Search Results (621)

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

Structural regulation is of great significance for improving the comprehensive performance of energetic materials (EMs). The structural regulation and properties of EMs were summarized. For single-component EMs, particle size control focuses on quality consistency and industrial scalability, morphology modification mainly improves sphericity through monomers or aggregates and explores the possibility of layered energetic materials in improving mechanical properties, and polycrystalline regulation suppresses metastable phases and explores novel crystalline forms using simulation-guided design. Composite EMs (CEMs) employ core–shell structures to balance safety with performance via advanced coating materials, cocrystal engineering to tailor energy release through intermolecular interactions, and lattice strain modulation, and mixing structures integrates component advantages while enhancing the reaction efficiency. Future directions emphasize computational simulations and novel fabrication methods to guide the rational design and precise preparation of next-generation EMs with specific functions. 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

Background/Objectives: Tegoprazan (TPZ) is a potassium-competitive acid blocker (P-CAB) used to treat conditions such as gastroesophageal reflux disease, peptic ulcer, and Helicobacter pylori infection. It exists in three solid forms: amorphous, Polymorph A, and Polymorph B. This study investigates the molecular basis of polymorph selection, focusing on conformational bias and solvent-mediated phase transformations (SMPTs). Methods: The conformational energy landscapes of two TPZ tautomers were constructed using relaxed torsion scans with the OPLS4 force field and validated by nuclear Overhauser effect (NOE)-based nuclear magnetic resonance (NMR). Hydrogen-bonded dimers were analyzed using DFT-D. Powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), solubility, and slurry tests were conducted using methanol, acetone, and water. Kinetic profiles were modeled with the Kolmogorov–Johnson–Mehl–Avrami (KJMA) equation. Results: Polymorph A was thermodynamically stable across all analyses. Both amorphous TPZ and Polymorph B converted to A in a solvent-dependent manner. Methanol induced direct A formation, while acetone showed a B → A transition. Crystallization was guided by solution conformers and hydrogen bonding. Conclusions: TPZ polymorph selection is governed by solution-phase conformational preferences, tautomerism, and solvent-mediated hydrogen bonding. DFT-D and NMR analyses showed that protic solvents favor the direct crystallization of stable Polymorph A, while aprotic solvents promote the transient formation of metastable Polymorph B. Elevated temperatures and humidity accelerate polymorphic transitions. This crystal structure prediction (CSP)-independent strategy offers a practical framework for rational polymorph control and the mitigation of disappearing polymorph risks in tautomeric drugs. 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

This work investigated the structural response and phase transformation dynamics of silica-bearing cherts subjected to high-temperature processing (up to 1400 °C) and prolonged mechanochemical activation. Through a combination of X-ray diffraction (XRD) with Rietveld refinement, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and transmission electron microscopy (HRTEM), we trace the crystallographic pathways of quartz, moganite, tridymite, and cristobalite under controlled thermal and mechanical stress regimes. The experimental results demonstrated that phase behavior is highly dependent on intrinsic properties such as initial phase composition, impurity presence, and crystallinity. Heating at 1400 °C induced irreversible conversion of quartz, moganite, and tridymite into cristobalite. Samples enriched in cristobalite and tridymite exhibited notable increases in crystallinity, whereas quartz-dominant samples showed either stability or a decline in structural order. Rietveld analyses underscored the critical influence of microstrain and crystallite size on thermal resilience and phase persistence. Thermal profiles revealed by DSC and TGA expose overlapping processes including polymorphic transitions, minor phase dehydration, and redox-driven changes, likely associated with trace components. Mechanochemical processing resulted in partial amorphization and the emergence of phases such as opal and feldspar minerals (microcline, albite, anorthite), interpreted as the product of lattice collapse and subsequent reprecipitation. Heat treatment of chert leads to a progressive rearrangement and recrystallization of its silica phases: quartz collapses around 1000 °C before recovering, tridymite emerges as an intermediate phase, and cristobalite shows the greatest crystallite size growth and least deformation at 1400 °C. These phase changes serve as markers of high-temperature exposure, guiding the identification of heat-altered lithic artefacts, reconstructing geological and diagenetic histories, and allowing engineers to adjust the thermal expansion of ceramic materials. Mechanochemical results provide new insights into the physicochemical evolution of metastable silica systems and offer valuable implications for the design and thermal conditioning of silica-based functional materials used in high-temperature ceramics, glasses, and refractory applications. From a geoarchaeological standpoint, the mechanochemically treated material could simulate natural weathering of prehistoric chert tools, providing insights into diagenetic pathways and lithic degradation processes. Full article

