Nonequilibrium Effects Research Articles

Effect of non-equilibrium thermochemistry on Pitot pressure measurements in shock tunnels (or: Is 0.92 really the magic number?)

Pitot pressure is the most common measurement in high total enthalpy shock tunnels for test condition verification. Nozzle calculations using multi-temperature non-equilibrium thermochemistry are needed in conjunction with Pitot measurements to quantify freestream properties. Pitot pressure is typically matched by tuning the boundary layer transition location in these simulations. However, non-equilibrium thermochemistry effects on the Pitot probe are commonly ignored. A computational study was undertaken to estimate the effect of non-equilibrium thermochemistry on Pitot pressure and freestream conditions. The test flow was produced by a Mach 7 nozzle in a reflected shock tunnel for air at a relatively low total enthalpy of 2.67MJ/kg. Three different thermochemical models (equilibrium, finite-rate chemistry and two-temperature thermochemistry) were employed to compute flow variables at the nozzle exit and Pitot probe. Pitot pressures from these simulations were compared against those obtained via experiments. The results show a departure from the commonly utilized C of 0.92 in the reduced Rayleigh-Pitot equation form for high Mach numbers. Additionally, calculations were done with a sweep of free-stream conditions and resulting in values for one- and two-temperature models to use in future shock tunnel studies. Overall, our results show that the influence of finite-rate thermochemistry should be taken into account, even at relatively low flow enthalpies.

Non-Equilibrium Enhancement of Classical Information Transmission.

Information transmission plays a crucial role across various fields, including physics, engineering, biology, and society. The efficiency of this transmission is quantified by mutual information and its associated information capacity. While studies in closed systems have yielded significant progress, understanding the impact of non-equilibrium effects on open systems remains a challenge. These effects, characterized by the exchange of energy, information, and materials with the external environment, can influence both mutual information and information capacity. Here, we delve into this challenge by exploring non-equilibrium effects using the memoryless channel model, a cornerstone of information channel coding theories and methodology development. Our findings reveal that mutual information exhibits a convex relationship with non-equilibriumness, quantified by the non-equilibrium strength in transmission probabilities. Notably, channel information capacity is enhanced by non-equilibrium effects. Furthermore, we demonstrate that non-equilibrium thermodynamic cost, characterized by the entropy production rate, can actually improve both mutual information and information channel capacity, leading to a boost in overall information transmission efficiency. Our numerical results support our conclusions.

Investigation of Magneto-convection in Viscoelastic Fluid Saturated Anisotropic Porous Layer Under Local Thermal Non-equilibrium Condition

The problem of magneto-convection in viscoelastic fluid saturated anisotropic porous layer under local thermal non-equilibrium (LTNE) effect is investigated. Extended Darcy model with time derivative term for viscoelastic fluid of the Oldroyd type with an externally imposed vertical magnetic field is used to model the momentum equation. The entire investigation has been split into two parts: (i) linear stability analysis (ii) weakly non-linear stability analysis. We perform normal mode technique to examine linear stability analysis while truncated representation of Fourier series method is used for weakly non-linear stability analysis. The onset of convection is set in through oscillatory rather than stationary mode due to competition between the processes of thermal, magnetic effect and viscoelasticity. A comparative study between anisotropic and isotropic porous medium is made as a function of Q (Chandrasekhar number), 𝛤 (non dimensional inter phase heat transfer coefficient), 𝜆1 (Relaxation time) and λ2 (Retardation time). Apart from this, Q, 𝛤 and λ2 stabilize the system in oscillatory case while 𝜆1 destabilize the system. Furthermore 𝜉 (mechanical anisotropic parameter), 𝜂s (thermal anisotropic parameter for solid phase), destabilizes the system and 𝜂f (thermal anisotropic parameter for fluid phase) stabilizes the system. The effect of Q, 𝜆1, λ2, 𝛤, 𝜉, 𝜂f and 𝜂s on heat transfer is also examined.

