Thermodynamic Properties Research Articles

Investigation on in-cylinder and in-intercooler thermodynamic properties of miniature multi-stage reciprocating compressor with insufficient inter-stage volumes

Investigation on in-cylinder and in-intercooler thermodynamic properties of miniature multi-stage reciprocating compressor with insufficient inter-stage volumes

Half-metallic and thermodynamic properties of Fe-based quaternary Heusler alloys: an ab initio study

Half-metallic and thermodynamic properties of Fe-based quaternary Heusler alloys: an ab initio study

Small-scale turbulent characteristics in transcritical wall-bounded flows

Considerable efforts have been devoted to the understanding of the small-scale characteristics in turbulent flows. While the universality of small-scale quantities has been established for incompressible flows, their extension to high-pressure transcritical flows remains an open area of research. To address this question, we investigate the real-fluid thermodynamic effects on small-scale velocity statistics of high-pressure transcritical wall-bounded turbulence. We show that in the locally isotropic region for transcritical flows, low-order moments of small-scale statistics collapse for all cases and Kolmogorov's (1941) theory holds. However, real-fluid thermodynamic effects introduce deviations in the tails of the probability density function for the velocity derivative and, consequently, high-order moments of velocity gradients and dissipation rate in transcritical flows cannot collapse in the locally isotropic region. Analysis of the intermittency shows that the low-order structure functions in transcritical flows follow extended self-similarity, while the dependence of the intermittency factor on real-fluid effects is observed for high-order structure functions. The real-fluid effects on intermittency are explained by turbulent structures related to rare events. Additionally, the dissipation rate moments for transcritical flows follow a universal scaling with Reynolds number, and the scaling exponents are different from those of incompressible flows. These results extend the small-scale universality in incompressible flows (Schumacher et al., Proc. Natl Acad. Sci. USA, vol. 111, 2014, pp. 10961–10965) to realistic flows with significant changes in thermodynamic properties, and provide a physical underpinning of the scaling laws of small-scale statistics at transcritical conditions.

A Combined Molecular Dynamics and Hydropathic INTeraction (HINT) Approach to Investigate Protein Flexibility: The PPARγ Case Study

Molecular Dynamics (MD) is a computational technique widely used to evaluate a molecular system’s thermodynamic properties and conformational behavior over time. In particular, the energy analysis of a protein conformation ensemble produced though MD simulations plays a crucial role in explaining the relationship between protein dynamics and its mechanism of action. In this research work, the HINT (Hydropathic INTeractions) LogP-based scoring function was first used to handle MD trajectories and investigate the molecular basis behind the intricate PPARγ mechanism of activation. The Peroxisome Proliferator-Activated Receptor γ (PPARγ) is an emblematic example of a highly flexible protein due to the extended ω-loop delimiting the active site, and it is responsible for the receptor’s ability to bind chemically different compounds. In this work, we focused on the PPARγ complex with Rosiglitazone, a common anti-diabetic compound and analyzed the molecular basis of the flexible ω-loop stabilization effect produced by the Oleic Acid co-binding. The HINT-based analysis of the produced MD trajectories allowed us to account for all of the energetic contributions involved in interconverting between conformational states and describe the intramolecular interactions between the flexible ω-loop and the helix H3 triggered by the allosteric binding mechanism.

Structural stability, mechanical, and thermodynamic properties under pressure of B2-type CuM (M = Be, Al, and Zn) alloys: a DFT investigation

In this work, we systematically examined the structural stability, mechanical properties, and thermodynamic behavior of B2-type CuBe alloy, and compared the results with isostructural Cu-based alloys (CuAl and CuZn) by employing first-principles calculations in the pressure range of −22 to 100 GPa. This study revealed the stable existence of CuBe alloy at low-density expansion states (e.g. ∼ −20 GPa), indicating its superior structural stability compared to CuAl and CuZn. The pressure dependence of properties such as cell parameter a (a/a 0) and density ρ (ρ/ρ 0), elastic parameters (elastic constants C ij , bulk modulus B, shear modulus G, and Young's modulus E), deduced parameters (B/G ratio, Poisson's ratio ν, Vickers hardness, sound velocity, and Debye termperature ΘD), and thermodynamic parameters (free energy F, entropy S, and heat capacity C v) were investigated. All CuM (M = Be, Al, and Zn) alloys had more difficulty undergoing uniaxial stress than shear stress. External pressure reduced the ductility of the CuBe alloy, while excess pressure (P > 50 GPa) resulted in increased ductility, which was similar to CuAl but different from CuZn. The hardness and ΘD values demonstrated consistent variation corresponding to the ductility changes. Thermodynamic parameters were minimally affected by pressure, and the stronger interactions led to greater F in the CuBe alloy. These findings offer confidence for the future design of ordered Cu-Be alloys with exceptional properties.

