Search Results (38)

This study investigates the structural and electronic transitions of sol–gel derived titanium dioxide (TiO₂) thin films using vacuum ultraviolet (VUV) spectroscopy, to elucidate the impact of annealing-induced phase evolution. As the annealing temperature increased from 400 °C to 800 °C, the films transitioned from amorphous to anatase, mixed anatase–rutile, and finally rutile phases. VUV spectroscopy revealed distinct absorption features: a high-energy σ → π* transition below 150 nm, associated with bonding to antibonding orbital excitations, and lower-energy absorption bands in the range 175–180 nm and near 280 nm, attributed to π → π* and t_2g(π) → t*_2g(π*) transitions, respectively. These spectral features highlight the material’s intrinsic electronic states and defect-related transitions. A slight redshift of the absorption band from 176 nm to 177 nm with annealing reflects bandgap narrowing, attributed to increased rutile content, crystallite growth, and defect-induced effects. Broadening and additional absorption features around 280 nm were attributed to oxygen vacancies and reduced titanium oxidation states (Ti³⁺), as corroborated by X-ray photoelectron spectroscopy (XPS). XPS further confirmed the presence of Ti³⁺ species and oxygen vacancies, providing complementary evidence of defect-mediated transitions observed in the VUV spectra. While complementary techniques such as X-ray diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed phase transitions and the reduction of hydroxyl groups, respectively, VUV spectroscopy uniquely captured the dynamic interplay between structural defects, phase evolution, and optical properties. This study underscores the utility of VUV spectroscopy as a powerful tool for probing the electronic structure of TiO₂ films, offering insights critical for tailoring their functional properties in advanced applications. Full article

This paper aims to explore the implications of $U{\left(1\right)}_{L_e-L_{\alpha }}$ gauge symmetries, where $\alpha =\tau ,\mu$, in the neutrino sector through type-(I+II) seesaw mechanisms. To achieve such a hybrid framework, we include a scalar triplet and three right-handed neutrinos. The model can successfully account for the active neutrino masses, mixing angles, mass squared differences, and the CP-violating phase within the $3\sigma$ bounds of NuFit v5.2 neutrino oscillation data. The presence of a new gauge boson at the MeV scale provides an explanation for the muon and electron $(g-2)$ within the confines of their experimental limits. Furthermore, we scrutinize the proposed models in the context of upcoming long-baseline neutrino experiments such as DUNE, P2SO, T2HK, and T2HKK. The findings reveal that P2SO and T2HK have the ability to probe both models in their $5\sigma$-allowed oscillation parameter region, whereas DUNE and T2HKK can conclusively test only the model with $U{\left(1\right)}_{L_e-L_{\mu }}$-symmetry within the $5\sigma$ parameter space if the true values of the oscillation parameters remain consistent with NuFit v5.2. Full article

Barium monofluoride (BaF) is a polar molecule of interest in measurements of the electron electric dipole moment. For this purpose, efforts are underway to investigate this molecule embedded within cryogenic matrices, e.g., in solid Ne. For a theoretical understanding of the electronic structure of such an embedded molecule, the need arises for efficient methods which are accurate but also able to handle a number of atoms which surround the molecule. The calculation for gas-phase BaF can be reduced to involve only outer electrons by representing the inner core of Ba with a pseudopotential, while carrying out a non-relativistic calculation with an appropriate basis set. Thus, the method is effectively at a scalar-relativistic level. In this work, we demonstrate to which extent this can be achieved using coupled-cluster methods to deal with electron correlation. As a test case, the SrF($X^2{\Sigma }^{+}\to B^2{\Sigma }^{+}$) transition is investigated, and excellent accuracy is obtained with the EOM-CC3 method. For the BaF($X^2{\Sigma }^{+}\to {A^{\prime }}^2\Delta$, $X^2{\Sigma }^{+}\to A^2\Pi$, $X^2{\Sigma }^{+}\to B^2{\Sigma }^{+}$) transitions, various coupled-cluster approaches are compared with very good agreement for EOM-CC3 with experimentally derived spectroscopic parameters, at the level of tens of ${\mathrm{cm}}^{-1}$. An exception is the excitation to the ${A^{\prime }}^2\Delta$ state, for which the energy is overestimated by $230{\mathrm{cm}}^{-1}$. The poor convergence behavior for this particular state is demonstrated by providing results from calculations with basis sets of n = 3, 4, 5)-zeta quality. The calculated excitation energy for the $B^2{\Sigma }^{+}$ state agrees better with a deperturbation analysis than with the effective spectroscopic value, with a difference of $120{\mathrm{cm}}^{-1}$. Full article

