanical characteristics. The hardness of TiAlCuN and TiAlCuCN coatings varies in the range of H = 25-36 GPa and Young modulus - E = 176-268 GPa. The impact strength index and the H/E* ratio, as well as the plastic deformation resistance index H3/E*2, were calculated. Due to their high mechanical properties, the formed nitride and carbonitride coatings are promising for use in space technologies.

First principles calculation to investigate the effect of Mn substitution on Cu site in CeCu3-x Mn x V4O12 (x = 0, 1, 2 and 3) system.

Structural, electronic, elastic and magnetic properties of CeCu3-x Mn x V4O12 (x = 0, 1, 2 and 3) system have been carried out through DFT using GGA, GGA+U and HF potential. The investigation of structural optimization reveals that lattice parameters of the understudy system is reliable with the reported results and are increasing with the Mn substitution due to their greater atomic radii as compare to Cu atom. Both the cohesive energy and the enthalpy show that CeCu3V4O12 is the most thermodynamically stable among these compounds. When Mn is replaced by Cu in these compounds, not only it become semi-metals, but the host compound also changes from non-magnetic to anti-ferromagnetic and their electrical resistance provides further credence to their electronic behavior. Mechanical stability, anisotropy, and ductility are all demonstrated through the elastic characteristics of these compounds. Due to anti-ferromagnetic ductile nature of the Mn base compounds, it is expected that the compounds in the system may use for spintronic application and in magnetic cloaking devices.

Mechanism of bubbles formation and anomalous phase separation in the CoNiP system.

This study announces the anomalous phase separation in CoNiP alloy electroplating. The observed phenomenon of the formation of magnetic bubbles was described for the first time for this triple CoNiP system. This study briefly covers all stages of magnetic bubble formation, starting from the formation of an amorphous phosphor-rich sublayer, followed by nucleation centers, and finally cobalt-rich bubbles. An explanation for the anomalous mechanism of bubble formation was found in the effects of additives and the phenomena of depolarization and superpolarization.

Electro-oxidation reconstitution of aluminium copper MOF-derived metal oxyhydroxides for a robust OER process.

It is common knowledge that the O2 evolution reaction (OER) is a crucial half-reaction in the electrolysis of water. However, it is currently difficult to create inexpensive OER electrode materials in a way that is efficient, simple, and environmentally friendly. In this research, metal oxy-hydroxides with numerous oxygen defects (M-OOHv) are created at surface of Cu foam (CF) using a unique, straightforward electro-oxidation reconstitution (ER) process. Different spectroscopic and microscopy methods are used to analyse the electrode characteristics of Al2Cu-MOF@M-OOHv-ER/CF; electrochemical measurements display a lower overpotential (η) of 366 mV @ 10 mA cm-2 and a Tafel slope of 95.2 mV dec-1 in 1.0 M KOH. X-Ray diffraction (XRD), scanning electron microscopy (SEM), and Raman studies confirm the phase transition of the metal-organic framework (MOF) to the M-OOH, which acts as the active site to boost the OER activity. Through spectroscopic and microscopic investigations, it is determined that the efficiency of bimetallic electrode materials and oxygen vacancies in the M-OOHv have an impact on the electron power density. The manufactured electrode material additionally showed good durability for 50 hours. As a result, the newly developed Al2Cu-MOF@M-OOHv-ER/CF nanomaterial has greater potential for both electrolysis of water and other energy storage equipment.

Microstructure and high frequency electromagnetic parameters of the soft/soft (CoFe2O4) x : (Ni0.4Cu0.2Zn0.4Fe2O4) y nanocomposites.