Ab Initio Prediction of the Structural, Elastic and Thermodynamic Properties Under Hydrostatic Pressure of the Ternary Tetragonal Phosphides XRh2P2 (X = Ca, Ba) for Superconducting Application

Ab Initio Prediction of the Structural, Elastic and Thermodynamic Properties Under Hydrostatic Pressure of the Ternary Tetragonal Phosphides XRh2P2 (X = Ca, Ba) for Superconducting Application

Advances in CALPHAD Methodology for Modeling Hydrides: A Comprehensive Review

AbstractHydrides enable handling hydrogen at low pressure and near room temperature, offering higher volumetric densities than compressed or liquid hydrogen and enhancing safety. The CALPHAD method, rooted in the principles of thermodynamics, offers a systematic approach for predicting phase equilibria and thermodynamic properties in multicomponent materials. This comprehensive review paper aims to provide a detailed overview of the application of the CALPHAD method in the realm of metallic and complex hydrides. After an introduction to the fundamental thermodynamic aspects of hydrides, key elements of applying the CALPHAD method to model metal-hydrogen systems and complex hydrides are discussed. Subsequently, recent publications are reviewed, highlighting key findings and recent progresses in the field. Finally, the challenges that must be overcome to achieve further progress in this area are explored.

Drying kinetics and thermodynamic properties of jabuticaba peel

Jabuticaba is a fruit of high nutritional value, and the peel, which is usually discarded, contains nutrients in greater concentration. An alternative for the use of jabuticaba bark is the preparation of flour. The aim of this research was to analyze the drying kinetics of jabuticaba bark by adjusting mathematical models and determining the effective diffusion coefficient, activation energy, and thermodynamic properties at different drying temperatures. The jaboticaba residues were dried in a forced ventilation oven at different temperatures of 45, 55, 65, and 75°C. Among the various models analyzed, Page was employed to streamline the drying phenomenon. The research observed that effective diffusion coefficient decreased with increasing temperature, and the activation energy for the liquid diffusion on drying was 32.63 kJ mol-1. Furthermore, enthalpy and entropy decreased with increasing drying temperature, while Gibbs’ free energy increased with increasing drying temperature.

2-in-1 Phase Space Sampling for Calculating the Absorption Spectrum of the Hydrated Electron.

The investigation of vibrational effects on absorption spectrum calculations often employs Wigner sampling or thermal sampling. While Wigner sampling incorporates zero-point energy, it may not be suitable for flexible systems. Thermal sampling is applicable to anharmonic systems yet treats nuclei classically. The application of generalized smoothed trajectory analysis (GSTA) as a postprocessing method allows for the incorporation of nuclear quantum effects (NQEs), combining the advantages of both sampling methods. We demonstrate this approach in computing the absorption spectrum of a hydrated electron. Theoretical exploration of the hydrated electron and its embryonic forms, such as water cluster anions, poses a significant challenge due to the diffusivity of the excess electron and the continuous motion of water molecules. In many previous studies, the wave nature of atomic nuclei is often neglected, despite the substantial impact of NQEs on thermodynamic and spectroscopic properties, particularly for hydrogen atoms. In our studies, we examine these NQEs for the excess electrons in various water systems. We obtained structures from mixed classical-quantum simulations for water cluster anions and the hydrated electron by incorporating the quantum effects of atomic nuclei with the filtration of the classical trajectories. Absorption spectra were determined at different theoretical levels. Our results indicate significant NQEs, red shift, and broadening of the spectra for hydrated electron systems. This study demonstrates the applicability of GSTA to complex systems, providing insights into NQEs on energetic and structural properties.

