Phase Diagram Research Articles

Thermodynamic modeling of pressure-dependent phase diagram in alkali metals Li, Na and K

The high-pressure behavior of the alkali metals has attracted much attention in both experimental and theoretical aspects. This study is focused on the thermodynamic optimization of the temperature and pressure dependence of the molar volumes, the compressibility and phase diagrams of Li, Na and K according to the CALPHAD method. The pressure- temperature phase diagrams of lithium, sodium and potassium up to 50-100 GPa were calculated using the obtained thermodynamic parameters. The available experimental data, such as extremely low melting temperatures at high pressure, pressure-induced structural transitions between simple bcc and fcc crystals and the molar volume changes with the increasing pressure, were well reproduced in our calculations. The good agreements between our calculations and the experiments assessed in the literature indicated that our thermodynamic parameters are reasonable. Our thermodynamic calculations would assist to understand the phase transitions and structural properties of alkali metals at high pressure.

Growth of stable SiC2N2-Si2CN4 phases during nitrogen incorporated sputter deposition of silicon carbide

The incorporation of nitrogen during sputtering of silicon carbide (Si-C) target facilitates formation of different technologically significant phases. The bonding nature in these phases serve as the means of enhancing the hardness and toughness of the overall film getting deposited as shown by nanoindentation tests. Raman spectra gives the carbonaceous point of view based on existing models. A heterogenous crystallization was evident from getting a G-peak doublet. The experimental evidence of theoretically predicted SiC2N2 and Si2CN4 phases as per the phase diagram were found and confirmed by EDAX studies. These stable phases provided enhanced mechanical properties of the coatings

Exploring the Fundamental Spatial Limits of Magnetic All-Optical Switching.

All-optical switching (AOS) results in ultrafast and deterministic magnetization reversal upon single laser pulse excitation, potentially supporting faster and more energy-efficient data storage. To explore the fundamental limits of achievable bit densities in AOS, we have used soft X-ray transient grating spectroscopy to study the ultrafast magnetic response of a GdFe alloy after a spatially structured excitation with a periodicity of 17 nm. The ultrafast spatial evolution of the magnetization in combination with atomistic spin dynamics and microscopic temperature model calculations allows us to derive a detailed phase diagram of AOS as a function of both the absorbed energy density and the nanoscale excitation period. Our results suggest that the minimum size for AOS in GdFe alloys, induced by a nanoscale periodic excitation, is around 25 nm and that this limit is governed by ultrafast lateral electron diffusion and by the threshold for optical damage.

Effect of global shrinkage parameter of horseshoe prior in compressed sensing

This study investigates the effect of the global shrinkage parameter τ of a horseshoe prior, one of the global–local shrinkage priors, on linear regression in sparse signal processing. Statistical mechanics methods are employed to examine the accuracy of signal estimation. The phase diagram of the success and failure of signal recovery in noiseless compressed sensing with varying τ is discussed from the viewpoint of dynamic characterization of approximate message passing (AMP) as a solving algorithm and static characterization of the free-energy landscape. It is found that there exists a parameter region where the AMP algorithm can hardly recover the true signal, even though the true signal is locally stable. The analysis of the free-energy landscape also provides important insight into the optimal choice of τ.

Phase relations in the Gd2O3-Sm2O3-ZrO2 system: Experimental studies and thermodynamic modeling

Sm2Zr2O7 and Gd2Zr2O7 are two promising transparent ceramic materials with high density and effective atomic number. However, the phase diagram of Gd2O3-Sm2O3-ZrO2 system has not been systematically studied. To determine the phase relationship of the ternary system Gd2O3-Sm2O3-ZrO2 at 1600°C and 1400°C, a serious of ceramic samples were prepared and studied by X-ray diffraction, scanning electron microscope, and electron probe microanalysis. In the range of 66.6 mol.% ZrO2, the solubility of Gd2O3 is 20–22.5 mol.% at 1600°C, and the binary intermediate phases Sm2Zr2O7 and Gd2Zr2O7 form a continuous solid solution at 1400°C. Using the experimental data as a foundation, thermodynamic modeling was performed using the approach. Based on the experimental data, the mixing parameters of fluorite, B and C phases were optimized, and thermodynamic modeling was performed using the CALPHAD (CALculation of PHAse Diagram) method. For the first time, a self-consistent database for Gd2O3-Sm2O3-ZrO2 ternary system was established.