This work shows how the presence of calcium carbonate and sodium carbonate (5% and 20%) affects the hydration of a commercial calcium sulfoaluminate clinker (KCSA). For this study, water-hydrated pastes were prepared and the mechanical compressive strength and hydration rate were determined. The hydration products were characterised by XRD, DTA/TG, FTIR and SEM. The incorporation of CaCO₃ can have a beneficial effect on the development of the mechanical strength of KCSA, especially at 90 days. It does not significantly alter the hydration kinetics and the hydration products formed are mainly ettringite and AH₃. However, sodium carbonate has a detrimental effect, slowing down the hydration kinetics and reducing the development of mechanical strength, especially at early ages. The 20% Na₂CO₃ favours the formation of calcium aluminate, gaylusite and thenardite over ettringite. These phases are metastable in the presence of sodium and decompose to form calcite, alumina gel and a large amount of thenardite, which leaches out as efflorescence, causing microcracks and loss of strength in the material. Full article

In this work, the influences of the Ar flow-rate and sublimation temperature on the phase composition and morphological structure of the sublimation products of analytical reagent MoO₃ are investigated. The results show that the sublimation products are always composed of thermodynamically stable orthorhombic molybdenum trioxide (α-MoO₃) and metastable monoclinic molybdenum trioxide (β-MoO₃) under different reaction conditions, among which the proportion of β-MoO₃ gradually increases with the increase in Ar flow-rate and the decrease in sublimation temperature. The formation temperature of α-MoO₃ is mainly between 780 K and 847 K, with the particles exhibiting an obvious sheet-like morphology. This work also finds that β-MoO₃ is mainly generated below 500 K; however, due to the co-actions of the deposition of gaseous MoO₃ molecules, the adsorption of Ar molecules, and the collision effect between the different particles, the newly formed β-MoO₃ is more inclined to take a spherical-shaped morphology in order to maintain its lowest energy state. Full article

The effect of strontium substitution on the crystal tructure, as well as the magnetic, and electrical properties of lanthanum ferrite (LaFeO₃) synthesized by high-energy ball milling, is studied, with an emphasis on magnetodielectric coupling. X-ray diffraction (XRD) confirmed the successful synthesis of orthorhombic La_1−xSr_xFeO₃ for doping levels up to 0.2 mol. At 0.3 mol Sr²⁺, two phases appear: La_0.6Sr_0.4FeO_2.976 and La_0.8Sr_1.2FeO_3.714, the latter being metastable. This phase vanishes at 0.5 mol. The Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis confirmed these results using a vibrating sample magnetometer (VSM), whose measurements show ferromagnetism at 0.1 and 0.3 mol Sr²⁺, attributed to crystal distortion, magnetic spin rearrangement, and as consequence, modifications in the double-exchange interactions. Dielectric tests reveal that higher Sr²⁺ concentrations lead to increased relative permittivity, dielectric losses, and conductivity, linked to oxygen vacancy formation. This study demonstrates a room-temperature magnetodielectric coupling of 32% in Sr-doped lanthanum ferrite, highlighting its potential for technological applications. Full article

Thin, dense and nanocrystal bismuth oxide films were prepared by the in situ plasma-assisted reactive evaporation (ARE) method using lead doping. Thin films were deposited at room temperature and at 500 °C temperature on glass and silicon substrates. X-ray diffraction, SEM, EDS, and optical measurements were applied to characterize these bismuth oxide films. The results showed that it is possible to synthesize the δ-Bi₂O₃ phase thin films at a temperature lower than 729 °C using an plasma-assisted reactive evaporation (ARE) method and stabilize it (to room temperature) using the additives of lead oxide. The influence of lead oxide concentration on phase formation was investigated. The optimal amount of lead oxide dopant was determined. An excess of lead oxide concentration forms PbO and δ-Bi₂O₃ mixture phases and nanorods appear in films. The synthesized δ-Bi₂O₃ phase was metastable; it transformed into the β-Bi₂O₃ phase after thermal impact during impedance measurements. The cross section of thin film sample shows the dense and monolithic structure. Optical measurements show that the optical band gap increases with increasing lead concentration. It was found that the highest total ionic conductivity of (Bi_1−xPb_0.26)₂O₃ is 0.165 S/cm at 1073 K temperature and activation energy is ΔE_tot = 0.5 eV. Full article

High-Cu-content (Cu-content > 1.3 at.%) nanocrystalline alloys exhibit wide heat-treatment windows and favorable soft magnetic properties due to the presence of pre-existing α-Fe nanocrystals. By fabricating ribbons with varying thicknesses to tailor cooling rates, distinct structural characteristics were achieved in Fe₈₂B_16.5Cu_1.5 alloy ribbons. Notably, the face-centered cubic (fcc) γ-Fe phase was identified in Fe-based nanocrystalline alloys. The precipitation of the fcc γ-Fe phase originates from a phase-selection mechanism under specific cooling conditions, while its retention in the as-quenched ribbon with a thickness of 27 μm is attributed to kinetic suppression during rapid cooling and the nanoscale stabilization effect. The formation of the fcc γ-Fe phase significantly reduced the saturation flux density (B_s) and increased coercivity (H_c), concurrently destabilizing the residual amorphous matrix. By suppressing the precipitation of the γ-Fe and Fe₃B phases through precise control of ribbon thickness and annealing parameters, the alloy ribbon with a thickness of 16 μm achieved an optimal combination of B_s (1.82 T) and H_c (8.3 A/m). These findings on anomalous fcc γ-Fe phase precipitation provide novel insights into metastable phase engineering and offer structural design guidelines for alloys containing pre-existing α-Fe nanocrystals. Full article