New analytical thermodynamic models developed for pure H2, CH4, CO2 and H2 containing mixtures based on molecular simulations

Pressure-volume-temperature-composition (PVTX) properties of gas mixtures are important to model and predict flow and compression performance in a range of industrial processes. It is time consuming and sometimes impractical to obtain these properties from experiments. Here, molecular dynamics (MD) simulations were conducted to compute the thermodynamic volumetric properties of pure H2, CH4, CO2, and binary mixtures of H2/CH4 and H2/CO2 at temperatures of 310.9–470 K, pressures up to 172 MPa. MD simulation results were used to develop five analytical equations explicit in pressure as a function of density or volume, temperature, and composition, for the pure gases and mixtures. Our simulated results matched very well with the predictions from the established GERG-2008 equation and data published by NIST. The simplified equations of state (EOS) developed in this work will be more computationally efficient than other EOS for mixed systems. This can be significant in reservoir simulations.

Thermodynamic properties of an interacting fermion-antifermion pair in a magnetized spacetime with a non-zero cosmological constant

Abstract In a magnetized three-dimensional Bonnor-Melvin spacetime with non-zero cosmological constant, we explore the
dynamics of a fermion-antifermion pair interacting through an attractive Coulomb potential. To analyze the relativistic
behavior, we seek an analytical solution for the fully covariant two-body Dirac equation derived from quantum electrody-
namics. The resulting equation provides a non-perturbative second-order wave equation that govers the relative motion of
the interacting pair. Remarkably, we find exact solubility when considering the interaction as short-range. Consequently,
we determine the energy eigenvalues and wave functions utilizing well-known special functions. By employing these
solutions, we determine the thermal properties of this system. Despite the divergence observed in the partition function,
we effectively tackle this issue by applying a regularization technique based on the mathematical zeta Hurwitz function.
This method facilitates the computation of various thermal quantities, such as free energy, total energy, entropy function,
and specific heat. Consequently, we provide an in-depth analysis of the thermodynamic characteristics of the system
under consideration.

Improved structure and enhanced properties of detonation sprayed W coating via hot isostatic pressing

Tungsten has garnered significant attention for its superior performance as a plasma-facing material in tokamak devices. However, its hardness and high ductile-to-brittle transition temperature present challenges for its application in plasma-facing components. To address these issues, this study employs the detonation spraying (DS) technique to prepare tungsten coatings on a TZM alloy substrate and further optimizes their properties through hot isostatic pressing (HIP) treatment. Advanced characterization techniques were utilized to conduct a detailed microstructural and compositional analysis of the coatings. The results indicated that the HIP treatment significantly reduced the porosity of the coatings, improving their density and overall quality. Additionally, HIP treatment led to a decrease in internal stress, a reduction in dislocations, and the grain growth within the coatings. The study also discussed how the HIP process improved the microstructure of the DS tungsten coatings through these mechanisms, thereby enhancing the coatings' thermodynamic properties. Mechanical property tests revealed that the coatings treated with HIP exhibited higher bonding strength and lower hardness, attributed to the increase in grain size and the reduction in dislocation density within the coatings. Thermal property tests demonstrated that the HIP-treated coatings possessed higher thermal diffusivity and specific heat capacity in the temperature range of 100 to 500 °C. Furthermore, the performance of the coatings under transient high heat flux conditions was significantly improved after the HIP treatment, showing better resistance to the thermal shock and cracking. These findings are of great importance for understanding the performance enhancement of DS tungsten coatings in nuclear fusion reactor applications via HIP, especially as candidate materials for the first wall of tokamak devices.

Estimation of the Shear Viscosity of Mixed-Polymer Materials for Screw Extrusion-Based Recycling Process Modeling

The scope of this work is the development of a method to estimate the temperature and shear rate-dependent viscosity of mixtures composed of two polymers. The viscosity curve of polymer mixtures is crucial for the modeling and optimization of extrusion-based recycling, which is the most efficient way to recycle polymeric materials. The modeling and simulation of screw extruders requires detailed knowledge of the properties of the processed material, such as the thermodynamic properties, the density, and the rheological behavior. These properties are widely known for pure materials; however, the incorporation of impurities, like other polymers in recycled materials, alters the properties. In this work, miscible, immiscible, and compatibilized immiscible polymer mixtures are considered. A new method based on shear stress is proposed and compared to the shear rate-based method. Several mixing rules are evaluated for their accuracy in predicting mixture viscosity. The developed methods allow the prediction of the viscosity of a compatibilized immiscible mixture with deviations below 5% and that of miscible polymer mixtures with deviations below 3.5%.

