Pressure-temperature Plane Research Articles

Cooling-heating properties of the FRW universe in gravity with a generalized conformal scalar field

In this paper, within the framework of modified gravity involving a conformal scalar field, we investigate the Joule-Thomson expansion of the Friedmann-Robertson-Walker (FRW) universe to identify cooling and heating regions. We observe a divergence in the Joule-Thomson coefficient (μ), precisely at the apparent horizon (RA=−2α) of the FRW universe, under conditions of negative gravitational coupling (α<0), which aligns with a thermodynamic singularity. Furthermore, we determine the inversion temperature and pressure for the FRW universe, and elucidate the salient features of inversion and isenthalpic curves in the temperature-pressure (T-P) plane. We compare these findings with results obtained under Einstein gravity, discussing the influence of the modification term on the cooling and heating properties of the FRW universe. This work presents insights into the formation of cooling and heating regions within the FRW universe, contributing to a deeper understanding of the physical mechanisms behind cosmic expansion history.

Temperature and volumetric effects on structural and dielectric properties of hybrid perovskites

Three-dimensional organic-inorganic perovskites are rapidly evolving materials with diverse applications. This study focuses on their two representatives - acetamidinium manganese(II) formate (AceMn) and formamidinium manganese(II) formate (FMDMn) – subjected to varying temperature and pressure. We show that AceMn undergoes atypical pressure-induced structural transformations at room temperature, increasing the symmetry from ambient-pressure P21/n phase II to the high-pressure Pbca phase III. In turn, FMDMn in its C2/c phase II displays temperature- and pressure-induced ordering of cage cations that proceeds without changing the phase symmetry or energy barriers. The FMD+ cations do not order under constant volume across the pressure-temperature plane, despite similar pressure and temperature evolution of the unit-cell parameters. Temperature and pressure affect the cage cations differently, which is particularly pronounced in their relaxation dynamics seen by dielectric spectroscopy. Their motion require a rearrangement of the metal-formate framework, resulting in the energy and volumetric barriers defined by temperature-independent activation energy and activation volume parameters. As this process is phonon-assisted, the relaxation time is strongly temperature-dependent. Consequently, relaxation times do not scale with unit-cell volume nor H-bond lengths in formates, offering the possibility of tuning their electronic properties by external stimuli (like temperature or pressure) even without any structural changes.

Experimental isochoric apparatus for bubble points determination: Application to CO2 binary mixtures as advanced working fluids

Carbon dioxide binary mixtures are increasingly considered as working fluids in transcritical power cycles, due to the capability to perform liquid-phase compression even at high environmental temperatures. However, a robust thermodynamic model is essential for optimal and reliable design conditions. It is widely recognised that fine-tuning the equation of state with experimental vapour-liquid equilibrium data of the mixture significantly enhances its reliability.In this work, a new apparatus dedicated to vapour-liquid equilibrium measurements of mixtures is presented. The proposed method consists of a constant-volume system, where bubble points are identified from the divergence of slope of the isochoric lines between the two-phase and liquid regions, in the temperature-pressure plane. The temperature and pressure limits of the apparatus are 503 K and 25 MPa.Bubble points of CO2 binary mixtures with hexafluorobenzene (C6F6) and n-pentane (C5H12) have been measured and compared with previous literature data for validation purposes. Then, the CO2 mixture with octafluorocyclobutane (c-C4F8) is experimentally studied, addressing a literature gap in bubble point data. The data are used to calibrate the thermodynamic model, leading to affordable design conditions of the power cycle compared to the non-optimised thermodynamics scenario, in a concentrated solar power tower plant.

Dissociation behavior of microbial nitrilase in temperature-pressure plane studied by using high pressure near-ultraviolet circular dichroism spectroscopy

ABSTRACT High pressure circular dichroism (HP-CD) spectroscopy below 200 MPa, especially in the near-ultraviolet region, has long been expected to probe the protein self-association phenomena. However, its experimental difficulties have hampered obtaining the data available for quantitative analyses. In this paper, near-ultraviolet CD spectra measurements under various temperatures and pressures were demonstrated on nitrilase from Rhodococcus rhodochrous J1 (J1-NTase), which thermally self-associates from inactive protomer to active oligomer at atmospheric pressure. The exploration of instrumental conditions and simple raw data correction enabled us to complete the spectra in a temperature-pressure plane. The quality of data was checked by multivariate curve resolution with the alternating least squares method (MCR-ALS), which gave model-free decomposition into component spectra and their concentration profiles. The resultant two components pointed out that the obtained data were self-consistent and appeared to reflect free and bound protomers.

