Thermodynamic Regime Research Articles

Effect of deposition regime transition on the properties of Al:ZnO transparent conducting oxide layer by radio frequency magnetron sputtering system

High-quality zinc oxide thin films doped with aluminium adatoms have effectively been fabricated on pristine soda-lime silica glass substrates via radio frequency magnetron sputtering system. The deposition temperature was varied to explore the impact of deposition regime transition of as-deposited Al:ZnO thin films on their performance as transparent conducting oxide layers. In particular, the depositions were conducted at room temperature, 100 °C, 200 °C, and 300 °C, allowing for a comprehensive assessment of the resulting films. The Raman spectra depicted the modulation of Raman bands in correlation with the deposition regime transition, illustrating the impact of thermal induction on various properties of the as-deposited aluminium-doped zinc oxide thin films. Atomic force microscopy reveals the transformation from nearly spherical to elongated shape structure was obtained as the deposition process shifted from kinetic limited to thermodynamic limited regimes. The phase analysis and grazing incident of x-ray diffractometer disclose a single crystal orientation has been achieved at thermodynamic limited regime. However, two different crystal planes were predominant comparing between the surface and structural of as-deposited aluminium-doped zinc oxide thin films. It is also evident that a highly transparent with low lattice strain and better carrier concentrations of as-deposited aluminium-doped zinc oxide thin films were realized at thermodynamic limited regimes.

Large-scale dynamic processes during the minor and major sudden stratospheric warming events in January–February 2023

Using data from reanalyses of meteorological information, this study examines peculiarities of the thermodynamic regime of the Arctic stratosphere in the winter season of 2022–2023. For this purpose, components of the global meridional circulation, wave activity fluxes, volume of polar stratospheric clouds type I (PSC NAT) are analyzed, as well as changes in these indicators during sudden stratospheric warming (SSW) events formed in January–February. The main features of the 2022–2023 winter season were the following: (1) a persistent cold stratospheric polar vortex was observed until mid-January, which caused the PSC NAT volume growth to its maximum values since 1980; (2) enhanced wave activity from mid-January led to the formation of a minor SSW at the end of January, an increase in the temperature of the lower stratosphere and a sharp reduction in PSC NAT; (3) a week of intensification of the polar vortex was then observed, followed by a weakening due to the next burst of wave activity propagation during the second SSW event in mid-February. This second SSW event was major, accompanied by a reversal of the mean zonal wind, which lasted until early March; (4) meridional heat flux in January–February 2023 was the highest since 1948, resulting in unprecedented warming of the lower Arctic stratosphere and preventing ozone depletion in March; (5) the minor SSW at the end of January was accompanied by a more intense change in the meridional circulation than the major SSW in mid-February. Formation of ozone mini-hole over Northern and Central Europe in February 2023 was associated with the strengthening of the anticyclone, leading to a stratopause elevation and northward transport of ozone-poor air masses from the subtropics along the western periphery of the anticyclone additionally to related to the major SSW temperature changes affected the ozone concentration in the lower stratosphere.

Identifying diffusive length scales in one-dimensional Bose gases

In the hydrodynamics of integrable models, diffusion is a subleading correction to ballistic propagation. Here we quantify the diffusive contribution for one-dimensional Bose gases and find it most influential in the crossover between the main thermodynamic regimes of the gas. Analysing the experimentally measured dynamics of a single density mode, we find diffusion to be relevant only for high wavelength excitations. Instead, the observed relaxation is solely caused by a ballistically driven dephasing process, whose time scale is related to the phonon lifetime of the system and is thus useful to evaluate the applicability of the phonon bases typically used in quantum field simulators.

