Search Results (651)

The aim of this work was to investigate the evolutionary mechanisms of an artificial sedimentary agglomerate formed by cathodic polarization in natural seawater during its abandonment to a natural environment. Previous studies indicate that the mineralogical evolution of the material is controlled by kinetic factors and/or the local precipitation of aragonite on the brucite surface. However, the observation of the precipitation of metastable phase precipitation during the initial immersion of this material (in powder form) has suggested the possibility of a more complex mechanism. The present study builds upon previous experimental work and includes thermogravimetric analysis and infrared spectrometry. The results are analyzed using numerical experimentation to evaluate the proposed hypotheses. Findings show that the transformation mechanism is characterized by the precipitation of metastable calcium carbonate phases. Under supersaturation conditions, these hydrated phases form on the brucite surface, limiting the mineral’s contact with the solution. The subsequent transformation of these amorphous phases into aragonite further reduces brucite–solution interaction, which explains the persistence of brucite both in the residual powder after 120 h of immersion and in the consolidated material after more than 20 years of exposure to natural seawater. Full article

ZrO₂-MgO-Al₂O₃ ceramics, despite a long history of research, still attract the attention of researchers due to the high potential of their applications as refractories and matrices for metal ceramics. A unique composition combining high strength and temperature stability is particularly in demand. In this paper, a comprehensive study of ceramics of the composition (90−x)·ZrO₂-10·MgO-x·Al₂O₃ (x = 10–80 wt.%) obtained by solid-phase sintering with preliminary annealing is carried out. Preliminary annealing was used for the possible formation of metastable phases with outstanding mechanical properties. Using the X-ray diffraction method, it was found that most of the samples consist of monoclinic zirconium oxide, magnesium–aluminum spinel, and corundum phases. The exception is the sample with x = 10 wt.%, in which the main phase was a cubic modification of zirconium oxide. By formation this type of ZrO₂ polymorph in the composition hardness and flexural strength significantly increased from 400 to 1380 and 50 to 210 MPa, respectively. The total porosity of ceramics under study lies in the range 6–28%. Using the scanning electron microscopy method, it was found that the phase composition significantly affects the morphology of the microstructure of the sintered bodies. Thus, for sintered ceramics with a high corundum content, the microstructure is characterized by high porosity and a large grain size. For the first time, by applying preliminary annealing, a new type of ternary ceramic ZrO₂-MgO-Al₂O₃ was sintered with potentially outstanding mechanical properties. The presence of a stabilized zirconium oxide phase, stresses in the crystal lattice of the matrix phase, and the formation of cracks in the microstructure are the main factors influencing shrinkage, porosity, microhardness, and biaxial flexural strength. Full article

The vibration properties of materials play a role in their conduction of electric charges. Ionic conductors such as electrodes and solid electrolytes are also relevant in this respect. The vibration properties are typically assessed with infrared and Raman spectroscopy, and inelastic neutron scattering, which all allow for the derivation of the phonon density of states (PDOS) in part of a full portion of the Brioullin zone. Nuclear resonant vibration spectroscopy (NRVS) is a novel method that produces the element-specific PDOS from Mössbauer-active isotopes in a compound. We employed NRVS operando on a pouch cell battery containing a Li⁵⁷FePO₄ electrode, and thus could derive the PDOS of the ⁵⁷Fe in the electrode during charging and discharging. The spectra reveal reversible vibrational changes associated with the two-phase conversion between LiFePO₄ and FePO₄, as well as signatures of metastable intermediate states. We demonstrate how the NRVS data can be used to tune the atomistic simulations to accurately reconstruct the full vibration structures of the battery materials in operando conditions. Unlike optical techniques, NRVS provides bulk-sensitive, element-specific access to the full phonon spectrum under realistic operando conditions. These results establish NRVS as a powerful method to probe lattice dynamics in working batteries and to advance the understanding of ion transport and phase transformation mechanisms in electrode materials. Full article