Revisiting thermodynamics in (LiF, NaF, KF, CrF2)–CrF3 by first-principles calculations and CALPHAD modeling

The thermodynamic description of the (LiF, NaF, KF, CrF2)–CrF3 systems has been revisited, aiming for a better understanding of the effects of Cr on the FLiNaK molten salt. First-principles calculations based on density functional theory (DFT) were performed to determine the electronic and structural properties of each compound, including the formation enthalpy, volume, and bulk modulus. DFT-based phonon calculations were carried out to determine the thermodynamic properties of compounds, for example, enthalpy, entropy, and heat capacity as functions of temperature. Phonon-based thermodynamic properties show a good agreement with experimental data of binary compounds LiF, NaF, KF, CrF3, and CrF2, establishing a solid foundation to determine thermodynamic properties of ternary compounds as well as to verify results estimated by the Neumann-Kopp rule. Additionally, DFT-based ab initio molecular dynamics (AIMD) simulations were employed to predict the mixing enthalpies of liquid salts. Using DFT-based results and experimental data in the literature, the (LiF, NaF, KF, CrF2)–CrF3 system has been remodeled in terms of the CALculation of PHAse Diagrams (CALPHAD) approach using the modified quasichemical model with quadruplet approximation (MQMQA) for liquid. Calculated phase stability in the present work shows an excellent agreement with experiments, indicating the effectiveness of combining DFT-based total energy, phonon, and AIMD calculations, and CALPHAD modeling to provide the thermodynamic description in complex molten salt systems.

Comprehensive analysis of the phase stability, optoelectronic, mechanical, thermodynamic, and vibrational properties for prospective optoelectronic applications of novel combinations of chalcogenides XScTe2 (X = Li, Rb) by employing density functional theory

Comprehensive analysis of the phase stability, optoelectronic, mechanical, thermodynamic, and vibrational properties for prospective optoelectronic applications of novel combinations of chalcogenides XScTe2 (X = Li, Rb) by employing density functional theory

Insights into optoelectronic, thermodynamic, and thermoelectric properties of novel GePtCh (Ch = S, Se, Te) semiconductors: first-principles perspective

Ternary chalcogenides are often studied for their remarkable heat resistance and flexible optical properties. We used density functional theory and examine complicated connections between the various physical features of the exclusive GePtCh (Ch = S, Se, and Te) ternary chalcogenides. The valence band is formed by the hybridization of the Ge-s/p/d, Pt-s/p/d, S-p, Se-p, and Te-p orbitals in the energy range of −6.0 eV to 0 eV. The materials under consideration are confirmed as indirect bandgap materials with estimated energy gaps of 1.29 eV, 0.86 eV, and 0.48 eV, respectively. By substituting Se and Te for S reduced the bandgap in these materials. The complex dielectric function’s components, absorption coefficients, real optical conductivity, energy loss functions, refractive index, reflectivity, and extinction coefficient, are studied and examined to identify their potential use in optoelectronic applications. The thermodynamic parameters of these ternary systems are calculated by employing the quasi-harmonic Debye model. The materials are suitable for thermoelectric devices, as evidenced by their considerable and outstanding thermoelectric features. The GePtTe possessed the highest absorption, indicating that it is a suitable material for the use in optoelectronic applications.

Drying kinetic, thermodynamic and quality analyses of infrared drying of truffle slices.

Kinetic and thermodynamic parameters are the most important part for making a suitable tool for drying agricultural products. Moreover, calculation of the energy required for the drying of product, the properties of the rehydration ratio, the food appearance changes, and the evaluation of the microstructure of food are crucial. Since the thermodynamic properties of truffle slices have not yet been reported, this study aims to establish a mathematical model to describe drying process of agriculture product, evaluate the effective moisture diffusion coefficient (Deff), determining the activation energy (Ea) to elucidate the thermodynamic characteristics, measure color characteristics, and rehydration ratio (RR) during the drying process of truffle slices. Truffle slices were dried in an infrared (IR) dryer at four temperatures of 50-80°C and two thicknesses of 0.5 and 1cm. The best model to describe the drying process of truffle slices was Midilli etal.'s model. The value of Deff, SEC, and RR were in the range of 3.06 × 10-8 to 2.48 × 10-7 m2/s, 79.68-191.271kWh/kg, and 5.99-7.49, respectively. The Deff of truffle slices increased with the above-mentioned parameters of the samples. The Ea obtained was 26.62-27.43kJ/mol. The results indicated that enthalpy and entropy decreased with increasing drying temperature, while Gibbs free energy improved. The enthalpy, entropy, and Gibbs free energy values changed between 24.48-25.28kJ/mol, -130.47 to -122.63 J/mol °K, and 63.97-70.17kJ/mol, respectively. In addition, the results of color attributes decreased with increasing temperature, while chroma oppositely increased.