Controlling the formation of ionic complex vesicles through double-tailed surfactants.

Liposomes are often used in cosmetics since they are naturally derived and have excellent texture enhancing capabilities. However, when preparing them by using phospholipids with unsaturated acyl groups, they easily suffer from oxidative degradation. Accordingly, hydrogenated phospholipids are preferred, however, it is difficult to prepare stable liposomes due to its high gel-liquid crystalline phase transition temperature. On the other hand, although dialkyl dimethyl ammonium type cationic surfactants are widely known to form vesicles, they have rarely been used for skincare products except for water-in-oil type emulsion creams stabilized by organically modified clay minerals. We decided to overcome all of the problems above through ionic complex vesicles formed by double-tailed cationic and anionic surfactants. Distearyl dimethyl ammonium chloride (DSAC) and sodium dilauramidoglutamide lysine (DLGL) were selected as cationic and anionic surfactants, respectively. Differential scanning calorimetry (DSC) and small- and wide-angle X-ray scattering (SWAXS) measurements were performed to confirm the DSAC/DLGL/water ternary phase diagram. Newly developed ionic complex vesicle formation was confirmed by cryogenic transmission electron microscopy (cryo-TEM). The adsorbed cosmetic film structure on the skin invivo was evaluated through the polarized infrared external reflection (PIR-ER). Finally, a cosmetic lotion formula was developed and the vesicle size was determined by dynamic light scattering (DLS). DSC and SWAXS data indicated that stable vesicles could be obtained at a molar ratio of DLGL to DSAC = 6:4. At this molar ratio, multi lamellar vesicles with diameters less than 100 nm were observed through cryo-TEM. PIR-ER data revealed that the developed vesicles formed a highly perpendicular orientation to the human skin surface. We have succeeded in formulating a cosmetic lotion containing developed vesicles with a mean diameter of 63.2 nm, which was stable over 1 month at 0, 37, and 50°C. Our newly developed vesicles can be easily obtained through a coagulation process. Also, the adsorbed film structure supported by PIR-ER experiments implies that the developed lotion has an excellent texture that is the same as cosmetic lotions containing liposomes. Therefore, it's possible that this ionic complex vesicle could take the place of liposomes.

Carbide Precipitation Behavior of High‐Alloy Steel During Solidification and Cooling Process

The precipitation, growth, and transformation of carbides rich in Cr and Mo during solidification and cooling process of high‐alloy steel for cold working dies are investigated. The Fe–C pseudobinary phase diagram of high‐alloy steel is calculated by Thermo‐Calc software to ascertain the critical phase transformation temperatures. The temperatures of phase transformation during the solidification process are determined by a differential scanning calorimeter. Then the microstructure of the samples at these characteristic temperatures is observed in situ by high‐temperature confocal microscope. The results show that the characteristic temperatures for phase transformation and carbide precipitation are 1380, 1315, 1140, and 980 °C, respectively. At 1315 °C, thick rod‐like or island‐like M7C3 carbides enriched in Cr and Fe are formed. At 1140 °C, secondary M7C3, adhering to the primary eutectic M7C3, grows rapidly in a rod‐like morphology and maintains a similar composition. The secondary M6C carbides of segregated Mo elements precipitate in fan‐shaped clusters near M7C3 through the dissolution of M7C3 and the conversion of M2C. Thermodynamic calculation further indicates that the eutectic Cr7C3 precipitates at 1213 °C, and secondary Cr7C3 remains under conditions favorable for precipitation below the solidus, preceding the precipitation of secondary carbides Cr23C6 and Mo2C.

Anomalous properties in normal and superconducting states of Sc2Ir4-xSix due to flat band effect driven by spin-orbit coupling

Correlation effect may be induced by the flat band(s) near the Fermi energy, as demonstrated in twisted graphene, Kagome materials, and heavy Fermion materials. Unconventional superconductivity may arise from this correlation effect and show deviation from the phonon-mediated pairing as well as the Landau Fermi liquid in the normal state. Here, we report the anomalous properties in normal and superconducting states in the Laves phase superconductor Sc2Ir4-xSix with a kagome lattice and silicon doping. By doping silicon to the iridium sites, a phase diagram with nonmonotonic and two-dome-like doping dependence of the superconducting transition temperature Tc was observed. The samples in the region of the second dome, including Sc2Ir3.5Si0.5 with the optimal Tc, exhibit non-Fermi liquid behavior at low temperatures after superconductivity is suppressed, as evidenced by the divergence of the specific heat coefficient and the semiconducting-like resistivity, together with a strong superconducting fluctuation in the optimally doped samples. Combined with first-principles calculations, we attribute the anomalous properties in normal and superconducting states to the correlation effect, which is intimately induced by the flat band effect when considering the strong spin-orbit coupling.