Phase molybdenum disulfide (1T-MoS₂) holds significant promise as an anode material for sodium-ion batteries (SIBs) due to its metallic conductivity and expanded interlayer distance. However, the practical application of 1T-MoS₂ is hindered by its inherent thermodynamic metastability, which poses substantial challenges for the synthesis of high-purity, long-term stable 1T phase MoS₂. Herein, a synergetic ethanol molecule intercalation and electron injection engineering is adopted to induce the formation and stabilization of 1T-MoS₂ (E-1T MoS₂). The obtained E-1T MoS₂ consists of regularly arranged sphere-like ultrasmall few-layered 1T-MoS₂ nanosheets with expanded interlayer spacing. The high intrinsic conductivity and enlarged interlayer spacing are greatly favorable for rapid Na⁺ or e⁻ transport. The elaborated nanosheets structure can effectively relieve volume variation during Na⁺ intercalating/deintercalating processes, shorten transport path of Na⁺, and enhance diffusion kinetics. Furthermore, a novel sodium reaction mechanism involving the formation of MoS₂ nanoclusters during cycling is revealed to produce the higher surface pseudocapacitive contribution to Na⁺ storage capacity, accelerating Na⁺ reaction kinetics, as confirmed by the kinetics analysis and ex-situ structural characterizations. Consequently, the E-1T MoS₂ electrode exhibits an excellent sodium storage performance. This work provides an important reference for synthesis and reaction mechanism analysis of metastable metal sulfides for advanced SIBs. Full article

Metal hydrides are an attractive way to store hydrogen in a compact and safe manner under low pressure. However, one of the hurdles to the widespread use of this method is the difficulty of the first hydrogenation, which increases the material cost. In this paper, we report the effect of substituting Zr with Ti in Zr_1−xTi_xCr₂ alloys (x = 0, 0.25, 0.5, 0.75, and 1) on the first hydrogenation. All the substituted alloys had similar microstructures and crystallized in the metastable C14 Laves phase. For x = 0, the first hydrogenation was possible at room temperature under 2 MPa of hydrogen pressure. As x increased, the hydrogen capacity decreased. For x = 0.75 and 1, first hydrogenation was practically impossible. Full article

Calcium aluminate cement (CAC) offers rapid strength development, chemical durability in harsh environments, and high-temperature resistance, but its long-term performance may be compromised by the conversion of metastable hexagonal hydrates into stable cubic phases. Concurrently, recycling spent fluorescent lamp glass (SFLG) is limited because of its residual mercury content. This study investigates the use of manually (MAN) and mechanically (MEC) processed SFLG as partial CAC replacements (up to 50 wt.%). Both SFLG types had irregular morphologies with mean particle sizes of ~20 µm and mercury concentrations of 3140 ± 61 ppb (MAN) and 2133 ± 119 ppb (MEC). Moreover, the addition of SFLG reduced the initial and final setting times, whilst MEC waste notably extended the plastic state duration from 20 min (reference) to 69 min (50 wt.% MEC). Furthermore, strength development was accelerated, with SFLG/CAC mortars reaching peak strengths at 7–10 days versus 28 days as in the CAC reference. CAC and 15 wt.% SFLG mortars showed strength loss over time by reason of their phase conversion, whereas mortars with 25–50 wt.% SFLG experienced significant long-term strength gains, reaching ~60 MPa (25 wt.%) and ~45 MPa (35 wt.%), respectively, after 365 days, with strength activity indexes (SAI) near 90% and 70%, respectively. These improvements are attributed to the formation of strätlingite (C₂ASH₈), which stabilized hexagonal CAH₁₀ and mitigated conversion to cubic katoite (C₃AH₆). Mercury leaching remained below 0.01 mg/kg dry matter for all mixes and curing ages, classifying the mortars as non-hazardous and inert under Spanish Royal Decree 646/2020. The results suggest that SFLG can be safely reused as a sustainable admixture in CAC systems, enhancing long-term mechanical performance while minimizing environmental impact. Full article