Discrete Boltzmann model with split collision for nonequilibrium reactive flows* *This work is supported by the National Natural Science Foundation of China (under Grant Nos. U2242214, 51806116 and 91441120), the Guangdong Basic and Applied Basic Research Foundation (under Grant Nos. 2022A1515012116 and 2024A1515010927), the Natural Science Foundation of Fujian Province (under Grant Nos. 2021J01652, 2021J01655), and the China Scholarship Council

A multi-relaxation-time discrete Boltzmann model (DBM) with split collision is proposed for both subsonic and supersonic compressible reacting flows, where chemical reactions take place among various components. The physical model is based on a unified set of discrete Boltzmann equations that describes the evolution of each chemical species with adjustable acceleration, specific heat ratio, and Prandtl number. On the right-hand side of discrete Boltzmann equations, the collision, force, and reaction terms denote the change rates of distribution functions due to self- and cross-collisions, external forces, and chemical reactions, respectively. The source terms can be calculated in three ways, among which the matrix inversion method possesses the highest physical accuracy and computational efficiency. Through Chapman–Enskog analysis, it is proved that the DBM is consistent with the reactive Navier–Stokes equations, Fick's law and the Stefan–Maxwell diffusion equation in the hydrodynamic limit. Compared with the one-step-relaxation model, the split collision model offers a detailed and precise description of hydrodynamic, thermodynamic, and chemical nonequilibrium effects. Finally, the model is validated by six benchmarks, including multicomponent diffusion, mixture in the force field, Kelvin–Helmholtz instability, flame at constant pressure, opposing chemical reaction, and steady detonation.

Surrogate multi-objective optimization of missile RCS performance in hypersonic rarefied flow of the near space

This study focuses on optimizing the lateral jet efficiency of THAAD-like (Terminal High Altitude Area Defense) missiles operating under hypersonic rarefied flow conditions. We employ the DSMC-QK algorithm to simulate the three-dimensional lateral jet flow field, accounting for thermochemical non-equilibrium effects. The analysis investigates how the force/momentum amplification coefficient varies with the angle of attack, jet pressure ratio, jet Mach number, and jet gas composition. Subsequently, we develop an artificial neural network (ANN) proxy model using the pyrenn toolbox, achieving an average prediction error of 0.866% and a maximum error of 1.60%. Utilizing this ANN model, we perform single- and multi-objective optimizations with a genetic algorithm to determine the optimal jet parameters. The results reveal that in multi-objective optimization, the proportion of helium in the jet gas composition increases, leading to a slight reduction in the force amplification coefficient but a substantial 61.4% decrease in the mass flow rate. This demonstrates that a judicious selection of jet gas composition can significantly reduce mass flow while maintaining high jet efficiency, thus achieving efficient lateral jet control.

The unreasonable effectiveness of equilibrium gene regulation through the cell cycle

Systems like the prototypical lac operon can reliably hold repression of transcription upon DNA replication across cell cycles with just 10 repressor molecules per cell and behave as if they were at equilibrium. The origin of this phenomenology is still an unresolved question. Here, we develop a general theory to analyze strong perturbations in quasi-equilibrium systems and use it to quantify the effects of DNA replication in gene regulation. We find a scaling law linking actual with predicted equilibrium transcription via a single kinetic parameter. We show that even the lac operon functions beyond the physical limits of naive regulation through compensatory mechanisms that suppress non-equilibrium effects. Synthetic systems without adjuvant activators, such as the cAMP receptor protein (CRP), lack this reliability. Our results provide a rationale for the function of CRP, beyond just being a tunable activator, as a mitigator of cell cycle perturbations.