Explicit Habit‐Prediction in the Lagrangian Super‐Particle Ice Microphysics Model McSnow

AbstractThe Monte‐Carlo ice microphysics model McSnow is extended by an explicit habit prediction scheme, combined with the hydrodynamic theory of Böhm. Böhm's original cylindrical shape assumption for prolates is compared against recent lab results, showing that interpolation between cylinder and prolate yields the best agreement. For constant temperature and supersaturation, the predicted mass, size, and density of the ice crystals agree well with the laboratory results, and a comparison with real clouds using the polarizability ratio shows regimes capable of improvement. An updated form of the inherent growth function to describe the primary habit growth tendencies is proposed and combined with a habit‐dependent ventilation coefficient. The modifications contrast the results from general mass size relations and significantly impact the main ice microphysical processes. Depending on the thermodynamic regime, ice habits significantly alter depositional growth and affect aggregation and riming. The influence of primary ice behavior on precipitation formation needs to be considered in future development of microphysical parameterizations, but the consideration of secondary habits and the geometry of aggregates should be further improved in future work.

Functional central limit theorems for local statistics of spatial birth–death processes in the thermodynamic regime

Functional central limit theorems for local statistics of spatial birth–death processes in the thermodynamic regime

Extreme thermodynamics in nanolitre volumes through stimulated Brillouin–Mandelstam scattering

Examining the physical properties of materials—particularly of toxic liquids—under a wide range of thermodynamic states is a challenging problem due to the extreme conditions the material has to experience. Such temperature and pressure regimes, which result in a change in the refractive index and sound velocity, can be accessed by optoacoustic interactions such as Brillouin–Mandelstam scattering. Here we demonstrate the Brillouin–Mandelstam measurements of nanolitre volumes of liquids in extreme thermodynamic regimes. This is enabled by a fully sealed liquid-core optical fibre containing carbon disulfide. Within this waveguide, which exhibits tight optoacoustic confinement and a high Brillouin gain, we are able to conduct spatially resolved measurements of the local Brillouin response, giving us access to a resolved image of the temperature and pressure values along the liquid channel. We measure the material properties of the liquid core at very large positive pressures (above 1,000 bar) and substantial negative pressures (below –300 bar), as well as explore the isobaric and isochoric regimes. The extensive thermodynamic control allows the tunability of the Brillouin frequency shift of more than 40% using only minute volumes of liquid.

Modeling aqueous association constants and mineral solubilities at subcritical and supercritical temperatures

The need for sustainable power generation has increased interest in the use of hydrothermal fluids for industrial applications. New high-enthalpy geothermal systems and biowaste-to-fuel processes are two relevant examples that employ supercritical fluids which require an in-depth understanding of complex chemical reactions occurring near the supercritical temperature of water (374 °C). As these processes operate in thermodynamic regimes that are not currently covered by a standard molar Gibbs energy of formation model, only empirical fits for single reaction systems are available which limit the use of multi-component phase equilibria calculations that are standard practice for less extreme environments. Here, we advance a standard molar Gibbs energy of formation model able to operate in these otherwise inaccessible thermodynamic states to include species needed for key mineral solubility systems and ion association reactions. This work extends a model based on molecular statistical thermodynamics (MST) into four new systems (Na3PO4-H2O, LiOH-H2O, KOH-H2O, and BaSO4-H2O) by extending the model to cover 10 new species. For each of these systems, model predictions were consistently within the experimental uncertainties for the new systems covered. A breakdown of MST contributions to the model revealed that electrostatic and hard sphere contributions were key to reproducing density dependencies of standard molar Gibbs energy of formation values around the critical point of water.

The nature of carbon deposits and their formation pathways during catalytic supercritical water gasification of glycerol

