Thermodynamic Transformation Research Articles

Quasiprobabilities in Quantum Thermodynamics and Many-Body Systems

In this tutorial, we present the definition, interpretation, and properties of some of the main quasiprobabilities that can describe the statistics of measurement outcomes evaluated at two or more times. Such statistics incorporate the incompatibility of the measurement observables and the state of the measured quantum system. We particularly focus on Kirkwood-Dirac quasiprobabilities and related distributions. We also discuss techniques to experimentally access a quasiprobability distribution, ranging from the weak two-point measurement scheme, to a Ramsey-like interferometric scheme and procedures assisted by an external detector. Once defined the fundamental concepts following the standpoint of joint measurability in quantum mechanics, we illustrate the use of quasiprobabilities in quantum thermodynamics to describe the quantum statistics of work and heat, and to explain anomalies in the energy exchanges entailed by a given thermodynamic transformation. On the one hand, in work protocols, we show how absorbed energy can be converted to extractable work and vice versa due to Hamiltonian incompatibility at distinct times. On the other hand, in exchange processes between two quantum systems initially at different temperatures, we explain how quantum correlations in their initial state may induce cold-to-hot energy exchanges, which are unnatural between any pair of equilibrium nondriven systems. We conclude the tutorial by giving simple examples where quasiprobabilities are applied to many-body systems: scrambling of quantum information, sensitivity to local perturbations, and quantum work statistics in the quenched dynamics of models that can be mapped onto systems of free fermions, for instance, the Ising model with a transverse field. Throughout the tutorial, we meticulously present derivations of essential concepts alongside straightforward examples, aiming to enhance comprehension and facilitate learning. Published by the American Physical Society 2024

Unravelling Ultra‐Stable Conversion‐Type Zinc‐Ion Storage in Copper Selenides for Flexible Aqueous Batteries

AbstractRocking‐chair configurations based on advanced anodes with reliable zinc‐ion storage can intrinsically avoid the deterioration of flexible zinc‐ion energy devices by corrosion, dendrites, and inadequate mechanical stability of zinc metal, yet the identification of durable anode materials is still challenging. Herein, the first reported conversion‐type Cu2‐xSe is proposed as an ultra‐stable anode for flexible rocking‐chair aqueous zinc‐ion batteries. Differing from these well‐recognized intercalation‐type copper selenide anodes, the unique Cu2‐xSe structure features a preferred thermodynamic deep transformation path, and the high‐reversible conversion reaction is fully illuminated by in situ synchrotron X‐ray diffraction and substantial ex situ characterization, demonstrating an outstanding performance combination of high capacity (150 mAh g−1 at 0.5 A g−1) and record‐high stability (91% capacity retention after 20 000 cycles at 5 A g−1 in Cu2‐xSe||ZnxMnO2 full cells). Consequently, fiber‐shaped batteries using Cu2‐xSe as the anode are successfully assembled and exhibited an ultra‐long life (89.8% capacity retention after 900 cycles) and extraordinary flexibility (98% capacity retention after 4500 cycles of bending), far exceeding those of representative flexible batteries previously reported. The findings provide novel insights into the energy storage mechanism of copper selenides and, as an elegant forerunner, offer a plausible path for the development of rocking‐chair flexible aqueous zinc‐ion batteries.

Prediction of Macrosegregation in Fe–C–Cr Alloy Casting through Coupling with Thermodynamic Phase Transformation Path

The continuum macroscopic transport approach combined with a tabulated thermodynamic phase transformation path is established to predict the macrosegregation in Fe‐1.05 wt% C‐1.65 wt% Cr hypereutectoid steel castings. A combined partial‐equilibrium (PE) and para‐equilibrium (PA) thermodynamic approximation is developed to retrieve the phase transformation path in steels. PA routine is performed on both austenite to stoichiometric cementite transition and austenite to α‐ferrite transition in eutectoid transformation. The approach is also applied to a hypoeutectoid alloy to predict austenite to α‐ferrite transition as well as δ‐ferrite to austenite transition in mushy zone. Thermodynamic properties in macroscopic transport approach are updated by group interpolation from tabulated phase transformation path. Results show that the interaction between substitutional solute Cr and interstitial C weakens the segregation of C and the amount of cementite in the center of casting, making the C distribution more consistent with that obtained by original position statistical distribution analysis in GCr15SiMn alloy castings. This implies that including the contribution of more components can make the estimate more reasonable. The results indicate the potential of macroscopic transport prediction coupled with tabulated phase transformation path through PE + PA approximation.