Implementation and validation of a generalized wall stress function

The generalized wall function by Shih et al. [Report No. M-1999-209398 (1999)], which accounts for non-equilibrium effects by the presence of favorable and adverse pressure gradients in turbulent flows, is addressed with the aim of performing high Reynolds number large-eddy simulations of the wall-bounded flow. The model uses a corrected law of the wall with a pressure gradient contribution to approximate the wall stress and applies to the entire viscous layer, buffer layer, and inertial region. A fully developed channel flow is first tested to validate the solver and model implementation, and then the wall function is assessed for the flow over a periodic hill. Wall-resolved simulations are in good agreement with reference results. A priori investigation with own experimental results corroborates the mathematical form of the model and suggests using different coefficients. The wall-modeled simulations show that the implemented wall model is able to improve the wall shear stress predictions compared to a standard equilibrium wall model. It corrects the underestimation of wall shear stresses by equilibrium models in the favorable pressure gradient region and the overestimation of wall shear stresses in the adverse pressure gradient region. The positions of the separation and reattachment points are also in good agreement with reference results. Furthermore, the prediction of the wall shear stress maximum in the favorable pressure gradient zone at the windward side of the hill is quite robust against coarsening the wall-normal grid spacing.

Thermo-chemical nonequilibrium effects on combustion characteristics of a transverse jet in the scramjet

As the Mach number increases, the local static temperature gradually approaches the characteristic gas vibration/dissociation temperature, and significant thermo-chemical relaxation processes occur. The thermo-chemical nonequilibrium phenomenona could affect the mixing and combustion process and become a factor that must be considered for scramjet design. In this paper, a large eddy simulation solver based on the two-temperature model is developed. The transfer terms between vibrational and trans-rotational energy are modeled by the Landau–Teller formulation and the vibrational-dissociation coupling is considered by adopting the Park model. Three sets of simulations based on the Hyshot Ⅱ engine configuration with different models were performed simultaneously to validate numerical methods and analyze results. The results reveal that the shock, cross-injection of fuel, and Prandtl-Meyer flow induce significant nonequilibrium regions. The vibration relaxation process in the jet mixing region is frozen, the vibration temperature is much higher than the trans-rotational temperature, and the extra energy is converted from the vibration mode to the trans-rotational mode, resulting in the increase of the trans-rotational temperature and the advance of auto-ignition in the nonequilibrium condition. Considering the vibration-dissociation coupling, the higher vibration temperature promotes dissociation. It inhibits the generation of active radicals in the ignition process, weakening the enhancement effect of nonequilibrium on auto-ignition. In the expanded nozzle, the concentrations of molecules and trans-rotational temperature in nonequilibrium cases are slightly lower than those in the equilibrium case due to the enhancement of dissociation.

Numerical simulation of Darcy–Forchheimer flow of Casson ternary hybrid nanofluid with melting phenomena and local thermal non-equilibrium effects

The Casson fluid flow over a stretching sheet is studied in this work in the presence of porous media with melting heat transfer and chemical reaction, combining nanoparticles of Ti4Al6V,AA7072 and AA7075 with a base fluid of sodium alginate (NaAlg). The porous medium Darcy Forchheimer effect is included in the momentum equation. Through the effects of melting, the process of heat transfer is described. In order to explore the features of heat transmission in the absenteeism of LTECs (local thermal equilibrium conditions), the current study employs a mathematical model that has been simplified. For both the solid and liquid phases, the LTNE model yields two different fundamental thermal gradients. This proposed model compares the YOM (Yamada-Ota model) and XM (Xue model), two well-known trihybrid nanofluid models, in terms of performance. After applying the proper transformations, modulated non-linear PDEs (partial differential equations) are simplified in ODEs (ordinary differential equations) and the bvp4c method is used to solve them numerically. A graphic discussion of the relevant factors' significance on the pertinent fields has been presented. It is observed that the Casson ternary hybrid nanofluid temperature and velocity distributions predominate at higher melting parameter. The solid phase's heat transport rate rises with an upsurge in the interphase heat transfer parameter.

A computational study of solidification kinetics in multicomponent alloys

Recent advances in materials processing technologies highlight the need to understand solidification kinetics in multicomponent alloys. Using a finite interface dissipation phase field model, we investigate planar front solidification rates in ternary alloys, used as a model system, as a function of various mass transport processes and nonequilibrium conditions. Simulation results reveal that the off-diagonal diffusion coefficients play an important role in controlling the solid–liquid (S–L) interface velocity and solute partition coefficients. Specifically, under various rapid solidification conditions negative values for the off-diagonal diffusion coefficients increase the solute partition coefficients due to the depletion of liquid phase concentrations ahead of the S–L interface. Given an undercooling, the S–L interface velocity increases with decreasing the off-diagonal diffusion coefficients. In broad terms, our work quantifies the role of coupled mass transport processes and nonequilibrium effects in solidification rates of multicomponent alloys.