Strong-coupling mean-field and classical percolation approach to produce the phase diagram of disordered Bose–Hubbard model at fixed n = 1 filling

We perform strong-coupling mean-field along with classical percolation analysis to produce the phase diagram of disordered Bose–Hubbard model with chemical potential disorder in two dimensional square lattice. The phase diagram in the disorder strength (Δ) and the on-site repulsion (U), for two and three dimensional system at fixed n = 1 filling show interesting re-entrant superfluid phase sandwiched between Bose-glass phases, as observed by the previous QMC results. We produce the phase diagram exhibiting the re-entrant phenomenon as well as phenomenologically demonstrate the robustness of the re-entrant phenomena within this method. We also discuss the importance of the method and applicability in further analysis of the same phase diagram.

Thermodynamics assessment of the Erbium-Ruthenium system by combining the Ab-initio and CALPHAD methods

ABSTRACT In the present study, the erbium-ruthenium system was optimised using the CALPHAD approach. The thermodynamic properties and the phase diagram were evaluated. The enthalpies of formation of the intermetallic compounds for the binary system Er-Ru were calculated by ab- initio methods. The liquid phase was treated with the exponential model, while a solution model was applied to represent the HCP (Er, Ru) solid solution. The five intermetallic compounds Er3Ru, Er5Ru2, Er3Ru2, ErRu2, and Er44Ru25 were considered as stoichiometric compounds. The calculations are in good agreement with the phase diagram information and experimental thermodynamic values documented in the literature.

Pressure-induced evolution of structures and phase transition of technetium diboride

Using the particle swarm optimization algorithm, we conducted an extensive search for the high-pressure stable structure of technetium diboride (TcB2) within the pressure range of 0–400 GPa. At zero pressure, the P63/mmc (hP6-TcB2) structure is considered the ground state configuration. As the pressure increases, a structural transition from hP6-TcB2 to P6/mmm (hP3-TcB2) occurs at approximately 174.9 GPa. We discuss the bonding between the two distinct phases and analyze the contribution of different atomic bonds to maintaining their structural stability. Meanwhile, the temperature–pressure phase diagram of TcB2 was successfully determined for the first time through the quasi-harmonic approximation method. It is predicted that the transition pressure from hP6-TcB2 to hP3-TcB2 can be reduced to about 164 GPa at a room temperature of 300 K. These results provide valuable insights into the behavior of TcB2 under different temperature and pressure conditions and open up new possibilities for exploring its potential applications in a variety of environments.

Large magnetocaloric effect and giant magnetoresistance in rare earth based intermetallic compound ErAl3: Construction of magnetic phase diagramΔΔΔ.

This study explores the magnetic and magnetotransport behavior of polycrystalline ErAl3 compound. The polycrystalline compound adopts HoAl3-type structures with the R-3m space group, No. 166-2 and hR60 configurations. Multiple magnetic orderings and two field induced metamagnetic transitions are observed. ErAl3 exhibits a significant magnetocaloric effect (MCE), ΔSM = 
15.25 J/kg-K and high relative cooling power (RCP) of 383 J/ kg with applied magnetic field change (ΔH) of 70 kOe near the paramagnetic to ferromagnetic transition, showcasing its potential for magnetic refrigeration technology. The compound also demonstrates metallic behavior, with a notable magnetoresistance of 48.5 % at 2 K due to the suppression of antiferromagnetism. The
magnetic phase diagram reveals four distinct phases influenced by temperature and magnetic field, identified through the study of the magnetocaloric effect.