Sensing and Imaging Molecular Oxygen in Mammals with Spin Lattice Relaxation Electron Paramagnetic Resonance.

Molecular oxygen and its thermodynamic transformation drive nearly all life processes. Quantitative measurement and imaging of oxygen in living systems is of fundamental importance for the study of life processes and their aberrations-disease- many of which are affected by hypoxia, or low levels of oxygen. Cancer is among the disease processes profoundly affected by hypoxia. Electron paramagnetic resonance has been shown to provide remarkably accurate images of normal and cancerous tissue. In this review, we emphasize the reactivity of molecular oxygen particularly highlighting the metabolic processes of living systems to store free energy in the reactants. The history of hypoxic resistance of living systems to cytotoxic therapy, particularly radiation therapy is also reviewed. The measurement and imaging of molecular oxygen with pulse spin lattice relaxation (SLR) electron paramagnetic resonance (EPR) is reviewed briefly. This emphasizes the advantages of the spin lattice relaxation based measurement paradigm to reduce the sensitivity of the measurement to the presence of the oxygen sensing probe itself. The involvement of a novel small mammal external beam radiation delivery system is described. This enables an experimental paradigm based on control by radiation of the last resistant clonogen. This is much more specific for tumor cure than growth delay assays which primarily reflects control of tumor cells most sensitive to therapy.

Transformation behavior of heavy metal during Co-thermal treatment of hazardous waste incineration fly ash and slag/electroplating sludge

In this study, the behavior of heavy metal transformation during the co-thermal treatment of hazardous waste incineration fly ash (HWIFA) and Fe-containing hazardous waste (including hazardous waste incineration bottom slag (HWIBS) and electroplating sludge (ES)) was investigated. The findings demonstrated that such a treatment effectively reduced the static leaching toxicity of Cr and Pb. Moreover, when the treatment temperature exceeded 1000 °C, the co-thermal treated sample exhibited low concentrations of dynamically leached Cr, Pb, and Zn, indicating that these heavy metals were successful detoxified. Thermodynamic analyses and phase transformation results suggested that the formation of spinel and the gradual disappearance of chromium dioxide in the presence of Fe-containing hazardous wastes contributed to the solidification of chromium. Additionally, the efficient detoxification of Pb and Zn was attributed to their volatilization and entry into the liquid phase during the co-thermal treatment process. Therefore, this study sets an excellent example of the co-thermal treatment of hazardous wastes and the control of heavy metal pollution during the treatment process.

Crystal Structure Analysis, Stability, Phase Transformation and Selective Nucleation Mechanism of Fluralaner Polymorphs

To better understand and control the crystallization of different polymorphs, a comprehensive crystal structure analysis was conducted by using fluralaner as a model compound, and the thermodynamic stability, phase transformation, and selective nucleation mechanisms were studied. Various analytical techniques such as powder X-ray diffraction, thermal analysis, and FT-IR spectra were used to comprehensively characterize Form I, Form Ⅱ, and Form III of fluralaner, and it was found that there is structural similarity between Form I and Form III, which was further confirmed by single crystal X-ray diffraction. However, it was found that Form Ⅱ had unique molecular conformation and packing pattern. The lattice energy was calculated by Materials Studio 7.0 and the thermodynamic stability of three forms was explored by phase transformation experiments, which suggested that the order of thermodynamic stability was Form Ⅱ > Form I > Form III. The selective nucleation of Form I and Form III with similar structure was studied through FT-IR spectra and molecular dynamics simulations. The results indicated that the addition of n-hexane may hinder the solute–solute interaction in the solution, thus resulting in the nucleation of different polymorphs.