Background/Objectives: Army Liposome Formulation with QS21 (ALFQ) is a vaccine adjuvant formulation consisting of liposomes that contain saturated zwitterionic and anionic phospholipids, 55 mol% cholesterol, and small molar amounts of monophosphoryl lipid A (MPLA) and QS21 saponin as adjuvants. A unique aspect of ALFQ is that after addition of QS21 to nanoliposomes (<100 nm), the liposomes self-assemble through fusion to form giant (≥1000 nm) unilamellar vesicles (GUVs). The purpose of this study was to introduce and investigate new intermediate structures in the fusion process that we term tethered incomplete microspheres (TIMs), which were discovered by us incidentally as structures that were visible by phase contrast microscopy. Methods: Differential centrifugation; phase contrast microscopy; confocal microscopy of vesicles or TIMs which contain fluorescent chromophores linked to phospholipids or cholesterol; ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) analysis of lipid components of liposomes and TIMs; and dynamic light scattering were all used for the characterization of TIMS. Results and Conclusions: (A) Sizes of TIMs range from overall aggregated structural sizes of ~1 µm to mega sizes of ≥200 µm. (B) Stable TIM structures occur when a fusion process is stopped by depletion of a fusogenic lipid during an evolving fusing of a lipid bilayer membrane. (C) TIMs consist of long-term stable (>2 years), but also metastable, tightly aggregated tear-drop or spherical incomplete GUVs tethered to visible masses of underlying vesicles that are not individually visible. (D) The TIMs and GUVs all contain phospholipid and cholesterol (when present) as bulk lipids. (E) Lyophilized liposomes lacking QS21 saponin, but which still contain MPLA (ALF55lyo), also self-assemble to form GUVs and TIMs. (F) Cholesterol is a required component in nanoliposomes for generation of GUVs and TIMs by addition of QS21. (G) Cholesterol is not required for production of GUVs and TIMs in ALFlyo, but cholesterol greatly reduces and narrows the polydisperse vesicle distribution. Full article

Developing structural materials capable of maintaining integrity under extreme irradiation conditions is a cornerstone challenge for advancing sustainable nuclear energy technologies. The complexity and severity of radiation-induced microstructural changes—spanning multiple length and timescales—pose significant hurdles for purely experimental approaches. This review critically evaluates recent advancements in atomistic modeling, emphasizing its transformative potential to decipher fundamental mechanisms driving microstructural evolution in irradiated alloys. Atomistic simulations, such as molecular dynamics (MD), have successfully unveiled initial defect formation processes at picosecond scales. However, the inherent temporal limitations of conventional MD necessitate advanced methodologies capable of exploring slower, thermally activated defect kinetics. We specifically traced the development of powerful potential energy landscape (PEL) exploration algorithms, which enable the simulation of high-barrier, rare events of defect evolution processes that govern long-term material degradation. The review systematically examines point defect behaviors in various crystal structures—BCC, FCC, and HCP metals—and elucidates their characteristic defect dynamics, respectively. Additionally, it highlights the pronounced effects of chemical complexity in concentrated solid-solution alloys and high-entropy alloys, notably their sluggish diffusion and enhanced defect recombination, underpinning their superior radiation tolerance. Further, the interaction of extended defects with mechanical stresses and their mechanistic implications for material properties are discussed, highlighting the critical interplay between thermal activation and strain rate in defect evolution. Special attention is dedicated to the diverse mechanisms of dislocation–obstacle interactions, as well as the behaviors of metastable grain boundaries under far-from-equilibrium environments. The integration of data-driven methods and machine learning with atomistic modeling is also explored, showcasing their roles in developing quantum-accurate potentials, automating defect analysis, and enabling efficient surrogate models for predictive design. This comprehensive review also outlines future research directions and fundamental questions, paving the way toward autonomous materials’ discovery in extreme environments. Full article