Intrinsic correlation between the generalized phase equilibrium condition and mechanical behaviors in hydrate-bearing sediments

The phase equilibrium and mechanical behaviors of natural gas hydrate-bearing sediment are essential for gas recovery from hydrate reservoirs. In heating closed systems, the temperature-pressure path of hydrate-bearing sediment deviates from that of pure bulk hydrate, reflecting the porous media effect in phase equilibrium. A generalized phase equilibrium equation was established for hydrate-bearing sediments, which indicates that both capillary and osmotic pressures cause the phase equilibrium curve to shift leftward on the temperature-pressure plane. In contrast to bulk hydrate, hydrate-bearing sediment always contains a certain amount of unhydrated water, which keeps phase equilibrium with the hydrate within the hydrate stability field. With changes in temperature and pressure, a portion of pore hydrate and unhydrated water may transform into each other, affecting the shear strength of hydrate-bearing sediment. A shear strength model is proposed to consider not only hydrate saturation but also the change in temperature and pressure of hydrate-bearing sediment. The model is validated by experimental data with various hydrate saturation, temperature and pressure conditions. The deformation induced by partial dissociation was studied through depressurization tests under constant effective stress. The reduction in gas pressure within the hydrate stability field indeed caused sediment deformation. The dissociation-induced deformation can be reasonably estimated as the difference in volume between hydrate-bearing and hydrate-free sediments from the compression curves.

Nanocrystallization of Bi2O3 based system from the glassy state under high compression

This report presents the pressure-temperature (p-T) plane of Bi2O3-Al2O3-SiO2 ternary system in the context of nanocrystallite formation from its amorphous state. The diagram was constructed through differential thermal analysis (DTA) performed in situ under high-pressure-high-temperature (HP-HT) conditions, with nitrogen serving as the pressurizing medium. Above the glass transition temperature Tg, a wide ultraviscous, supercooled liquid state spanning approximately 150 K is observed. Later heating transforms this state into nanocrystallites embedded within an amorphous matrix, thereby keeping distinctive structural characteristics even after the decompression process. The p-T plane serves as a fundamental prerequisite for the design of nanocrystallites within a glass matrix, a well-established technique known as glass-ceramics. Various paths within the p-T plane, followed by annealing just below Tg, can be explored, potentially leading to the development of Bi2O3-based materials with enhanced electrical, dielectric, photonic, and mechanical properties, predicated on nanocrystallites formed by high-pressure treatment.

Experiment and simulation of hydrogen oxidation in a high-pressure turbulent flow reactor

Hydrogen oxidation has a complex dependence on pressure. Despite the well-known, reverse S-shape explosion limits, variation of hydrogen oxidation reactivity with pressure has rarely been investigated in a quantitative manner, particularly in the peninsula between the second and third ignition branches when the overall reactivity is low. This work investigates hydrogen oxidation in a turbulent flow reactor at 10 to 48 bar with an inlet temperature of 950 K and an equivalence ratio of 0.03–0.05, which complements our recent study at 1–8 bar in the same reactor (Lu et al. Proc. Combust. Inst. 2021, 243–250). The elevated pressures show a weak promoting effect, in contrast to the strong inhibiting effect at lower pressures in crossing the second ignition branch. Analyzing the hydrogen consumption rates across the pressure range revealed that the reactivity remains at a low level and is barely affected by pressure between 2 and 20 bar, suggesting the existence of a broad low-reactivity valley on the temperature–pressure plane which could be potentially important for practical applications.The measured species-time concentrations, combined with ignition delays selected from the literature, are used to develop a new hydrogen oxidation model focusing on hydrogen autoignition behavior. A comprehensive review of elementary reactions incorporating the latest updates for the rate coefficients is conducted to determine the prior uncertainties. A global optimization method incorporating random sampling and high-dimensional model representation is used to identify the most sensitive reactions and to constrain their uncertainty with the selected experimental targets. An optimized model is then obtained which shows excellent agreement with hydrogen autoignition experiments.

Nonlinearity effect on Joule–Thomson expansion of Einstein–Power–Yang–Mills AdS black hole

Considering the nonlinearity of the Yang Mills charge, we investigate the Joule–Thomson expansion for the Einstein–Power–Yang–Mills AdS black holes in the context of the gauge-gravity duality. Under this framework, we calculate the Joule–Thomson coefficient, describe all relevant inversion and isenthalpic curves in the temperature-pressure plane that determining in this manner the corresponding cooling and heating regions. Finally we analyze the effect of the charge nonlinearity on the Joule–Thomson expansion.