Entangled two-photon quantum heat engine: Dissipative nonequilibrium dynamics and correlated statistics

Recently, the thermodynamics of open quantum systems driven by light fields has been investigated in the framework of quantum heat engines, whose output work can be measured as a spectroscopic signal. In this work, we investigate a four-level quantum heat engine that generates cascaded entangled photon pairs, treating the hot bath as an incoherent thermal pump and focusing on the correlation statistics of the output work and photon indistinguishability. We show that the dissipative nonequilibrium dynamics of this thermodynamic open quantum system can be reconstructed by correlation measurements under carefully mediated optical control. Comparing our findings with the traditional coherently pumped model, we find that the thermal pumping has the potential to generate nonclassical correlations resulting in photon indistinguishability, displaying an advantage in probing the nonequilibrium effects induced by the baths at different temperatures. Our work also demonstrates that incoherent pumping can optimize such correlations in output work beyond the classical limit. Lastly, we show that nonclassical correlations and resonant power at steady state cannot be simultaneously maximized in the weak coupling regime. Published by the American Physical Society 2024

Variance sum rule: proofs and solvable models

We derive, in more general conditions, a recently introduced variance sum rule (VSR) (Di Terlizzi et al 2024 Science 383 971) involving variances of displacement and force impulse for overdamped Langevin systems in a nonequilibrium steady state (NESS). This formula allows visualising the effect of nonequilibrium as a deviation of the sum of variances from normal diffusion 2Dt, with D the diffusion constant and t the time. From the VSR, we also derive formulas for the entropy production rate σ that, differently from previous results, involve second-order time derivatives of position correlation functions. This novel feature gives a criterion for discriminating strong nonequilibrium regimes without measuring forces. We then apply and discuss our results to three analytically solved models: a stochastic switching trap, a Brownian vortex, and a Brownian gyrator. Finally, we compare the advantages and limitations of known and novel formulas for σ in an overdamped NESS.

Freeze out of multi-mode Richtmyer–Meshkov instability using particles

Richtmyer–Meshkov instability (RMI) occurs when a shock wave traverses an interface separated by two fluids with different densities. Achieving “freeze out” (i.e., “killing” of RMI), a critical objective in RMI research for engineering applications, remains an open problem in the context of multi-mode RMI. Here, we introduce particles into the flow field to achieve freeze out, which is attributed to the momentum non-equilibrium effect inherent in the gas–particle phases. This effect facilitates the transfer of momentum and energy from the fluid to the particles, thereby mitigating the amplification of initial perturbations within the mixing zone. We developed a one-dimensional model to predict the velocities of the mixing zone boundaries in multiphase RMI. The growth of RMI was suppressed by controlling the velocities of the mixing zone boundaries through particle effects. A non-dimensional freeze out criterion was derived, incorporating the gas–particle coupling along with the particle volume fraction effect. The condition for freezing a multi-mode RMI was specially designed to estimate the required particle volume fraction to achieve the freeze out. A series of simulations were conducted using a well-verified compressible multiphase particle-in-cell method to validate the realization of freeze out. Further analysis reveals that the designed condition exhibits applicability across a spectrum of multi-mode perturbations, including both broadband and narrowband perturbations, as well as various initial Mach numbers.

Numerical investigation of thermochemical non-equilibrium effects in Mach 10 scramjet nozzle