The demonstration of bioequivalence proposed in the European Medicines Agency’s (EMA’s) draft guideline for topical products with the same qualitative and quantitative composition requires the confirmation of the internal structure equivalence. The impact of the shelf-life on the parameters proposed for internal structure comparison has not been studied. The objectives of this work were: (1) to quantify the effect of the time since manufacturing on the mean value and variability of the parameters proposed by the EMA to characterize the internal structure and performance of topical formulations of a complex topical formulation, and (2) to evaluate the impact of these changes on the assessment of the microstructure equivalence. A total of 5 batches of a topical emulgel containing 1% diclofenac diethylamine were evaluated 5, 14, and 23 months after manufacture. The zero-shear viscosity (η₀), viscosity at 100 s⁻¹ (η₁₀₀), yield stress (σ₀), elastic (G′) and viscous (G″) moduli, internal phase droplet size and in vitro release of the active ingredient were characterized. While no change in variability over time was detected, the mean value of all the parameters changed, especially the droplet size and in vitro release. Thus, combining data from batches of different manufacturing dates may compromise the determination of bioequivalence. The results confirm that to assess the microstructural similarity of complex formulations (such as emulgel), the 90% confidence interval limit for the mean difference in rheological and in vitro release parameters should be 20% and 25%, respectively. Full article

Arc welded 316 stainless steel coatings with flux-cored wires are very promising for marine service environments due to their low cost, high efficiency, and satisfactory performance, while they suffers from Cr dilution during the preparation process. Herein, based on the consideration of increasing the Cr content and ensuring the same value of the Cr/Ni equivalence ratio (Cr_eq/Ni_eq), 316-modified flux-cored wires, 316F (19Cr-12Ni-3Mo) and 316G (22Cr-14Ni-3Mo), were designed under the guidance of a Schaeffler diagram for the improvement of the electrochemical and mechanical properties of 316 stainless steel coatings. The designed flux-cored wires were welded into a three-layer cladding by the tungsten inert gas welding (TIG) process, and the microstructure, corrosion resistance, and mechanical properties of the claddings were investigated. The results showed that 316F and 316G consist of γ-Fe (austenite) and a small portion of δ-Fe (ferrite) as the Cr_eq/Ni_eq is approximately 1.5. However, due to the higher value of the equivalent Cr content (ECC), 316G has an additional intermetallic phase (σ), which precipitates as a strengthening phase at grain boundaries, significantly increasing the tensile and yield strength of 316G but reducing its plasticity. In addition, the corrosion current density (i_corr) and pitting potential (E_b) for 316G are 0.20447 μA·cm⁻² and 0.634 V, respectively, while the values for 316F are 0.32117 μA·cm⁻² and 0.603 V, respectively, indicating that 316G has better anti-corrosion performance. Full article

Mechanical recycling is the most efficient way to reduce plastic pollution due to its ability to maintain the intrinsic properties of plastics as well as provide economic benefits involved in other types of recycling. On the other hand, molecular dynamics (MD) simulations provide key insights into structural deformation, lamellar crystalline axis (c-axis) orientations, and reorganization, which are essential for understanding plastic behavior during structural deformations. To simulate the influence of structural deformations in high-density polyethylene (HDPE) during mechanical recycling while paying attention to obtaining an alternate lamellar orientation, the authors examine a specific way of preparing stacked lamella-oriented HDPE united atom (UA) models, starting from a single 1000 UA (C₁₀₀₀) chain of crystalline conformations and then packing such chain conformations into 2-chain, 10-chain, 15-chain, and 20-chain semi-crystalline models. The 2-chain, 10-chain, and 15-chain models yielded HDPE microstructures with the desired alternating lamellar orientations and entangled amorphous segments. On the other hand, the 20-chain model displayed multi-nucleus crystal growth instead of the lamellar-stack orientation. Structural characterization using a one-dimensional density profile and local order parameter {P₂(r)} analyses demonstrated lamellar-stack orientation formation. All semi-crystalline models displayed the total density (ρ) and degree of crystallinity (χ) range of 0.90–0.94 g/cm⁻³ and ≥42–45%, respectively. A notable stress yield (σ_yield) ≈ 100–120 MPa and a superior elongation at break (ε_break) ~250% was observed under uniaxial strain deformation along the lamellar-stack orientation. Similarly, during the MD simulations, the microstructure phase change represented the average number of entanglements per chain (<Z>). From the present study, it can be recommended that the 10-chain alternate lamellar-stack orientation model is the most reliable miniature model for HDPE that can mimic industrially relevant plastic behavior in various conditions. Full article