Mechanism of thermoviscoelasticity driven solid-liquid interface reducing friction for polymer alloy coating

High-temperature ablation is a common failure phenomenon that limits the service life of the transmission parts on heavy-duty machines used in heavy load, high temperature, high shock conditions due to in-sufficient supply of lubricating oil and grease. Traditional self-lubricating coatings prepared by inorganic, organic or organic-inorganic hybrid methods are prone to be oxidated at high temperatures to lose their friction reducing function, so that it is difficult to meet the engineering requirements of high-temperature lubrication. We design viscoelastic polymer coatings by a high-temperature self-lubricating and wear-resistant strategy. Polytetrafluoroethylene (PTFE, Tm = 329 °C) and polyphenylene sulfide (PPS, Tg = 84 °C, Tm = 283 °C) are used to prepare a PTFE/PPS polymer alloy coating. As the temperature increases from 25 to 300 °C, the PTFE/PPS coating softens from glass state to viscoelastic state and viscous flow state, which is owing to the thermodynamic transformation characteristic of the PPS component. Additionally the friction coefficient (µ) decreased from 0.096 to 0.042 with the increasing of temperature from 25 to 300 °C. The mechanism of mechanical deformation and surface morphology evolution for the PTFE/PPS coating under the multi-field coupling action of temperature (T), temperature-centrifugal force (T-Fω), temperature-centrifugal force-shearing force (T-Fω-Fτ) were investigated. The physical model of “thermoviscoelasticity driven solid-liquid interface reducing friction” is proposed to clarify the self-lubricating mechanism determined by the high-temperature viscoelastic properties of polymers. The high-temperature adjusts the viscosity (η) of the coating, increases interface slipping and intensifies shear deformation (τ), reducing the friction coefficient. The result is expected to provide a new idea for designing anti-ablation coatings served in high temperature friction and wear conditions.

Thermodynamic transformation determining the essence of time

The consistent application of thermodynamic knowledge makes it possible to analyze in detail and modify the definition of time formulated by Isaac Newton. It also makes it possible to integrate Immanuel Kant's ideas about the relationship of human sensuality with the modern category of time. As a result of these analyses, there is an updated definition and indication of the constant that determines the rate of passage of time. A distinction between the concepts of time and duration emerged, making it possible to conclude that only processes described by the category of duration can be reversible. Other processes considered in terms of time are irreversible. The main purpose of this article is to precisely define the original thermodynamic transformation, which is the basis for measuring the pace and feeling of the course of time.

Thermodynamic Behavior and Energy Transformation Mechanism of the Multi-Period Evolution of Cavitation Bubbles Collapsing near a Rigid Wall: A Numerical Study

The dynamic behavior and energy transformation mechanism of the multi-period evolution of bubbles collapsing near a wall have been essential considerations in bubble dynamics research. In this study, a compressible two-phase solver considering thermodynamics and phase transitions is developed on OpenFOAM (version v2112). This model is validated via comparison with analytical solutions and experimental results. The dynamics of the multi-period evolution of bubbles collapse process at different dimensionless stand-off distances (γ) were accurately reproduced. The results indicate that the shock wave emitted by the collapse of cavitation bubbles impacts the wall, causing the fluid temperature along the wall to increase. Moreover, the liquid jet has a dual effect on the wall temperature increase, depending on the initial stand-off distance between the bubble and the wall. When γ is small, the jet carries the low-temperature fluid to occupy the high-temperature region, and when γ is large, the jet carries the high-temperature fluid to occupy the low-temperature region. Compared with the mechanisms above of wall temperature increase, the collapse process of cavitation, when directly attached to the wall, increases the fluid temperature along the wall more significantly. Additionally, an energy transformation mechanism is proposed considering the internal bubble energy based on the analysis of the internal bubble energy and acoustic radiation energy with different γ values. Both the internal and acoustic radiation energy initially decreased and subsequently increased with increasing γ values. These findings provide deeper insights into the near-wall collapsing cavitation process mechanism.