Supercritical water gasification (SCWG) is a promising technology to convert wet biomass to renewable natural gas. The present study sheds light on the chemical composition and the formation mechanism of coke deposits on a Ru/CNF catalyst during continuous SCWG of glycerol in a fixed-bed reactor. SCWG experiments were performed using pristine carbon nanofibers (CNF) and 5 wt% Ru/CNF catalysts, which suffered from partial deactivation. Transmission electron microscopy (TEM) indicated a 34–42 % dispersion loss independently of the conditions, only partially explaining the activity loss observed during the test at very high space velocity. When operated under thermodynamic conditions, no deposits could be observed. A nanometric layer of deposits on the catalysts was present under intermediate conditions, while in the kinetic regime (conversion of glycerol down to 4 %), significant carbon deposition was observed. The chemical compositions of aqueous phases and organic deposits extracted from the catalysts and support showed that the presence of Ru enhanced the formation of unsaturated compounds from glycerol. In particular, molecules containing aromatic rings were detected. The space velocity significantly affected the composition of the coke deposits. The number of carbons in the molecules increased from 5–25 to 10–45 when moving away from the thermodynamic regime (full conversion), and the O/C ratio significantly decreased from 0.3–0.6 to 0.05–0.3, maintaining a very broad H/C ratio. The extracted organic deposits contained various aromatic compounds but were mostly represented by unsaturated aliphatic compounds. All these results were used to elucidate a reaction pathway for the formation of organic deposits from glycerol.

Blackbody thermodynamics in the presence of Casimir’s effect

This paper is a study of the electromagnetic radiation at temperature T in a rectangular slab whose walls are made of a perfect conductor. The two large parallel walls of area A are apart by a distance . We take T, A, and d as thermodynamic parameters, obtaining the free energy from a procedure that involves the integration over the slab of the ensemble average of the stress–energy–momentum tensor calculated long ago by Brown and Maclay. Both thermodynamic regimes and are fully addressed. We show that certain thermodynamic quantities that are notoriously ill defined (or trivial) in ordinary blackbody thermodynamics are now well defined (or nontrivial) due to the presence of boundary conditions at the walls of the slab (‘Casimir’s effect’). The relationships among such quantities are fully explored and it is speculated that they may be experimentally checked. Stability is addressed, showing that electromagnetic radiation in the slab is thermally stable; but mechanically unstable. We investigate thermodynamic processes where temperature, internal energy, entropy and enthalpy are each taken to be constant, revealing rather atypical behaviors. For example, in sharp contrast with what one would expect from a gas, when , ‘free expansion’ gives place to ‘free contraction’ in accordance with the second law of thermodynamics. As a check of consistency of the formulae we remark that various Carnot cycles have been examined and verified that they correctly lead to Carnot’s efficiency.

Thermodynamic quasi-equilibria in high power magnetron discharges: a generalized Poisson–Boltzmann relation

The Poisson–Boltzmann (PB) equation is a nonlinear partial differential equation that describes the equilibria of conducting fluids. Using a thermodynamic variational principle based on the balances of particle number, entropy, and electromagnetic enthalpy, it can also be justified for a wide class of unmagnetized technological plasmas (Köhn et al 2021 Plasma Sources Sci. Technol. 30 105014). This study extends the variational principle and the resulting PB equation to high power magnetron discharges as used in planar high power pulsed magnetron sputtering. The example in focus is that of a circular high power magnetron. The discharge chamber and the magnetic field are assumed to be axisymmetric. The plasma dynamics need not share the symmetry. The domain is split into the ionization region close to the cathode where electrons are confined, i.e. can escape from their magnetic field lines only by slow processes such as drift and diffusion, and the outer region , where the electrons are largely free and the plasma is cold. With regard to the dynamics of the electrons and the electric field, a distinction is made between a fast thermodynamic and a slow dissipative temporal regime. The variational principle established for the thermodynamic regime is similar to its counterpart for unmagnetized plasmas but takes magnetic confinement explicitly into account by treating the infinitesimal flux tubes of as individual thermodynamic units. The obtained solutions satisfy a generalized PB relation and represent thermodynamic equilibria in the fast regime. However, in the slow regime, they must be interpreted as dissipative structures. The theoretical characterization of the dynamics is corroborated by experimental results on high power magnetrons published in the literature. These results are briefly discussed to provide additional support.