The soft/soft (CoFe2O4) x : (Ni0.4Cu0.2Zn0.4Fe2O4) y (CFO x /NCZO y ) nanocomposites (NCs) based on spinel ferrites were produced by the sol-gel method with varying phase's ratio (x : y = 0 : 1; 1 : 1; 2 : 1; 3 : 1; 1 : 3; 1 : 2 and 1 : 0). All NCs consisted of 2 single phases (initial spinels) without any impurities and the absence of chemical interaction between phases. Structural features were investigated and analyzed. The varying of the structural parameters was non-linear and correlated well with the lattice parameter for initial components. There were two maxima observed for all NCs on particle size distribution. It was demonstrated that an increase in the CFO content leads to an increase in the most probable size of the coarse fraction and a decrease in the most probable grain size of the fine fraction. An increase in the NCZO content leads to a decrease in the average size of both fine and coarse fractions. This is obviously due to the large number of defects in the NCZO crystal lattice. The high frequency electromagnetic parameters (real and imaginary parts of the permittivity and permeability, reflection losses) were analyzed in the range of 2-10 GHz. The increase of the energy losses with frequency increase was observed. The nature of the attenuation of the reflected energy associated with the electromagnetic absorption processes due to magnetic losses. Maximal values of the electromagnetic absorption were observed for CFO2/NCZO1 (-18.9 dB). This correlates with the lattice parameters of the composites. The result of the electromagnetic characteristics opens broad perspectives for practical applications such kind of NCs for antenna technology (5G technology) and for electromagnetic absorbing coatings.

The influence of saccharin adsorption on NiFe alloy film growth mechanisms during electrodeposition.

This article deals with the effects of current modes on saccharin adsorption during NiFe electrodeposition, and, as a consequence, its effect on chemical composition, crystal structure, and microstructure of deposited films. For this purpose, we obtained NiFe films using direct, pulse, and pulse-reverse electrodeposition modes. The deposit composition, crystal structure, and surface microstructure are studied. Direct current (DC) and pulse current (PC) films have a smooth surface, while a pulse-reverse current (PRC) film surface is covered by a volumetric cauliflower-like microstructure. The mechanism of the film surface development was considered from the point of view of saccharin adsorption and its action as an inhibitor of vertical grain growth during different current modes. During the DC and PC modes, saccharin is freely adsorbed on the growth centers and restrains their vertical growth. Whereas in the case of the PRC electrodeposition, saccharin adsorbs during cathodic pulses and desorbs during anodic pulses. Therefore, its inhibiting action decreases, vertical grain growth rises, and a rougher surface develops.

Mechanically Stable Magnetic Metallic Materials for Biomedical Applications.

The structural, electrical, and magneto-elastic properties of lanthanide base nitride (Ln = Dy-Lu) anti-perovskites were investigated using density functional theory (DFT). The reported structural outcomes are consistent with the experiment and decrease from Dy to Lu due to the decrease ofatomic radii of Ln atoms. According to the electronic band profile, the metallic characteristics of these compounds are due to the crossing over of Ln-f states at the Fermi level and are also supported by electrical resistivity. The resistivity of these compounds at room temperature demonstrates that they are good conductors. Their mechanical stability, anisotropic, load-bearing, and malleable nature are demonstrated by their elastic properties. Due to their metallic and load-bearing nature, in addition to their ductility, these materials are suitable as active biomaterials, especially when significant acting loads are anticipated, such as those experienced by such heavily loaded implants as hip and knee endo-prostheses, plates, screws, nails, dental implants, etc. In thesecases, appropriate bending fatigue strength is required in structural materials for skeletal reconstruction. Magnetic properties show that all compounds are G-type anti-ferromagnetic, with the Neel temperatures ranging from 24 to 48 K, except Lu3Nin, which is non-magnetic. Due to their anti-ferromagnetic structure, magnetic probes cannot read data contained in anti-ferromagnetic moments, therefore, data will be unchanged by disrupted magnetic field. As a result, these compounds can be the best candidates for magnetic cloaking devices.

Impact of Nd3+ Substitutions on the Structure and Magnetic Properties of Nanostructured SrFe12O19 Hexaferrite.

In this study, SrFe12-xNdxO19, where x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5, was prepared using high-energy ball milling. The prepared samples were characterized by X-ray diffraction (XRD). Using the XRD results, a comparative analysis of crystallite sizes of the prepared powders was carried out by different methods (models) such as the Scherrer, Williamson-Hall (W-H), Halder-Wagner (H-W), and size-strain plot (SSP) method. All the studied methods prove that the average nanocrystallite size of the prepared samples increases by increasing the Nd concentration. The H-W and SSP methods are more accurate than the Scherer or W-H methods, suggesting that these methods are more suitable for analyzing the XRD spectra obtained in this study. The specific saturation magnetization (σs), the effective anisotropy constant (Keff), the field of magnetocrystalline anisotropy (Ha), and the field of shape anisotropy (Hd) for SrFe12-xNdxO19 (0 ≤ x ≤ 0.5) powders were calculated. The coercivity (Hc) increases (about 9% at x = 0.4) with an increasing degree of substitution of Fe3+ by Nd3+, which is one of the main parameters for manufacturing permanent magnets.