Joule-Thomson expansion of AdS black holes in quasitopological electromagnetism

We study the Joule-Thomson expansion in Einstein-Maxwell theory supplemented with the so-called quasitopological electromagnetism, this in the extended phase space thermodynamic approach. We compute the Joule-Thomson coefficient and depict all relevant inversion and isenthalpic curves in the temperature-pressure plane, determining in this manner the corresponding cooling and heating regions. In contrast with previous related works we show the existence of three branches for the inversion curves which depends on suitable selections of the parameter space of the theory, thus departing from the usual van der Waals behavior which exhibits up to two branches.

Heat and cold denaturation of yeast frataxin: The effect of pressure

Yfh1 is a yeast protein with the peculiar characteristic to undergo, in the absence of salt, cold denaturation at temperatures above the water freezing point. This feature makes the protein particularly interesting for studies aiming at understanding the rules that determine protein fold stability. Here, we present the phase diagram of Yfh1 unfolding as a function of pressure (0.1–500 MPa) and temperature 278–313 K (5–40°C) both in the absence and in the presence of stabilizers using Trp fluorescence as a monitor. The protein showed a remarkable sensitivity to pressure: at 293 K, pressures around 10 MPa are sufficient to cause 50% of unfolding. Higher pressures were required for the unfolding of the protein in the presence of stabilizers. The phase diagram on the pressure-temperature plane together with a critical comparison between our results and those found in the literature allowed us to draw conclusions on the mechanism of the unfolding process under different environmental conditions.

Temperature, Pressure, and Length-Scale Dependence of Solvation in Water-like Solvents. II. Large Solvophovic Solutes.

We use molecular simulation to determine solvation free energies, isochoric solvation energies and entropies, isobaric solvation enthalpies and entropies, partial molecular volumes, and isothermal density derivatives of the solvation free energy as a function of temperature and pressure for hard-sphere solutes with diameters ranging from 4 to 36 Å in TIP4P/2005 and Jagla water-like solvents exhibiting unusual thermodynamics. An important piece of our discussion focuses on the nanometer-sized solutes, for which simulation results are found to be accounted for by the most basic classical thermodynamic treatment contemplating bulk and interfacial contributions to the solvation free energy. Thus, since water's liquid-vapor surface tension is only special inasmuch as it takes unusually large values, solvent's water-like unusual thermodynamics manifests through a term proportional to the pressure in the solvation free energy. As a result, such solvent's unusual thermodynamics is found to be relevant to the temperature and pressure dependence of the isochoric solvation energy and entropy as well as to the isothermal density derivative of the solvation free energy. This sharply contrasts with the findings of the first part of this series indicating that the solvation free energy of small hard spheres responds to temperature and pressure changes as solvent's density does, with such a contrasting picture embodying a "pressure-density dichotomy." As for the length-scale dependence, we find the zero nominal pressure and the solvent's temperature of the maximum density as singular conditions for cavity surface-area size scaling of large solutes to occur for all solvation quantities. We finally argue that the overall study undertaken in this series suggests that water's unusual thermodynamics may be relevant to the thermodynamic stability of clusters of solvophobic units in the temperature-pressure plane. Some comments on the role of solute-solvent attractive interactions are also depicted.

Path-Dependent Supercooling of the ^{3}He Superfluid A-B Transition.

We examine the discontinuous first-order superfluid ^{3}He A to B transition in the vicinity of the polycritical point (2.232mK and 21.22bar). We find path-dependent transitions: cooling at fixed pressure yields a well-defined transition line in the temperature-pressure plane, but this line can be reliably crossed by depressurizing at nearly constant temperature after transiting T_{c} at a higher pressure. This path dependence is not consistent with any of the standard B-phase nucleation mechanisms in the literature. This symmetry breaking transition is a potential simulator for first order transitions in the early Universe.

Solid-liquid coexistence of neon, argon, krypton, and xenon studied by simulations.

The noble elements constitute the simplest group of atoms. At low temperatures or high pressures, they freeze into the face-centered cubic (fcc) crystal structure (except helium). This paper investigates neon, argon, krypton, and xenon by molecular dynamics using the simplified atomic potentials recently proposed by Deiters and Sadus [J. Chem. Phys. 150, 134504 (2019)], which are parameterized using data from accurate ab initio quantum-mechanical calculations by the coupled-cluster approach at the single-double-triple level. We compute the fcc freezing lines and find good agreement with the empirical values. At low pressures, predictions are improved by including many-body corrections. Hidden scale invariance of the potential-energy function is established by showing that mean-squared displacement and the static structure factor are invariant along the lines of constant excess entropy (isomorphs). The isomorph theory of melting [Pedersen et al., Nat. Commun. 7, 12386 (2016)] is used to predict from simulations at a single state point the freezing line's shape, the entropy of melting, and the Lindemann parameter of the crystal at melting. Finally, our results suggest that the body-centered cubic crystal is the thermodynamically stable phase at high pressures.