Protein enzymes are highly efficient catalysts that exhibit adaptability and selectivity under diverse biological conditions. In some organisms, such as bacteria, structurally similar enzymes, for instance, shikimate kinase (SK) and adenylate kinase (AK), coexist and act on chemically related ligands. This raises the question of whether these enzymes can accommodate and potentially react with each other’s ligands. In this study, we investigate the stability of non-cognate ligand binding in SK and explore whether external electric fields (EFs) can modulate this interaction, leading to cross-reactivity in SK. Using molecular dynamics simulations, we assess the structural integrity of SK and the binding behavior of ATP and AMP under EF-off and EF-on cases. Our results show that EFs enhance protein structure stability, stabilize non-cognate ligands in the binding pocket, and reduce local energetic frustration near the R116 residue located in the binding site. In addition to this, dimensionality reduction analyses reveal that EFs induce more coherent protein motions and reduce the number of metastable states. Together, these findings suggest that external EFs can reshape enzyme–ligand interactions and may serve as a tool to modulate enzymatic specificity and functional promiscuity. Thus, we provide computational evidence that supports the concept of using an EF as a tunable parameter in enzyme engineering and synthetic biology. However, further experimental investigation would be valuable to assess the reliability of our computational predictions. Full article

Under normal conditions, the novel zinc blende beryllium oxide (zb BeO) exhibits in a metastable crystalline phase, which is less stable than its wurtzite counterpart. Ultrathin zb BeO epifilms have recently gained significant interest to create a wide range of advanced high-resolution, high-frequency, flexible, transparent, nano-electronic and nanophotonic modules. BeO-based ultraviolet photodetectors and biosensors are playing important roles in providing safety and efficiency to nuclear reactors for their optimum operations. In thermal management, BeO epifilms have also been used for many high-tech devices including medical equipment. Phonon characteristics of zb BeO at ambient and high-pressure P ≠ 0 GPa are required in the development of electronics that demand enhanced heat dissipation for improving heat sink performance to lower the operating temperature. Here, we have reported methodical simulations to comprehend P-dependent structural, phonon and thermodynamical properties by using a realistic rigid-ion model (RIM). Unlike zb ZnO, the study of the Grüneisen parameter γ(T) and thermal expansion coefficient α(T) in zb BeO has revealed atypical behavior. Possible reasons for such peculiar trends are attributed to the combined effect of the short bond length and strong localization of electron charge close to the small core size Be atom in BeO. Results of RIM calculations are compared/contrasted against the limited experimental and first-principle data. Full article

Finite-time thermodynamics (FTT) describes the study of thermodynamic processes that take place in finite time. Due to the finite-time requirement, in general the system cannot move from equilibrium state to equilibrium state. As a consequence, excess entropy is generated, available work is reduced, and/or the maximally achievable efficiency is not achieved; minimizing these negative side-effects constitutes an optimal control problem. Particularly challenging are processes and cycles that involve phase transitions of the working fluid material or the target material of a synthesis process, especially since most materials reside on a highly complex energy landscape exhibiting alternative metastable phases or glassy states. In this perspective, we discuss the issues and challenges involved in dealing with such materials when performing thermodynamic processes that include phase transitions in finite time. We focus on thermodynamic cycles with one back-and-forth transition and the generation of new materials via a phase transition; other systems discussed concern the computation of free energy differences and the general applicability of FTT to systems outside the realm of chemistry and physics that exhibit cost function landscapes with phase transition-like dynamics. Full article

This study investigates the ionization balance of Sn ions in an electron beam ion trap (EBIT). Highly charged Sn ions are produced via collisions with a quasi-monochromatic electron beam, and the charge state distribution is analyzed using a Wien filter. Significant Sn¹⁵⁺ production occurs at electron energies below the ionization potential of Sn¹⁴⁺ (379 eV). Calculations attribute this to electron-impact ionization from metastable Sn¹⁴⁺ states. Full article