Thermodynamic Transformation of Crystalline Organic Hybrid Iron Selenide to FexSey@CN Microrods for Sodium Ion Storage.

Carbon-coated metal chalcogenide composites have been demonstrated as one type of promising anode material for sodium-ion batteries (SIBs). However, combining carbon materials with micronanoparticles of metal chalcogenide always involve complicated processes, such as polymer coating, carbonization, and sulfidation/selenization. To address this issue, herein, we reported a series of carbon-coated FexSey@CN (FexSey = FeSe2, Fe3Se4, Fe7Se8) composites prepared via the thermodynamic transformation of a crystalline organic hybrid iron selenide [Fe(phen)2](Se4) (phen = 1,10-phenanthroline). By pyrolyzing the bulk crystals of [Fe(phen)2](Se4) at different temperatures, FexSey microrods were formed in situ, where the nitrogen-doped carbon layers were coated on the surface of the microrods. Moreover, all the as-prepared FexSey@CN composites exhibited excellent sodium-ion storage capabilities as anode materials in SIBs. This work proves that crystalline organic hybrid metal chalcogenides can be used as a novel material system for the in situ formation of carbon-coated metal chalcogenide composites, which could have great potential in the application of electrochemical energy storage.

Investigation of atropisomeric transformation of a novel PDE4 inhibitor with tetrahydroisoquinoline-based amide group and its primary study of binding to HSA

In this study a kinetic and thermodynamic atropisomeric transformation due to a hindered rotation around the tetrahydroisoquinoline-based amide group was investigated. Quantum chemistry calculations were applied to investigate the transformation under the gas phase and several solvents with different polarity, and then evaluated by dynamic HPLC determination. It was found that the transformation rate of constants and the half-life time varied under the influence of solvent polarity and temperature and the energies of rotational barrier were determined ranging between 87 and 92 kJ∙mol−1. A primary binding study with HSA confirmed a rapid interconversion under the simulated physiological conditions. It is therefore suggested to take this atropisomeric compound as a racemic mixture for its future drug development.

Numerical analysis of two-stage vacuum ejector performance considering the influence of phase transition and non-condensable gases

Multi-effect distillation with thermal vapor compression system has not been able to penetrate the market because of the low coefficient of performance. The two-stage vacuum ejector is an effective vehicle to maintain system condensing temperature, discharge non-condensable gases and improve the system performance. Improving performance of two-stage vacuum ejector relies on the understanding of the fluid dynamic phenomena. Unfortunately, few studies paid attention to the effect of inner fluid phase transition and non-condensable gas mass fraction on the performance of vacuum ejector. Therefore, this paper contributes to proposing a Species transport and Phase transition model to investigate the two-stage vacuum ejector numerically considering the physical properties of non-condensable gases, thermodynamic transformation caused by condensation and evaporation with experimental validation. The results indicate that the entrainment performance of the ejector increases by about 14.95% when the non-condensable gases mass fraction increases from 0% to 100%. Meanwhile, with the consideration of heat and mass transfer in the phase change process, the mean error is 4.9%, which is much lower than single-phase model. Meanwhile, the internal fluid pressure, Mach number, shock waves and expansion degree can be largely influenced by the consideration of Species transport and Phase transition. The results of this paper proved that influence of non-condensable gases and phase transition cannot be ignored in the design and prediction of vacuum ejector and it can contribute to ejector optimization and enhancing the stability and efficiency of multi-effect distillation with thermal vapor compression system.

Free Energy Changes during Spherical Droplet Deposition—Mechanistic Model

On the basis of theoretical considerations (mechanistic model), an equation was determined that allowed to calculate the free energy (Helmholtz) of a spherical droplet deposited on a flat surface in a system without external forces. Assuming isochoric and isothermal transformation of the system and a very fast conversion of mechanical energy into heat, the obtained equation allows to determine the trajectory of thermodynamic transformation consisting of the spreading of the droplet on the surface of the substrate. The similarities and differences in the behaviour of spherical droplets described by the mechanistic model and Young’s model, together with its improvements, were discussed. The trajectories of free energy changes during the spreading of droplets in a system in which the adhesive force acting perpendicular to the wetted surface was considered as well.