Cu–Sn shape-memory microw ires were fabricated by a glass-coated melt spinning method. Effects of Sn content on the microstructure and mechanical properties of microwires were investigated. The phase transforms from martensite to austenite with an increase in Sn from 14.0 atomic percent (at.%) to 16.5 at.%. When the Sn content exceeds 16.5 at.%, a highly ordered intermetallic phase, δ, formed. The fracture stress (σ_f) and the critical stress for martensitic transformation (σ_Ms) increases with an increase in Sn content. The mechanical properties as well as the superelasticity were greatly improved by a high cooling rate in the glass-coated melt spinning method. A bamboo-grained structure was formed in the Cu–Sn microwire with a Sn content of 16 at.% by annealing at 750 °C for 5 h before quenching in water. The results indicate that two opposite strategies of refining the grain size to the micrometer level, or increasing the grain size to a one dimensional size of specimen, e.g., the diameter of the wire, are both effective in improving the superelasticity of the Cu–Sn alloy. Full article

Carbon dioxide (CO₂) dissolution is the secondary trapping mechanism enhancing the long-term security of CO₂ in confined geological formations. CO₂ injected into a randomly multilayered formation will preferentially migrate along high permeability layers, increasing CO₂ dissolution efficiency. In this study, sequential Gaussian simulation is adopted to construct the stratified saline formations, and two-phase flow based on MRST is established to illustrate the spatial mobility and distribution of CO₂ migration. The results show that gravity index $G$ and permeability heterogeneity ${\sigma }_Y^2$ are the two predominant factors controlling the spatial mobility and distribution of CO₂ transports. The CO₂ migration shows a totally different spatial mobility under different gravity index and heterogeneity. When the permeability discrepancy is relatively larger, CO₂ preferentially migrates along the horizontal layer without accompanying the vertical migration. For the formation controlled by gravity index, CO₂ migration is governed by supercritical gaseous characteristics. For the medium gravity index, the upward and lateral flow characteristics of the CO₂ plume is determined by gravity index and heterogeneity. When the gravity index is smaller, permeability heterogeneity is the key factor influencing CO₂ plume characteristics. Permeability heterogeneity is the decisive factor in determining final CO₂ dissolution efficiency. This investigation of CO₂ mobility in randomly multilayered reservoirs provides an effective reference for CO₂ storage. Full article

Based on the data of the gas electron diffraction/mass spectrometry (GED/MS) experiment, the composition of the vapor over rhenium tetrafluoride at T = 471 K was established, and it was found that species of the Re₂F₈ is present in the gas phase. The geometric structure of the Re₂F₈ molecule corresponding to D_4h symmetry was found, and the following geometric parameters of the r_h1 configuration were determined: r_h1(Re-Re) = 2.264(5) Å, r_h1(Re-F) = 1.846(4) Å, α(Re-Re-F) = 99.7(0.2)°, φ(F-Re-Re-F) = 2.4 (3.6)°. Calculations by the self-consistent field in full active space approximation showed that for Re₂F₈, the wave function of the ¹A_1g ground electronic state can be described by the single closed-shell determinant. For that reason, the DFT method was used for a structural study of Re₂X₈ molecules. The description of the nature of the Re-Re bond was performed in the framework of Atom in Molecules and Natural Bond Orbital analysis. The difference in the experimental values of r(Re-Re) in the free Re₂F₈ molecule and the [Re₂F₈]²⁻ dianion in the crystal corresponds to the concept of a triple σ²π⁴ (Re^IV-Re^IV) bond and a quadruple σ²π⁴δ² (Re^III-Re^III) bond, respectively, which are formed between rhenium atoms due to the interaction of d-atomic orbitals. The enthalpy of dissociation of the Re₂F₈ molecular form in two monomers ReF₄ (Δ_dissH°(298) = 109.9 kcal/mol) and the bond energies E(Re-Re) and E(Re-X) in the series Re₂F₈→Re₂Cl₈→Re₂Br₈ molecules were estimated. It is shown that the Re-Re bond energy weakly depends on the nature of the halogen, while the symmetry of the Re₂Br₈ (D_4d) geometric configuration differs from the symmetry of the Re₂F₈ and Re₂Cl₈ (D_4h) molecules. Full article