Features of Galvanostatic Electrodeposition of NiFe Films with Composition Gradient: Influence of Substrate Characteristics.

NiFe films with a composition gradient are of particular interest from the point of view of fundamental science and practical applications. Such gradient magnetic structures may exhibit unique functional properties useful for sensory applications and beyond. The issue surrounds the anomaly concerning the compositional gradient formed near the substrate in electrolytically deposited binary and ternary iron-containing alloys, which has not previously been clearly explained. In this work, light is shed on this issue, and a clear relationship is found between the structure and surface properties of the substrate, the initially formed NiFe layers and the film composition gradient.

Modeling and X-ray Analysis of Defect Nanoclusters Formation in B4C under Ion Irradiation.

In the presented work, B4C was irradiated with xenon swift heavy ions at the energy of 167 MeV. The irradiation of the substrate was done at room temperature to a fluence of 3.83 × 1014 ion/cm2. The samples were then analyzed with the X-ray diffraction technique to study the structural modification, as it can probe the region of penetration of xenon atoms due to the low atomic number of the two elements involved in the material under study. The nano-cluster formation under ion irradiation was observed. Positron lifetime (PLT) calculations of the secondary point defects forming nanoclusters and introduced into the B4C substrate by hydrogen and helium implantation were also carried out with the Multigrid instead of the K-spAce (MIKA) simulation package. The X-ray diffraction results confirmed that the sample was B4C and it had a rhombohedral crystal structure. The X-ray diffraction indicated an increase in the lattice parameter due to the Swift heavy ion (SHI) irradiation. In B12-CCC, the difference between τ with the saturation of H or He in the defect is nearly 20 ps. Under the same conditions with B11C-CBC, there is approximately twice the value for the same deviation.

Temperature-Driven Transformation of the Crystal and Magnetic Structures of BiFe0.7Mn0.3O3 Ceramics.

The compound BiFe0.7Mn0.3O3 consisting at room temperature of coexistent anti-polar orthorhombic and polar rhombohedral phases has a metastable structural state, which has been studied by laboratory X-ray, synchrotron and neutron diffraction, magnetometry, differential thermal analysis, and differential scanning calorimetry. Thermal annealing of the sample at temperatures above the temperature-driven phase transition into the single phase rhombohedral structure (~700 K) causes an increase of the volume fraction of the rhombohedral phase at room temperature from ~10% up to ~30%, which is accompanied by the modification of the magnetic state, leading to strengthening of a ferromagnetic component. A strong external magnetic field (~5 T) applied to the sample notably changes its magnetic properties, as well as provides a reinforcement of the ferromagnetic component, thus leading to an interaction between two magnetic subsystems formed by the antiferromagnetic matrix with non-collinear alignment of magnetic moments and the nanoscale ferromagnetic clusters coexisting within it. The modification of the structural state and magnetic properties of the compounds and a correlation between different structural and magnetic phases are discussed focusing on the effect of thermal annealing and the impact of an external magnetic field.

Impact of Ga3+ Ions on the Structure, Magnetic, and Optical Features of Co-Ni Nanostructured Spinel Ferrite Microspheres.