Cation/Anion Dual-Vacancy Pair Modulated Atomically-Thin Sex -Co3 S4 Nanosheets with Extremely High Water Oxidation Performance in Ultralow-Concentration Alkaline Solutions.

The density functional theory calculation results reveal that the adjacent defect concentration and electronic spin state can effectively activate the CoIII sites in the atomically thin nanosheets, facilitating the thermodynamic transformation of *O to *OOH, thus offering ultrahigh charge transfer properties and efficiently stabilizing the phase. This undoubtedly evidences that, for metal sulfides, the atom-scale cation/anion vacancy pair and surface electronic spin state can play a great role in enhancing the oxygen evolution reaction. Inspired by the theoretical prediction, interconnected selenium (Se) wired ultrathin Co3 S4 (Sex -Co3 S4 ) nanosheets with Co/S (Se) dual-vacancies (Se1.0 -Co3 S4 -VS/Se -VCo ) pairs are constructed by a simple approach. As an efficient sulfur host material, in an ultralow-concentration KOH solution (0.1 m), Se1.0 -Co3 S4 -VS/Se -VCo presents outstanding durability up to 165 h and a low overpotential of 289.5mV at 10mA cm-2 , which outperform the commercial Co3 S4 nanosheets (NSs) and RuO2 . Moreover, the turnover frequency of Se1.0 -Co3 S4 -VS/Se -VCo is 0.00965 s-1 at an overpotential of 0.39V, which is 5.7 times that of Co3 S4 NSs, and 5.8 times that of commercial RuO2 . The finding offers a rational design strategy to create the multi-defect structure in catalysts toward high-efficiency water electrolysis.

Modeling mechanical equilibration processes of closed quantum systems: A case study.

We model the dynamics of a closed quantum system brought out of mechanical equilibrium, undergoing a nondriven, spontaneous, thermodynamic transformation. In particular, we consider a quantum particle in a box with a moving and insulating wall, subjected to a constant external pressure. Under the assumption that the wall undergoes classical dynamics, we obtain a system of differential equationsthat describes the evolution of the quantum system and the motion of the wall. We study the dynamics of such a system and the thermodynamics of the process of compression and expansion of the box. Our approach is able to capture several properties of the thermodynamic transformations considered and goes beyond a description in terms of an ad hoc time-dependent Hamiltonian, considering instead the mutual interactions between the dynamics of the quantum system and the parameters of its Hamiltonian.

Hawking decay and thermodynamic transformation of a black hole: two examples

Hawking decay and thermodynamic transformation of a black hole: two examples

Transformation behaviour of pyrite during microwave desulfurization from coal: Phase and structural change of Fe-S compounds

The selective heating of pyrite (FeS2) in coal by microwave makes its removal more efficient, but the gas produced by high-sulfur coal during microwave irradiation may affect the conversion process of pyrite. In this article, the transformation mechanism of pyrite in coal during microwave desulfurization was investigated experimentally and computationally. X-ray diffraction (XRD) was used to analyze the phase change of pyrite in air and inert atmosphere. The thermodynamic transformation patterns of pyrite under different atmospheres were further determined by FactSage. Materials Studio was used to derive the changes of atomic coordination, density of states, band structure, and bond length of iron sulfides to elucidate the causes of pyrite transformation behavior. The results show that the transformation paths of pyrite in different atmospheres are similar, troilite (FeS) can be produced directly from FeS2 or indirectly from pyrrhotite (Fe7S8). The generation temperatures of FeS2 are different for the four atmospheric conditions, however, the theoretical generation temperature of Fe7S8 is 612.5 °C for all of them. From the calculated results, Fe7S8 is the least stable, while pyrite is the most stable. With the addition of an electric field equivalent to a microwave field, FeS becomes the final product of the pyrite sulfur conversion process due to a significant decrease in bond length.