A scalar–tensor theory of gravity was considered, wherein the gravitational coupling G and the speed of light c were admitted as space–time functions and combined to form the definition of the scalar field $\varphi$. The varying c participates in the definition of the variation of the matter part of the action; it is related to the effective stress–energy tensor, which is a result of the requirement of symmetry under general coordinate transformations in our gravity model. The effect of the cosmological coupling $\Lambda$ is accommodated within a possible behavior of $\varphi$. We analyzed the dynamics of $\varphi$ in the phase space, thereby showing the existence of an attractor point for reasonable hypotheses on the potential $V\left(\varphi \right)$ and no particular assumption on the Hubble function. The phase space analysis was performed both with the linear stability theory and via the more general Lyapunov method. Either method led to the conclusion that the condition $\dot{G}/G=\sigma \left(\dot{c},/,c\right)$, where $\sigma =3$ must hold for the rest of cosmic evolution after the system arrives at the globally asymptotically stable fixed point and the dynamics of $\varphi$ ceases. This result realized our main motivation: to provide a physical foundation for the phenomenological model admitting $\left(G,/,G_0\right)={\left(c,/,c_0\right)}^3$, used recently to interpret cosmological and astrophysical data. The thus covarying couplings G and c impact the cosmic evolution after the dynamical system settles to equilibrium. The secondary goal of our work was to investigate how this impact occurs. This was performed by constructing the generalized continuity equation in our scalar–tensor model and considering two possible regimes for the varying speed of light—decreasing c and increasing c—while solving our modified Friedmann equations. The solutions to the latter equations make room for radiation- and matter-dominated eras that progress to a dark-energy-type of accelerated expansion. Full article

This study focuses on clarifying the regulation of chicken 14-3-3σ protein on the fibrous histiocyte proliferation caused by ALV-J-SD1005 strain infection. DF-1 cells were inoculated with 10² TCID₅₀ of ALV-J-SD1005 strain; the cell proliferation viability was dramatically increased and 14-3-3σ expressions were dramatically decreased within 48 h after inoculation. Chicken 14-3-3σ over-expression could significantly decrease the cell proliferation and the ratio of S-phase cells, but increase the ratio of G2/M-phase cells in ALV-J-infected DF-1 cells; by contrast, chicken 14-3-3σ knockdown expression could cause the opposite effects. Additionally, chicken 14-3-3σ over-expression could also dramatically down-regulate the expressions of CDK2/CDC2, but up-regulate p53 expressions in the DF-1 cells; in contrast, the knockdown expression could significantly increase the expressions of CDK2/CDC2 and decrease p53 expressions. It can be concluded that chicken 14-3-3σ can inhibit cell proliferation and cell cycle by regulating CDK2/CDC2/p53 expressions in ALV-J-infected DF1 cells. ALV-J-SD1005 strain can promote cell proliferation by reducing 14-3-3σ expressions. This study helps to clarify the forming mechanism of acute fibrosarcoma induced by ALV-J infection. Full article

As an important strengthening phase in Al-Mg-Fe alloy, the elastic and ductile–brittle characteristics of Al₁₃Fe₄ intermetallics hold prime significance in ascertaining the mechanical properties and potential application of Al-Mg-Fe alloys. In this study, multialloying of Co, Cu, Cr, Mn, and Ni has been adopted for tuning the mechanical characteristics of the Al₁₃Fe₄ phase; their effects on mechanical features and electronic structure of the Al₁₃Fe₄ phase have been scrutinized systematically by first-principles calculations employing the density functional theory. The replacement of Fe with M (M = Co, Cu, Cr, Mn, and Ni) is energetically advantageous at 0 K, as evidenced by the negative cohesive energy and mixing enthalpy of all Al₁₃(Fe,M)₄ phases. Cu and Ni, on the contrary, have a detrimental impact on Al₁₃Fe_4′s modulus and hardness due to the evolution of chemical bonding strength. Co, Cr, and Mn are thus, interesting candidate elements. In the light of B/G and Poisson’s ratio (σ) criteria, Al₁₃Fe₄, Al₁₃(Fe,Cu)₄, and Al₁₃(Fe,Ni)₄ have superior ductility; however, Al₁₃(Fe,Co), Al₁₃(Fe,Mn), and Al₁₃(Fe,Cr)₄ tend to be brittle materials. Calculation-based findings show that Co, Cr, and Mn are appropriate alloying elements for enhancing fracture toughness, whereas Mn reduces Al₁₃Fe_4′s elastic anisotropy. The electronic structure assessment found that the mechanical properties of the intermetallics are predominantly influenced by the Al-M bonds when the alloying element M replaced Fe. Full article