Development of an equation of state to characterize an electron beam interacting with an aluminum target

The Equations Of State (EOS) of materials under extreme conditions of temperature and pressure can be experimentally studied, thanks to intense electron beam-target experiments. The latter are powerful tools to probe materials in the warm dense matter regime. At CEA/CESTA, we use the CESAR pulsed generator (1 MV, 300 kA). During an experimental shot, a high-power 800 keV, 100 kA, 20 mm-diameter, 100 ns electron pulse produces shock waves in an aluminum target. The behavior of the latter is explored by analyzing the time-history of its rear face velocity, as measured by photon Doppler velocimetry. Using simulations, we can test the accuracy of an EOS over a wide range of densities and temperatures. In addition, an accurate EOS allows for reduction of the uncertainties of the beam parameters that have an impact on beam energy deposition. We have observed that the measurements are not correctly restituted by the simulation codes when they use the available EOS (BLF, SESAME). Thanks to both published data and ab initio calculations, which are valid in the considered thermodynamic regime, we have developed a new EOS describing precisely the thermodynamic (isochoric) regime from one-half to one-third the normal density. The corresponding hydrodynamic simulations appear to be in much better agreement with the measurements. In addition, this new EOS has allowed us to refine the knowledge of the input electron beam parameters that have an impact on beam energy deposition.

Is Direct DME Synthesis Superior to Methanol Production in Carbon Dioxide Valorization? From Thermodynamic Predictions to Experimental Confirmation

CO2 valorization is a key measure to reach climate neutrality. Thermodynamics suggest direct conversion of CO2 into dimethyl ether (DME) to have greater potential than the indirect route via methanol synthesis, followed by purification of methanol and then a separate dehydration into DME. In this work, we introduce heteropoly acids as a capable class of dehydration catalysts for direct DME synthesis from CO2 and H2. To clarify if direct DME synthesis is in fact superior to sole MeOH synthesis, accurate thermodynamic equilibrium calculations are performed and pose as the base of our argumentation. An efficient Cu/ZnO/ZrO2 (CZZ) methanol catalyst is used to compare the methanol synthesis using a feedstock with stoichiometric CO2/3H2 mixture against bifunctional catalysts, containing CZZ and a dehydration component. The dehydration components include a commercial ferrierite (FER) and heteropoly acid (HPA) coated alumina and zirconia. For direct DME synthesis, the CO2 feed gas at gas hourly space velocities (GHSVs) between 1,250 and 158,400 NL kgcat–1 h–1, at temperatures of 210–270 °C and 40 bar pressure, was investigated. Based on the wide parameter window investigated, the following can be concluded at 250 °C: under a thermodynamic regime, CO2 conversion is close to the theoretical limit (30%exp/32%theo) and the direct DME synthesis is superior to sole methanol synthesis (+20%exp/+33%theo). The amount of valuable products (methanol, DME) profits significantly more (+70%exp/+88%theo) from the direct DME synthesis than CO2 conversion indicates. Under a kinetic regime, HPA-coated catalysts show superior apparent activation energies for DME production than the widely used ferrierite (HPA: 45 kJ mol–1/FER: 80 kJ mol–1), making HPA coatings a great option for highly capable dehydration catalysts under CO2- and water-rich conditions.

Data-Driven Modeling of General Fluid Density Under Subcritical and Supercritical Conditions

Advanced propulsion and power-generation systems often operate under extreme conditions, where thermophysical properties of the working fluids undergo complex variations in a wide range of fluid states, where empirical cubic equations of state could yield substantial errors in density prediction. The present work develops data-driven models for accurate density estimation of general fluids across all thermodynamic regimes. The model starts with the cubic equation of state, whose alpha function is calibrated in a data-driven manner with statistical correction accounting for inherent correlations among training data samples. The developed models are examined for the representative pure substances in aerospace propulsion systems, including oxygen, nitrogen, carbon dioxide, and hydrocarbon fuels. Results show that the model with pressure and temperature as input variables provides consistently superior accuracy over wide ranges of temperatures and pressures, especially in the compressed-liquid region, where the Peng–Robinson equation of state significantly underperforms. The corresponding absolute average relative deviation for the studied substances is below 0.65% at different pressures, compared to 7.16% by the Peng–Robinson equation of state. The model is also extended to examine the density calculations of the selected binary and ternary mixtures, and the consistent result is obtained. The data-driven approach can be adopted to evaluate other thermodynamic properties of fluids and fluid mixtures and characteristics of vapor–liquid equilibrium, and further incorporated into large-scale multiphysics simulations where nonideal gas behavior occurs in the future.