Co-Ni ferrite is one of the crucial materials for the electronic industry. A partial substitution with a rare-earth metal brings about modification in crystal lattice and broadens knowledge in the discovery of new magnetic material. Current work reports a Ga3+ substitution in the Co-Ni ferrite with composition Co0.5Ni0.5Fe2-xGaxO4 (where x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0), herein referred to as spinel ferrite microspheres (CoNiGa-SFMCs). The samples were crystallized hydrothermally showing a hollow sphere morphology. The crystal phase, magnetic, morphology, and optical behaviour were examined using various microscopy and spectroscopic tools. While the XRD confirmed the phase of SFMCs, the crystallite size varied between 9 and 12 nm. The Tauc plot obtained from DRS (diffuse reflectance spectroscopy) shows the direct optical energy bandgap (Eg) of the products, with the pristine reading having the value of 1.41 eV Eg; the band gap increased almost linearly up to 1.62 eV along with rising the Ga3+ amount. The magnetic features, on the other hand, indicated the decrease in coercivity (Hc) as more Ga3+ is introduced. Moreover, there was a gradual increase in both saturation magnetization (Ms) and magnetic moment (nB) with increasing amount of Ga3+ till x = 0.6 and then a progressive decline with increases in the x content; this was ascribed to the spin-glass-like behavior at low temperatures. It was detected that magnetic properties correlate well with crystallite/particle size, cation distribution, and anisotropy.

The Interrelation of Synthesis Conditions and Wettability Properties of the Porous Anodic Alumina Membranes.

The results of studies on the wettability properties and preparation of porous anodic alumina (PAA) membranes with a 3.3 ± 0.2 µm thickness and a variety of pore sizes are presented in this article. The wettability feature results, as well as the fabrication processing characteristics and morphology, are presented. The microstructure effect of these surfaces on wettability properties is analyzed in comparison to outer PAA surfaces. The interfacial contact angle was measured for amorphous PAA membranes as-fabricated and after a modification technique (pore widening), with pore sizes ranging from 20 to 130 nm. Different surface morphologies of such alumina can be obtained by adjusting synthesis conditions, which allows the surface properties to change from hydrophilic (contact angle is approximately 13°) to hydrophobic (contact angle is 100°). This research could propose a new method for designing functional surfaces with tunable wettability. The potential applications of ordinary alumina as multifunctional films are demonstrated.

Flowery ln2MnSe4 Novel Electrocatalyst Developed via Anion Exchange Strategy for Efficient Water Splitting.

Oxygen and hydrogen generated by water electrolysis may be utilized as a clean chemical fuel with high gravimetric energy density and energy conversion efficiency. The hydrogen fuel will be the alternative to traditional fossil fuels in the future, which are near to exhaustion and cause pollution. In the present study, flowery-shaped In2MnSe4 nanoelectrocatalyst is fabricated by anion exchange reaction directly grown on nickel foam (NF) in 1.0 M KOH medium for oxygen evolution reaction (OER). The physiochemical and electrical characterization techniques are used to investigate the chemical structure, morphology, and electrical properties of the In2MnSe4 material. The electrochemical result indicates that synthesized material exhibits a smaller value of Tafel slope (86 mV/dec), lower overpotential (259 mV), and high stability for 37 h with small deterioration in the current density for a long time. Hence, the fabricated material responds with an extraordinary performance for the OER process and for many other applications in the future.

Fully Active Bimetallic Phosphide Zn0.5Ge0.5P: A Novel High-Performance Anode for Na-Ion Batteries Coupled with Diglyme-Based Electrolyte.

Metal phosphides are promising candidates for sodium-ion battery (SIB) anode owing to their large capacities with suitable redox potential, while the reversibility and rate performances are limited due to some electrochemically inactive transition-metal components and sluggish reaction kinetics. Here, we report a fully active bimetallic phosphide Zn0.5Ge0.5P anode and its composite (Zn0.5Ge0.5P-C) with excellent performance attributed to the Zn, Ge, and P components exerting their respective Na-storage merit in a cation-disordered structure. During Na insertion, Zn0.5Ge0.5P undergoes an alloying-type reaction, along with the generation of NaP, Na3P, NaGe, and NaZn13 phases, and the uniform distribution of these phases ensures the electrochemical reversibility during desodiation. Based on this reaction mechanism, excellent electrochemical properties such as a high reversible capacity of 595 mAh g-1 and an ultrafast charge-discharge capability of 377.8 mAh g-1 at 50C for 500 stable cycles were achieved within the Zn0.5Ge0.5P-C composite in a diglyme-based electrolyte. This work reveals the Na-storage reaction mechanism within Zn0.5Ge0.5P and offers a new perspective on designing high-performance anodes.