The aim of this study was to develop a robust methodology for evaluating the spatiotemporal dynamics of the inundation status in tropical wetlands with the currently available Global Navigation Satellite System-Reflectometry (GNSS-R) data by proposing a new quality control technique called the “precision index”. The methodology was applied over the Mekong Delta, one of the most important rice-production systems comprising aquaculture areas and natural wetlands (e.g., mangrove forests, peatlands). Cyclone Global Navigation Satellite System (CyGNSS) constellation data (August 2018–December 2021) were used to evaluate the spatiotemporal dynamics of the reflectivity Γ over the delta. First, the reflectivity Γ, shape and size of each specular footprint and the precision index were calibrated at each specular point and reprojected to a 0.0045° resolution (approximately equivalent to 500 m) grid at a daily temporal resolution (Lv. 2 product); then, the results were obtained considering bias-causing factors (e.g., the velocity/effective scattering area/incidence angle). The Lv. 2 product was temporally integrated every 15 days with a Kalman smoother (+/− 14 days temporal localization with Gaussian kernel: 1σ = 5 days). By applying the smoother, the regional-annual dynamics over the delta could be clearly visualized. The behaviors of the GNSS-R reflectivity and the Advanced Land Observing Satellite-2 Phased-Array type L-band Synthetic Aperture Radar-2 quadruple polarimetric scatter signals were compared and found to be nonlinearly correlated due to the influence of the incidence angle and the effective scattering area. Full article

The paper describes the production and study of spherical powder made from corrosion-resistant 316L steel with the addition of 0.2% and 0.5% Ag. The study of granulometric composition, morphology, fluidity and bulk density, phase composition, microhardness and impurity composition of the spherical powders was carried out. The study showed compliance of the spherical powders with the requirements for powders used for additive manufacturing. The fluidity of the powders was 17.9 s, and the bulk density was 3.76 g/cm³. The particles have a spherical shape with a minimum number of defects and an austenitic-ferritic structure. The study of the phase composition of ingots, wires and powders showed that the ingot structure of all samples consists of austenite. According to the results of studies of the phase composition of the wire, there is a decrease in γ–Fe and an increase in α–Fe and σ–NiCr in going from wire No. 1 to wire No. 3. According to the results of studies of the phase composition of the powder particles, there are three phases, γ-Fe, α-Fe, and Fe₃O₄. The study of microhardness showed a decrease in HV depending on the increase in silver. The hardness of the powder is lower than that of the ingot by 16–24% due to the presence of a ferritic phase in the powder. As a result of plasma spraying, an increase in residual oxygen is observed, which is associated with the oxidation of the melt during plasma dispersion. The amount of nitrogen and sulfur does not change, while the amount of carbon and hydrogen decreases, and the impurities content corresponds to the standards for corrosion-resistant steel. Qualitative and quantitative analysis of the silver content in the samples indicates that it was not affected by the stages involved in obtaining the spherical powder. Full article

Sp²-hybridized monolayer semiconductors (e.g., planar group III-V and IV-IV binary compounds) with inversion symmetry breaking (ISB) display piezoelectricity governed by their σ- and π-bond electrons. Here, we studied their bond-orbital-resolved electronic piezoelectricity (i.e., the σ- and π-piezoelectricity). We formulated a tight-binding piezoelectric model to reveal the different variations of σ- and π-piezoelectricity with the ISB strength ($\Delta$). As $\Delta$ varied from positive to negative, the former decreased continuously, but the latter increased piecewise and jumped at $\Delta =0$ due to the criticality of the π-electrons’ ground-state geometry near this quantum phase-transition point. This led to a piezoelectricity predominated by the π-electrons for a small $|\Delta |$. By constructing an analytical model, we clarified the microscopic mechanisms underlying the anomalous π-piezoelectricity and its subtle relations with the valley Hall effect. The validation of our models was justified by applying them to the typical sp² monolayers including hexagonal silicon carbide, Boron-X (X = N, P, As, Ab), and a BN-doped graphene superlattice. Full article