An improved reduction method for phase stability testing in the single-phase region

AbstractA new reduction method for mixture phase stability testing is proposed, consisting in Newton iterations with a particular set of independent variables and residual functions. The dimension of the problem does not depend on the number of components but on the number of components with nonzero binary interaction parameters in the equation of state. Numerical experiments show an improved convergence behavior, mainly for the domain located outside the stability test limit locus in the pressure–temperature plane, recommending the proposed method for any applications in which the problematic domain is crossed a very large number of times during simulations.

Anharmonicity and Phase Diagram of Magnesium Oxide in the Megabar Regime.

With density functional molecular dynamics simulations, we computed the phase diagram of MgO from 50 to 2000GPa up to 20 000K. Via thermodynamic integration (TDI), we derive the Gibbs free energies of the B1, B2, and liquid phases and determine their phase boundaries. With TDI and a pseudo-quasi-harmonic approach, we show that anharmonic effects are important and stabilize the B1 phase in particular. As a result, the B1-B2 transition boundary in the pressure-temperature plane exhibits a steep slope. We predict the B1-B2-liquid triple point to occur at approximately T=10000 K and P=370 GPa, which is higher in pressure than was inferred with quasiharmonic methods alone. We predict the principal shock Hugoniot curve to enter the B2 phase stability domain but only over a very small range of parameters. This may render it difficult to observe this phase with shock experiments because of kinetic effects.

Images of a First‐Order Spin‐Reorientation Phase Transition in a Metallic Kagome Ferromagnet

AbstractFirst‐order phase transitions, where one phase replaces another by virtue of a simple crossing of free energies, are best known between solids, liquids, and vapors, but they also occur in a wide range of other contexts, including even elemental magnets. The key challenges are to establish whether a phase transition is indeed first order, and then to determine how the new phase emerges because this will determine thermodynamic and electronic properties. Here it is shown that both challenges are met for the spin reorientation transition in the topological metallic ferromagnet Fe3Sn2. The magnetometry and variable temperature magnetic force microscopy experiments reveal that, analogous to the liquid–gas transition in the temperature–pressure plane, this transition is centered on a first‐order line terminating in a critical end point in the field‐temperature plane. The nucleation and growth associated with the transition is directly imaged, indicating that the new phase emerges at the most convoluted magnetic domain walls for the high temperature phase and then moves to self‐organize at the domain centers of the high temperature phase. The dense domain patterns and phase coexistence imply a complex inhomogenous electronic structure, which can yield anomalous contributions to the electrical conductivity.

A pseudo-kinetic model to simulate phase changes in gas hydrate bearing sediments

Modeling of the phase transitions anticipated in gas hydrate bearing sediments (GHBS) is critical for a proper understanding of time-dependent changes in states and volumes (e.g. the production of methane from this type of soils). We propose a new pseudo-kinetic approach to simulate the typical phase changes anticipated in GHBS, using published experimental results involving gas hydrate dissociation that are the basis of a widely used kinetic model. The proposed pseudo-kinetic model is formulated in the pressure-temperature (P-T) plane and assumes a rate of gas hydrate dissociation (or formation) proportional to the distance between the current state and the phase boundary. The model consists of only one parameter and is simple to implement in numerical simulators. A similar concept is used to model ice formation/thawing phenomena, but based on the ice/liquid-water phase boundary. We implemented the pseudo-kinetic model in a fully coupled thermo-hydro-chemo-mechanical (THCM) finite element code and validated it against experimental results performed on the dissociation of synthetic gas hydrate. We also evaluated the pseudo-kinetic model using synthetic cases covering several scenarios associated with gas hydrate formation/dissociation and ice formation/thawing. The model successfully reproduced the gas production test from a natural GHBS core from Korea (scaled gas venting experiment over 14 h), and also the formation of gas hydrate and ice in permafrost in Alaska (over 2 × 106 years). -The analyses show the versatility of the proposed pseudo-kinetic approach by applying it to model the different types of phase transitions typically encounter in GHBS. The simple formulation, easy implementation in numerical simulator, and reduced number of parameters (only one per phase change) make this model an attractive option for simulating phase transformations in problems involving GHBS.