AbstractHigh-temperature non-equilibrium effects are prominent in scramjet nozzle flows at high Mach numbers. Hence, the thermochemical non-equilibrium gas model incorporating the vibrational relaxation process of molecules in the hydrocarbon-air reaction is developed to numerically simulate the flow of a hydrocarbon fuel scramjet nozzle at Mach 10. Besides, the results computed by the models of the thermally perfect gas, chemically non-equilibrium gas, and thermally non-equilibrium chemically frozen gas are applied for comparative studies. Results indicate that chemical non-equilibrium effects are more significant for the flow-field structure and parameters compared to thermal non-equilibrium effects. Meanwhile, vibrational relaxation and chemical reactions interact in the flow-field. The heat released from the chemical reactions in the flow-field of the thermochemical non-equilibrium gas model makes the thermal non-equilibrium effects weaker compared to the thermally non-equilibrium chemically frozen gas model; the chemical reactions in the thermochemical non-equilibrium gas model are more intense than in the chemically non-equilibrium gas model. Due to the slow relaxation of vibrational energy, the thermal non-equilibrium models predicted nozzle thrust lower than the thermal equilibrium models by approximately 1.11% to 1.33%; when considering the chemical reactions, the chemical non-equilibrium models predicted nozzle thrust higher than the chemical frozen models by approximately 7.30% to 7.54%. Hence, the structural design and performance study of the high Mach numbers scramjet nozzle must consider thermochemical non-equilibrium effects.

Numerical investigation on transpiration cooling with phase change based on multiphysics coupled finite element method

Transpiration cooling with phase change is an efficient active thermal protection method in aerospace. However, conducting numerical simulation of transpiration cooling with phase change is still a challenge, because porous flow, heat transfer and phase change are coupled with each other, which lead to numerical difficulties. In this article, the previous model is modified and the Zero Thickness Area Model (ZTAM) is proposed, which improves the efficiency and convergence significantly. In addition, the local thermal nonequilibrium effect and latent heat can be considered. To verify this ZTAM model, one-dimensional control equations of mass, momentum, and energy transpiration are solved using finite element method. Furthermore, the position of phase change is determined by fixed point iteration numerical algorithm, which shows good convergence. Finally, the influence on cooling effect by heat flux, coolant mass flow rate, porosity and pore diameter is investigated numerically.

On the second law of thermodynamics: A global flow spontaneously induced by a locally nonchaotic energy barrier

It is well known that, inherently, certain small-scale nonchaotic particle movements are not governed by thermodynamics. Usually, such phenomena are studied by kinetic theory and their energy properties are considered “trivial”. In current research, we show that, beyond the boundaries of the second law of thermodynamics where Boltzmann’s H-theorem does not apply, there may also be large-sized systems of nontrivial energy properties: when the system is isolated, entropy can decrease; from a single thermal reservoir, the system can absorb heat and produce useful work without any other effect. The key concept is local nonchaoticity, demonstrated by using a narrow energy barrier. The barrier width is much less than the nominal particle mean free path, so that inside the barrier, the particle-particle collisions are sparse and the particle trajectories tend to be locally nonchaotic. Across the barrier, the steady-state particle flux ratio is intrinsically in a non-Boltzmann form. With a step-ramp structure, the nonequilibrium effect spreads to the entire system, and a global flow is generated spontaneously from the random thermal motion. The deviation from thermodynamic equilibrium is steady and significant, and compatible with the basic principle of maximum entropy. These theoretical and numerical analyses may shed light on the fundamentals of thermodynamics and statistical mechanics.

Characterization of near-wall flow and in-cylinder free-stream turbulence during the intake phase of a direct-injection engine: A flow bench study