Behind the Non-Uniform Breakup of Bubble Slug in Y-Shaped Microchannel: Dynamics and Mechanisms

Bubble flow in confined geometries is a problem of fundamental and technological significance. Among all the forms, bubble breakup in bifurcated microchannels is one of the most commonly encountered scenarios, where an in-depth understanding is necessary for better leveraging the process. This study numerically investigates the non-uniform breakup of a bubble slug in Y-shaped microchannels under different flow ratios, Reynolds numbers, and initial bubble volumes. Overall, the bubble can either breakup or non-breakup when passing through the bifurcation and shows different forms depending on flow regimes. The flow ratio-Reynolds number phase diagrams indicate a power–law transition line of breakup and non-breakup. The bubble takes longer to break up with rising flow ratios yet breaks earlier with higher Reynolds numbers and volumes. Non-breakup takes less time than the breakup patterns. Flow ratio is the origin of non-uniform breakup. Both the Reynolds number and initial volume influence the bubble states when reaching the bifurcation and thus affect subsequent processes. Bubble neck dynamics are analyzed to describe the breakup further. The volume distribution after breaking up is found to have a quadratic relation with the flow ratio. Our study is hoped to provide insights for practical applications related to non-uniform bubble breakups.

Numerical Investigation of Heat Transfer Characteristics of Trapezoidal Fin Phase Change Thermal Energy Storage Unit

Abstract: In order to enhance the heat transfer performance of a phase change thermal energy storage unit, the effects of trapezoidal fins of different sizes and arrangement modes were studied by numerical simulation in the heat storage and release processes. The optimal enhancement solution was obtained by comparing the temperature distribution, instantaneous liquid-phase ratio, solid–liquid phase diagram and comprehensive heat storage and release performance of the thermal energy storage unit under different fin sizes. During the heat storage process, the results show that when the ratio of the length of the upper and lower base of the trapezoid h1/h2 is 1:9, the heat storage time is shortened by 9.03% and 18.21% compared with h1/h2 = 3:7 and 5:5, respectively. During the heat release process, the optimal heat transfer effect is achieved when h1/h2 = 5:5. To further improve the heat transfer effects, the energy storage unit is placed upside down; then, the least time is achieved when h1/h2 = 2:8. When heat storage and release are considered together, the energy storage unit with h1/h2 = 2:8 takes the shortest time to melt in upright placement and then to solidify in upside-down placement.

First‐Principles Investigations of the Structural Phases of Low‐Spin State of BiCoO3

Herein, from first‐principles calculations, the phase diagram of the low‐spin (LS) state of BiCoO3 is scrutinized. The phonon‐dispersion curves of the cubic phase are analyzed to identify all the possible unstable modes and assessed the energy gain of the resulted distorted phases. In the findings, the presence of similar phases is revealed in both LS and high‐spin (HS) states, including ferroelectric and octahedra rotations distortions. However, the relative energy ordering of these phases differs significantly between the two states. Notably, the energy gain from mode condensation is considerably less pronounced in the LS case compared to HS state. Furthermore, it is identified that the common Pnma phase is the ground state of the LS state of BiCoC3, closely followed by the Imma octahedra rotation phase and the R3c ferroelectric phase, hence, different from the P4mm ferroelectric ground state of the HS state.

Modelling the first droplet emission from an electrified liquid meniscus hanging at the nozzle tip

Electrohydrodynamic (EHD)-induced droplet emission is an efficient method for the production of micron- and submicron-sized droplets in technological applications. Existing studies propose several scaling laws to determine the size of the emitted droplet. However, they have usually focused on the tip streaming phenomena of a droplet when subjected to a uniform electric field. In most applications, a non-uniform distribution of the electric field is created owing to the nozzle-to-plate configuration. Here, we employ an arbitrary Lagrangian–Eulerian method to demonstrate the mechanism of the first droplet emission from an electrified liquid meniscus with a fixed volume hanging at the nozzle tip. The critical condition when tip streaming occurs is determined using our numerical results. A phase diagram in terms of the electric field and initial liquid volume is presented to obtain the commonly used jetting mode. The effects of the liquid volume, electric field strength and electrical conductivity of the liquid on the processes of jet formation and breakup are further investigated. We find a particularly non-monotonic dependence of the size of the emitted droplet on the electrical conductivity. These findings could be useful for generating microdroplets and improving injection frequency in EHD printing technology.

A Concise 4D Conservative Chaotic System with Wide Parameter Range, Offset Boosting Behavior and High Initial Sensitivity

In this paper, we present a concise four-dimensional (4D) conservative chaotic system with a wide parameter range. Since there are no terms higher than first order, the circuit does not contain multipliers, resulting in a simple circuit implementation. The nonlinear dynamic characteristics, such as phase diagrams, equilibrium points, divergence, Poincaré cross-sections, Lyapunov exponents, bifurcation diagrams, and Lyapunov dimension, are analyzed in detail, which illustrates the conservativity. Besides, the system exhibits different offset boosting behaviors. Through offset boosting, the system can propagate along a line, convert signal polarity, control variable amplitude, generate coexisting attractors, and even induce changes in its state. Specially, we realize the transition from a single-vortex attractor to a multivortex one by some changes in the initial values. Furthermore, the Pearson correlation coefficient is used to demonstrate the higher initial value sensitivity of the system. Finally, the system is implemented through Multisim simulation and analog circuit separately, and their consistency validates the system effectively.