Reciprocity relations for mechanically induced spin currents in metals in a nonlinear regime

In the Markov relaxation and locally quasi-equilibrium distribution approximation, analogues of Onzager's relations for the response functions of the spin current in the nonlinear by intense mechanical and thermodynamic effects regime were obtained by the Kubo method. Keywords: locally quasi-equilibrium distribution, spin Hamiltonian, spin current, nonlinearity, reciprocity, streintronics, spin caloritronics, Peltier spin effect, Zeebeck spin effect.

Dirac Materials and an Identity for the Grand Potential of the Nondegenerate Statistical Thermodynamic Regime

We examine the question “Can Dirac materials exist in a nondegenerate statistical state?,” deriving and employing an identity for the thermodynamic Grand Potential <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$\Omega$</tex-math></inline-formula> (per unit volume/area) in the low density nondegenerate statistical regime, relating it to the density <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$n$</tex-math></inline-formula> as <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$\Omega = -\beta ^{-1} n$</tex-math> </inline-formula> ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$\beta ^{-1} = \kappa _{B} T$</tex-math></inline-formula> is thermal energy, <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$\kappa _{B}$</tex-math></inline-formula> is the Boltzmann constant, and <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$T$</tex-math></inline-formula> is Kelvin temperature). The implications of this identity for Dirac materials are explored. The identity is universally valid for all thermodynamic systems in equilibrium in the nondegenerate, low density statistical regime, irrespective of size, dimensionality or applied static fields. Phenomena that may contribute to the realization of such a nondegenerate statistical equilibrium state in Dirac materials are discussed.

Non-ideal gas behavior matters in hydrodynamic instability

Hydrodynamic instability, the foundation for flow’s laminar-turbulent transition and various predicting models, has been helping to understand the physics and shape the design of aerodynamic devices. While for hypersonic flow it is clear that thermodynamic/-chemical effects need be accounted for due to the high temperatures occurring, this letter unveils that also for low-speed flow at ambient temperatures non-ideal, i.e. real-gas effects can play a strong role—a feature missed by the classic theory for Newtonian fluids. By considering a three-dimensional low-speed boundary-layer flow in different thermodynamic regimes—subcritical, supercritical and transcritical—we show the importance of coupling thermodynamics by sensitivity studies of the perturbation growth rate to various inputs of the full stability equations. High sensitivities are found, and not only the transition-onset location but also the transition mechanism may be concerned.

Kinetic and thermodynamic studies on [Omim]Cl/ZnCl2 catalyzed synthesis of polyoxymethylene dimethyl ethers

AbstractPolyoxymethylene dimethyl ethers (OMEs) emerging as green additives for soot emission suppression receive significant attention due to their similar physical properties to diesel. Herein, the transformative pathways of dimethoxymethane (DMM) and trioxane reactions for OMEs production catalyzed by [Omim]Cl/ZnCl2 having different ZnCl2 content were demonstrated in combination with the clarification of active species, kinetic and thermodynamic properties, and chemical nature for trioxane decomposition and subsequential formaldehyde insertion steps. The role of [Omim]Cl, which could transform to [Omim]ZnCl3 or [Omim]Zn2Cl5 under different ZnCl2 content, laid in the formation of active zinc species and promotion of their homogeneity with reactants. The DMM chain growth, which followed the same mechanism and kinetic law, showed kinetic and thermodynamic regimes and had identical equilibrium distribution of OMEs. Only Zn2Cl5− species were active for trioxane decomposition, which was the kinetic‐relevant step, while both ZnCl3− and Zn2Cl5− were effective for DMM chain elongation.