Cardanol grafted reclaimed rubber by in-situ reaction for better properties

Cardanol grafted reclaimed rubber (CGRR) was prepared by in-situ reaction between reclaimed rubber (RR) and cardanol, during reclamation of waste rubber powder (WRP) in an internal mixer at 190 °C. Dicumyl dioxide (DCP) acted as an initiator. The percent grafting, grafting efficiency, structural characteristics, reclamation degree and storage stability of RR, as well as the mechanical properties of re-vulcanized CGRR (rCGRR) were all investigated by the effect of DCP content. The FTIR and 1H-NMR proved that cardanol was successfully grafted onto the backbone of RR. Both grafting reaction and the reclaiming reaction could be affected by DCP content. The percent grafting, grafting efficiency of CGRR increase with DCP content. While DCP over 0.5 phr, the reclamation degree of CGRR decrease which had an adverse influence on mechanical properties of rCGRR. By comparison, the optimum content of DCP should be 0.5 phr. In addition, the CGRR (0.5 phr DCP) shows obviously improved mechanical properties and storage stability (70 days detection) than that of aromatic oil filled reclaimed rubber. The thermal stability of cardanol and WRP, also thermodynamic transformation of CGRR were characterized by TGA and DSC respectively.

Thermodynamic Simulation and Transformation Behaviours of Lead during Iron Ore Sintering

Lead (Pb) increases the corrosion rate of refractory lining in blast furnaces. The iron ore sintering process plays a vital role in decreasing lead content of the feeding materials for blast furnaces. In this paper, lead compounds in the raw materials blend and the sinter product were leached out sequentially and classified into four categories. In the raw materials blend, PbS accounted for about 66.25% of lead compounds and 23.57% of lead was found as PbO. While in the sinter product, the main lead compounds were PbSO4, PbO·Fe2O3 and PbO. The transformation and removal behaviours of lead compounds were simulated via Factsage7.1 and tube furnace tests. It was confirmed Pb could be removed in forms of PbCl2, metallic Pb and PbO during iron ore sintering process. The lead removal rate in the industry was 49.77%. While, with the increasing carbon to 15%, over 93% of the lead was removed in lab. In addition, increasing the maximum sintering temperature and CaO content properly could also enhance the removal of lead.

Thermodynamics and Chemical Behavior of Uranyl Superoxide at Elevated Temperatures.

Understanding the alteration mechanisms of UO2-based nuclear fuel has a range of practical implications for both short- and long-term storage of spent fuel rods and environmental ramifications for the mobility of radioactive material at the Chernobyl and Fukushima sites. The major identified alteration phases on the surface of nuclear waste are analogues of schoepite UO3·2H2O, studtite UO2(O2)·4H2O, rutherfordine UO2CO3, and čejkaite Na4UO2(CO3)3. While α-radiolysis has been shown to cause the ingrowth of uranyl peroxide alteration phases, the prevalence of uranyl carbonate phases on solid waste forms has not been mechanistically explained to date, especially since the alteration chemistry is largely affected by the high temperatures of the spent nuclear material. Herein, we demonstrate the first mechanistic link between the formation of the uranyl superoxide (KUPS-1) phase, its reactivity at temperature ranges relevant to the spent nuclear fuel (40-350 °C), and its thermodynamic transformation into a potassium uranyl carbonate mineral phase, agricolaite K4[UO2(CO3)3], using thermogravimetric analysis, calorimetry, vibrational spectroscopy, and powder X-ray diffraction techniques. The thermodynamics data reveal the metastability of the uranyl superoxide KUPS-1 phase through decomposition of the hydrogen peroxide within the solid-state lattice. Increasing the temperature does not result in the breakdown of the superoxide anion bound to the uranyl cation but instead enhances its reactivity in the presence of CO2 gas, resulting in potassium carbonate phases at intermediate temperatures (150 °C) and in uranyl carbonate phases at higher temperatures (350 °C).