Force-field coefficient optimization of coarse-grained molecular dynamics models with a small computational budget

Coarse-grained models in molecular dynamics are low-fidelity models developed to study the properties and behavior of materials. These force-field models are popular due to their simpler implementation and significant computational benefit of their use as compared to complex high-fidelity atomistic models. On the other hand, these advantages often come at the expense of accuracy. One effective way to resolve this issue is tuning their corresponding force-field coefficients such that the estimation error of atomistic properties is minimal with respect to high-fidelity reference data. However, acquisition/computation of these data is often costly, and in most practical cases in materials sciences only a small experimental/computational budget is available to obtain high-fidelity reference data. In this work, a multi-fidelity surrogate modeling strategy for resolving the trade-off between accuracy of a full of set of quantities of interest for an atomistic system and computational expenses is proposed. The proposed procedure takes advantage of the multi-fidelity upper error bound calculated using low-fidelity data by (i) employing an efficient point selection mechanism in the design space and obtaining a set of coarse-grained models, (ii) building stochastic collocation models corresponding to each selected low-fidelity model and obtaining the optimal small group of physical input parameter sets at which a high-fidelity model is evaluated, (iii) constructing a non-intrusive spectral polynomial-based surrogate based on the error of the low-fidelity emulators corresponding to the selected coarse-grained models, and (iv) optimizing force-field coefficients using the resultant surrogate with the objective of error minimization. Moreover, in the context of using a multi-fidelity framework and in order to construct a more accurate emulator, an approach for optimal kernel function selection is implemented in this work. Also, for the purpose of obtaining a set of optimal force-field coefficients using the constructed surrogate model, we used a heuristic population-based optimization approach. For the proof of concept, we applied the proposed approach for the force-field coefficient optimization of the coarse-grained monatomic water (mW) model based on the data obtained from the high-fidelity TIP4P/2005 water model simulations. The outcome of this study is an optimal coarse-grained monatomic water model that along with the TIP4P/2005 water model, provides an accurate emulator for exploration of the properties of water in the designated pressure-temperature input parameter space. Furthermore, this approach provides a more accurate way of sampling important points in the pressure-temperature plane. Finally, the cross-validation results indicate that a certain combination of quantities of interest can produce a more accurate multi-fidelity emulator for the TIP4P/2005 water model.

P–T–х-диаграмма состояния системы магний–никель

The analysis of equilibrium in the Mg–Ni system was carried out. Alloys on its basis are promising for use as sorbents and hydrogen storage (START). The conditions for the production and operation of such alloys imply strict control of the pressure of hydrogen. In this regard, phase equilibria in the Mg–Ni system must be considered not only depending on the composition and temperature, but also on the pressure of hydrogen. The most complete graphical representation of the equilibrium in the Mg–Ni system is given by a three-dimensional state diagram: pressure-temperature-composition (p–T–x), the projection of the three-phase equilibrium lines of this diagram on the pressure-temperature plane (p–T-state diagram), isobaric and isothermal sections of the diagram, diagram in pMg–T coordinates. Based on the analysis of experimental data on equilibrium in this system, the article presents the most important options of the listed types of diagrams. The presented diagram variants can be useful in optimizing the technology and operation of sorbents and START alloys of the Mg–Ni system.

Critical phenomena in the temperature-pressure-crowding phase diagram of a protein.

In the cell, proteins fold and perform complex functions through global structural rearrangements. Function requires a protein to be at the brink of stability to be susceptible to small environmental fluctuations, yet stable enough to maintain structural integrity. These apparently conflicting behaviors are exhibited by systems near a critical point, where distinct phases merge-a concept beyond previous studies indicating proteins have a well-defined folded/unfolded phase boundary in the pressure-temperature plane. Here, by modeling the protein phosphoglycerate kinase (PGK) on the temperature (T), pressure (P), and crowding volume-fraction (ϕ) phase diagram, we demonstrate a critical transition where phases merge, and PGK exhibits large structural fluctuations. Above the critical point, the difference between the intermediate and unfolded phases disappears. When ϕ increases, the critical point moves to lower T c. We verify the calculations with experiments mapping the T-P-ϕ space, which likewise reveal a critical point at 305 K and 170 MPa that moves to lower T c as ϕ increases. Crowding places PGK near a critical line in its natural parameter space, where large conformational changes can occur without costly free energy barriers. Specific structures are proposed for each phase based on simulation.