Destabilization of binary mixing layer in supercritical conditions

Compressible mixing layer instabilities are of importance to a wide range of environmental and industrial applications. Past studies have focused on either ideal-gas or real-fluid thermodynamic regimes of single-species mixing layers. However, mixing layers of binary mixtures at supercritical conditions, commonly encountered in fuel injection systems, introduce additional complexities due to the added compositional degree-of-freedom. Moreover, the effect of strong variations in thermodynamic response functions across the Widom line on the binary mixing layer stability remains poorly understood. Thus, the objective of this study is to examine the coupling between the hydrodynamic instability and the real-fluid thermodynamics across the Widom line and its effects on the overall binary mixing layer dynamics. To this end, we develop a linear stability analysis of the full binary-species compressible transport equations coupled with the PC-SAFT equation of state. Analysis shows the existence of a novel instability mechanism that arises from juxtapositioning of the Widom-line transition and the hydrodynamic inflection point. This novel thermodynamically induced instability mechanism has the net effect of destabilizing the binary mixing layer at lowering supercritical conditions towards the critical pressure point. This is in contrast to previous stability analyses of supercritical single-species mixing layers, where increasing pressure destabilizes the flow due to its effect on reducing the density stratification. The discovered thermodynamically induced instability mechanism of binary mixing flows highlights the need for an extension of classical instability criteria to incorporate the effect of strong variations in the thermodynamic response functions across the Widom line on mixing layer instability.

Sub-tree counts on hyperbolic random geometric graphs

AbstractThe hyperbolic random geometric graph was introduced by Krioukov et al. (Phys. Rev. E82, 2010). Among many equivalent models for the hyperbolic space, we study the d-dimensional Poincaré ball ( $d\ge 2$ ), with a general connectivity radius. While many phase transitions are known for the expectation asymptotics of certain subgraph counts, very little is known about the second-order results. Two of the distinguishing characteristics of geometric graphs on the hyperbolic space are the presence of tree-like hierarchical structures and the power-law behaviour of the degree distribution. We aim to reveal such characteristics in detail by investigating the behaviour of sub-tree counts. We show multiple phase transitions for expectation and variance in the resulting hyperbolic geometric graph. In particular, the expectation and variance of the sub-tree counts exhibit an intricate dependence on the degree sequence of the tree under consideration. Additionally, unlike the thermodynamic regime of the Euclidean random geometric graph, the expectation and variance may exhibit different growth rates, which is indicative of power-law behaviour. Finally, we also prove a normal approximation for sub-tree counts using the Malliavin–Stein method of Last et al. (Prob. Theory Relat. Fields165, 2016), along with the Palm calculus for Poisson point processes.

Teaching an Old Compound New Tricks: Reversible Transamidation in Maleamic Acids.

Dynamic combinatorial chemistry is a method widely used for generating responsive libraries of compounds, with applications ranging from chemical biology to materials science. It relies on dynamic covalent bonds that are able to form in a reversible manner in mild conditions, and therefore requires the discovery of new types of these bonds in order to progress. Amides, due to their high stability, have been scarcely used in this field and typically require an external catalyst or harsh conditions for exchange. Compounds able to undergo uncatalysed transamidation at room temperature are still rare exceptions. In this work, we describe reversible amide formation and transamidation in a class of compounds known as maleamic acids. Due to the presence of a carboxylic acid in β‐position, these compounds are in equilibrium with their anhydride and amine precursors in organic solvents at room temperature. First, we show that this equilibrium is responsive to external stimuli: by alternating the additions of a Brønsted acid and a base, we can switch between amide and anhydride several times without side‐reactions. Next, we prove that this equilibrium provides a pathway for reversible transamidation without any added catalyst, leading to thermodynamic distributions of amides at room temperature. Lastly, we use different preparation conditions and concentrations of Brønsted acid to access different library distributions, easily controlling the transition between kinetic and thermodynamic regimes. Our results show that maleamic acids can undergo transamidation in mild conditions in a reversible and tunable way, establishing them as a new addition to the toolbox of dynamic combinatorial chemistry.