Local temperature measurement is crucial for understanding nanoscale thermal transport and developing nanodevices for biomedical, photonic, and optoelectronic applications. The rise of photothermal therapy for cancer treatment has increased the demand for high-resolution nanothermometric techniques capable of non-contact intracellular temperature measurement and modification. Raman spectroscopy meets this need: the ratio of anti-Stokes to Stokes Raman intensities for a specific vibrational mode correlates with local temperature through the Boltzmann distribution. The present study proposes a novel photothermal therapy agent designed to advance the current state of the art while adhering to green chemistry principles, thereby favoring low-temperature synthesis involving limited energy consumption. A key challenge in this field is to achieve close contact between plasmonic nanosystems, which act as nanoheaters, and local temperature sensors. This is achieved by employing silver nanoparticles as a heat release agent, coated with anatase-phase titanium dioxide, as a local temperature sensor. The proposed synthesis, which combines refluxing and subcritical solvothermal treatments, enables direct anatase formation, despite its metastability under standard conditions, thus eliminating the need for a calcination step. Structural characterization through SAED-HRTEM and Raman spectroscopy confirms the successful crystallization of the desired phase. Moreover, the nanothermometry measurements conducted at various wavelengths ultimately demonstrate both the effectiveness of these nanomaterials as thermometric probes, with a relative sensitivity of about 0.24 K⁻¹%, and their capability as local heaters, with a release of a few tens of degrees. This work demonstrates a new synthetic strategy for these nanocomposites, which offers a promising pathway for the optimization of nanosystems in therapeutic applications. Full article

We investigated the morphological patterns, crystalline structures and their thermal stability in solidified Au–Ge nanoparticles ranging in size from 10 to 500 nm. Liquid Au–Ge alloy nanoparticles with hypoeutectic composition were rapidly cooled from a temperature of 500 °C in a TEM and characterized using advanced TEM techniques. We demonstrated that Au–Ge nanoparticles 10–80 nm in size predominantly solidified into a Janus-like morphology with nearly pure single-crystalline hcp Au and diamond cubic Ge domains. These particles remained stable up to the eutectic temperature, indicating that Ge doping and particle size play key roles in stabilizing the hcp Au phase. In turn, larger nanoparticles exhibited a metastable core–shell morphology with polycrystalline Ge shell and hcp Au-Ge alloy core under solidification. It was shown that the mentioned morphology and crystalline structure evolved into the equilibrium Janus morphology with fcc Au and diamond Ge domains at temperatures above ≈160 °C. Full article

The structural evolution of Ho₂Ce₂O₇ under high pressure was systematically investigated using synchrotron X-ray diffraction (up to 31.5 GPa) and Raman spectroscopy (up to 41.7 GPa). At ambient pressure, the compound adopts a common C-type cubic rare earth oxide structure (space group Ia-3). A pressure-induced phase transition was observed to commence at 23.8 GPa, characterized by a gradual structural evolution that persisted through the maximum experimental pressure of 31.5 GPa. This transition involves cation disordering accompanied by coordination environment modifications. High-pressure X-ray diffraction analysis reveals the coexistence of two distinct phases above the transition threshold: the parent cubic phase (Ia-3) and a metastable hexagonal phase (R-3c). Notably, the high-pressure phase configuration persists upon complete decompression to ambient conditions, demonstrating the irreversible nature of this pressure-induced structural transition. Full article

Preparative protein crystallization is regarded as an economically sustainable protein purification alternative to chromatography in biotechnological downstream processing. However, protein crystallization is a not-well-understood process that is usually slow and poorly reproducible. A promising strategy for enhancing protein crystallization is exploiting the metastable liquid–liquid phase separation (LLPS) of protein solutions. Here, we report an enhancement of lysozyme-crystallization yield by using a combination of two additives under LLPS conditions. The first additive, NaCl (0.15 M), is necessary to introduce protein–protein attractive interactions and induce LLPS by lowering temperature. The second additive, 4-(2-hydroxyethyl)-1-piperazineethanesulfonate (HEPES, 0.10 M, pH 7.4), accumulates in the metastable protein-rich liquid phase and thermodynamically stabilizes lysozyme crystals. We found that this combination of additives leads to crystallization yields of higher than 90% under LLPS conditions at a lysozyme concentration of 5% by weight and a fairly low ionic strength (0.2 M) within an operational time of the order of one hour. This crystallization yield is more than three-fold larger than that obtained from samples containing NaCl without HEPES at the same pH and ionic strength. Moreover, we determined crystallization yield as a function of incubation time, and temperature below and above the LLPS boundary. As crystallization temperature intersects with LLPS temperature, a significant increase in crystallization yield is observed. This is consistent with LLPS boosting protein crystallization. Our work suggests a possible strategy for increasing the crystallization success of other proteins, with applications in protein purification. Full article