Limits of coefficient of performance of adsorption cooling cycle based on refrigerant’s type

This research work discusses how the thermodynamic properties of refrigerant constrain the upper limit of the coefficient of performance (COP) of adsorption cooling (AC) cycle. A mathematical model is developed based on the mass and energy balance across the adsorption bed and used to estimate the maximum COP. Langmuir model is used to derive the ideal COP. Besides, Carnot COP and exergy efficiency are derived to evaluate the adsorption cooling cycle further. These new parameters are applied to the available cycles in the open literature to assess how much room for improvement is still left in the adsorption technology based on the refrigerant type. Water, ammonia, methanol, ethanol, Butane, R134a, R32, CO2 and R1234ze are used in this study. The maximum cooling COP cannot exceed 1.0 for cooling applications and is always less than 2.0 for heat pumps. Results show that AC cycles using water or ethanol as refrigerants achieve the highest exergy efficiency. The AC cycle using water as an adsorbate and silica gel as an adsorbent has the highest relative COP, about 80 % at 85 °C regeneration temperature. In turn, CO2 exhibits the lowest one. This work is merely an attempt to save experimental effort and time by identifying the most suitable refrigerant based on its physical and thermal properties and the cycle operating conditions.

Experimental measurement and molecular dynamics simulation analysis of thermal aging performance in composite solid propellants

As a complex mixed system, the aging mechanism of high-energy composite materials involves the aging of each component itself, interactions between components, and transformation of microstructural and thermodynamic properties. The study of a single component or performance parameter has great limitations for elaborating the cognitive complexity of aging processes, making it difficult to reveal the underlying principles of physicochemical property transformation. Thus, it can only be applied as an empirical summary. In view of this, this study comprehensively utilized numerical analysis and experimental detection to explore the evolution of micromolecular conformation and changes in macro aging performance from four aspects of composite systems, including binder aging, plasticizer migration, bond interface debonding, and mechanical property transformation. There was good consistency observed between molecular simulation and thermal aging experiments, indicating that there was basically no post curing process for HTPB propellants using TDI as the curing agent. In the early stage of aging, scission chain was the main process and, in the later stage of aging, oxidation crosslinking the main process. Oxidative crosslinking increased the mean square radius of gyration and glass transition temperature of the binder system, reduced the peak value of radial distribution function, and revealed the reason for the change of propellant hardness and CC and CO double bond content. However, chain degradation increased the number of polar groups, enhanced intermolecular polarity, reduced the solubility parameter, and increased the free volume fraction of the mixed system and the dioctyl sebacate diffusion coefficient. This resulted in an increase in the tangent value of the HTPB propellant loss angle from 0.43 to 0.44° and a decrease in the glass transition temperature from 203.3 to 202.0 K. The binding energy at the interfaces of AP/HTPB and Al/HTPB increased first and then decreased, which was consistent with SEM images of bonding interfaces. The joint effect of binding energy and mechanical properties of the binder system promoted the transformation of the stress-strain curve of aging propellant.

Binding Curve Viewer: Visualizing the Equilibrium and Kinetics of Protein-Ligand Binding and Competitive Binding.

Understanding the thermodynamics and kinetics of the protein-ligand interaction is essential for biologists and pharmacologists. To visualize the equilibrium and kinetics of the binding reaction with 1:1 stoichiometry and no cooperativity, we obtained the exact relationship of the concentration of the protein-ligand complex and the time in the second-order binding process and numerically simulated the process of competitive binding. First, two common concerns in measuring protein-ligand interactions were focused on how to avoid the titration regime and how to establish the appropriate incubation time. Then, we gave examples of how the commonly used experimental conditions of [L]0 ≫ [P]0 and [I]0 ≫ [P]0 affected the estimation of the kinetic and thermodynamic properties. Theoretical inhibition curves were calculated, and the apparent IC50 and IC50 were estimated accordingly under predefined conditions. Using the estimated apparent IC50, we compared the apparent Ki and Ki calculated by using the Cheng-Prusoff equation, Lin-Riggs equation, and Wang's group equation. We also applied our tools to simulate high-throughput screening and compare the results of real experiments. The visualization tool for simulating the saturation experiment, kinetic experiments of binding and competitive binding, and inhibition curve, "Binding Curve Viewer," is available at www.eplatton.net/binding-curve-viewer.