Effects of tensor spin polarization on the chiral restoration and deconfinement phase transitions

Effects of tensor spin polarization (TSP) on the chiral restoration and deconfinement phase transitions are studied in Polyakov loop extended Nambu–Jona-Lasinio (PNJL) model. For chiral phase transition, the higher the polarized degree of quark-antiquark pairs under the strong magnetic field, the higher the phase transition temperature. The TSP corrects the position of the critical end point. The small impact of TSP on the phase transition temperature is found for the deconfinement phase transition. On the other hand, we divide the phase space into three ranges based on the phase diagram obtained from the PNJL model: the confinement phase with chiral symmetry broken, the deconfinement phase with restored chiral symmetry, and the confinement phase with restored chiral symmetry (quarkyonic phase). It is found that TSP has only a very small effect on the anisotropic pressure in the deconfined phase with chiral symmetry restored and the quarkyonic phase, but it has a very strong effect on the anisotropic pressure in the confined phase with chiral symmetry broken. This is because TSP is closely related to chiral symmetry. The restoration of chiral symmetry means the dissociation of spin polarization condensate. Published by the American Physical Society 2024

Breakdown of steady-state superradiance in extended driven atomic arrays

Recent advances in generating well controlled dense arrangements of individual atoms in free space have generated interest in understanding how the extended nature of these systems influences superradiance phenomena. Here, we provide an in-depth analysis on how space-dependent light shifts and decay rates induced by dipole-dipole interactions modify the steady-state properties of coherently driven arrays of quantum emitters. We characterize the steady-state phase diagram, with particular focus on the radiative properties in the steady state. Interestingly, we find that diverging from the well-established Dicke paradigm of equal all-to-all interactions significantly modifies the emission properties. In particular, the prominent quadratic scaling of the radiated light intensity with particle number in the steady state—a hallmark of steady-state Dicke superradiance—is entirely suppressed, resulting in only linear scaling with particle number. We show that this breakdown of steady-state superradiance occurs due to the emergence of additional dissipation channels that populate not only superradiant states but also subradiant ones. The additional contribution of subradiant dark states in the dynamics leads to a divergence in the time scales needed to achieve steady states. Building on this, we further show that measurements taken at finite times for extended atom ensembles reveal properties closely mirroring the idealized Dicke scenario. Published by the American Physical Society 2024

Thermodynamic descriptions of the CaO–Al2O3 and CaO–Al2O3–SiO2 systems over the whole composition and temperature ranges

AbstractThe CaO–Al2O3–SiO2 system is a fundamental system in aluminosilicate materials, and its thermodynamic description provides key information for ceramic design, cement production, slag tapping, and geological prediction. However, the existing thermodynamic calculations for the CaO–Al2O3 system show inaccurate heats of formation for the compounds and consequently a decomposition of the CA2 (CaO⋅2Al2O3) phase at a low temperature. Besides, the solid solutions in anorthite and cristobalite have never been considered in the previous thermodynamic assessments for the CaO–Al2O3–SiO2 system. Therefore, thermodynamic reassessments of the CaO–Al2O3 and CaO–Al2O3–SiO2 systems are carried out in the present work using the CALculation of PHAse Diagram method, considering the solid solution in anorthite and cristobalite for the first time. The anorthite and cristobalite phases are modeled based on the individual mechanism of solid solution, with the anorthite described by (Ca+2, Va)1(Al+3, Si+4)2(Si+4)2(O−2)8 and the cristobalite described by (Va, Ca+2)1(Si+4, Al+3)2(O−2)4. The present assessment solves the above issues and provides consistent thermodynamic descriptions for the liquid and solid phases. Based on the established thermodynamic database, a Scheil solidification simulation is carried out for a cement clinker and the variations of mass fractions of the phases as well as the composition of liquid during Scheil cooling are calculated. The present work guides the design of relevant materials and lays an essential foundation for the establishment of the thermodynamic database of multicomponent aluminosilicate materials.