This paper presents the results of a comprehensive study of the structure, phase composition, thermal corrosion, and tribological properties of multilayer gradient coatings based on YSZ/NiCrAlY obtained using detonation spraying. X-ray phase analysis showed that the coatings consist entirely of metastable tetragonal zirconium dioxide (t’-ZrO₂) phase stabilized by high temperature and rapid cooling during spraying. SEM analysis confirmed the multilayer gradient phase distribution and high density of the structure. Wear resistance, optical profilometry, wear quantification, and coefficient of friction measurements were used to evaluate the operational stability. The results confirm that the structural parameters of the coating, such as porosity and phase gradient, play a key role in improving its resistance to thermal corrosion and CMAS melt, which makes such coatings promising for use in high-temperature applications. It is shown that a dense and thick coating effectively prevents the penetration of aggressive media, providing a high barrier effect and minimal structural damage. Tribological tests in the temperature range from 21 °C to 650 °C revealed that the best characteristics are observed at 550 °C: minimum coefficient of friction (0.63) and high stability in the stage of stable wear. At room temperature and at 650 °C, there is an increase in wear due to the absence or destabilization of the protective layer. Full article

TbCu₇-type Sm-based compounds can be produced in bulk and potentially surpass Nd₂Fe₁₄B as permanent magnets. However, as the processes to prepare anisotropic magnetic particles are limited, the full potential of TbCu₇-type Sm-based compounds cannot be exploited. In this study, metastable TbCu₇-type phases of anisotropic Sm–Fe–N ultrafine particles were prepared using the low-oxygen induction thermal plasma (LO-ITP) process. X-ray diffraction analysis revealed that the obtained TbCu₇-type Sm–Fe alloy nanoparticles exhibited a c/a value of 0.8419, with an Fe/Sm atomic ratio of ~8.5. After nitrogenation, the obtained Sm–Fe–N nanoparticles were aligned under an external magnetic field, indicating that each alloy particle exhibited anisotropic magnetic properties. A substantially high degree of alignment of 91 ± 2% was achieved, quantitatively estimated via pole figure measurements. Numerical analysis following Sm–Fe nanoparticle formation showed that, compared with Fe condensation, Sm condensation persisted even at low temperatures, because of a significant difference in vapor pressure between Sm and Fe. Though this led to a relatively large compositional distribution of Sm within particles with a Sm concentration of 9–12 at%, the preparation of single-phase TbCu₇-type Sm–Fe–N particles could be facilitated by optimizing several parameters during the LO-ITP process. Full article

Emotional intelligence is a crucial determinant of socioemotional adaptation, psychological well-being and healthy habits in a population, although it has been barely studied in Generation Z. Therefore, the following research objectives were established: (1) to measure the levels of attention, clarity and emotional repair of Spanish university students in teaching undergraduates and (2) to design predictive models of emotional intelligence considering sex, anthropometric measurements, physical activity and the use of social networks as factors. A cross-sectional study was conducted with the involvement of Spanish teaching undergraduates. An online questionnaire integrating sociodemographic questions, the International Physical Activity Questionnaire Short Form, Trait Meta-State Mood Scale TMMS-24 and Social Network Addiction Scale SNAddS-6S were administered. University students exhibited higher levels of emotional attention (30.32 ± 6.08) than those of emotional clarity (28.18 ± 6.34) and emotional repair (28.51 ± 6.02). Most students use X, Pinterest, TikTok, Instagram, YouTube and WhatsApp most days of the week. There are positive relationships between attention and emotional clarity (r = 0.33; p ≤ 0.001), attention and emotional repair (r = 0.18; p ≤ 0.001) and clarity and emotional repair (r = 0.44; p ≤ 0.001). In conclusion, males have higher levels of emotional clarity and emotional repair, but females show higher levels of emotional attention. The model with the highest explanatory power is the one obtained for men’s emotional attention. Full article