This study investigates the characteristics of the near-wall flow and pressure-induced wall-influenced turbulence inside a direct-injection engine during the intake phase by utilizing a wall-resolved Large Eddy Simulation. An engine flow bench operating under stationary conditions is used to reduce the complexity of engine flows and to shed light on the in-cylinder flow during the intake phase. The investigation focuses on in-cylinder turbulence on symmetry (SP) and valve planes (VP), particularly emphasizing the flow close to the intake valves and the impingement region on the liner wall. An experimental dataset acquired through 2D high-speed particle image velocimetry (PIV) facilitates validation of the simulation of both time-averaged velocity field and associated turbulence structure. Turbulence anisotropy analysis shows that, in complex wall-bounded flows, the IC engine-related in-cylinder turbulence structure is characterized by the anisotropic states that cope with both axisymmetric expansion and contraction straining events. Due to the strong influence of the intake flow, the turbulence anisotropy level, expressed in terms of the two-componentality parameter F, retains its value of less than 0.85, and no turbulence occurs in accordance with the fully three-component isotropic state, characterized by the F-parameter value of 1. In the vicinity of the intake valve near wall area, the turbulence anisotropy state transitions from that resembling a canonical channel flow characteristic to curvature-induced acceleration after impingement, which aligns with axisymmetric expansion in the anisotropy invariant map. The presence of intake flow sustains turbulence anisotropy. Limitations in applying wall-function treatments for near-wall flow in engine contexts due to simplifications, such as the zero-pressure gradient assumption, are highlighted. In this respect, the interplay of non-equilibrium effects in the near-wall region needed to be further explored. Accordingly, analysis of the viscosity-affected layer near the intake valve and the flow impingement area of the liner wall underscores the importance of the wall-tangential pressure gradient in shaping the near-wall behavior. A budget analysis of the turbulent kinetic energy equation at the intake valve emphasizes the dominance of fluctuating pressure-induced diffusive transport in turbulence generation.

Single-Step Control of Liquid-Liquid Crystalline Phase Separation by Depletion Gradients.

Fine-tuning nucleation and growth of colloidal liquid crystalline (LC) droplets, also known as tactoids, is highly desirable in both fundamental science and technological applications. However, the tactoid structure results from the trade-off between thermodynamics and nonequilibrium kinetics effects, and controlling liquid-liquid crystalline phase separation (LLCPS) in these systems is still a work in progress. Here, a single-step strategy is introduced to obtain a rich palette of morphologies for tactoids formed via nucleation and growth within an initially isotropic phase exposed to a gradient of depletants. The simultaneous appearance is shown of rich LC structures along the depleting potential gradient, where the position of each LC structure is correlated with the magnitude of the depleting potential. Changing the size (nanoparticles) or the nature (polymers) of the depleting agent provides additional, precise control over the resulting LC structures through a size-selective mechanism, where the depletant may be found both within and outside the LC droplets. The use of depletion gradients from depletants of varying sizes and nature offers a powerful toolbox for manipulation, templating, imaging, and understanding heterogeneous colloidal LC structures.

Instantaneous Marcus theory for photoinduced charge transfer dynamics in multistate harmonic model systems

Modeling the dynamics of photoinduced charge transfer (CT) in condensed phases presents challenges due to complicated many-body interactions and the quantum nature of electronic transitions. While traditional Marcus theory is a robust method for calculating CT rate constants between electronic states, it cannot account for the nonequilibrium effects arising from the initial nuclear state preparation. In this study, we employ the instantaneous Marcus theory (IMT) to simulate photoinduced CT dynamics. IMT incorporates nonequilibrium structural relaxation following a vertical photoexcitation from the equilibrated ground state, yielding a time-dependent rate coefficient. The multistate harmonic (MSH) model Hamiltonian characterizes an organic photovoltaic carotenoid-porphyrin-fullerene triad dissolved in explicit tetrahydrofuran solvent, constructed by mapping all-atom inputs from molecular dynamics simulations. Our calculations reveal that the electronic population dynamics of the MSH models obtained with IMT agree with the more accurate quantum-mechanical nonequilibrium Fermi’s golden rule. This alignment suggests that IMT provides a practical approach to understanding nonadiabatic CT dynamics in condensed-phase systems.

Numerical investigations on flow and heat transfer characteristics of a high-enthalpy double-cone in thermal and chemical non-equilibrium for hypersonic propulsion

There are strong interests in hypersonic propulsion communities in predicting the flow and heat transfer characteristics over a hypersonic vehicle. However, this is quite challenging due to the emergence of thermal and chemical out-of-equilibrium effects as prominent in a high-temperature flow. In this work, we conduct 2D numerical investigations on the hypersonic double cone flow in a surrounding of the stagnation enthalpy of 15.23 MJ/kg by solving the laminar Navier–Stokes equation systems with the vibrational non-equilibrium processes and seven species air reactions. We then conduct the sensitivities analyses on the flow and heat transfer features, as different transport models and different thermochemical models are applied. It is shown that the aerodynamic heat is more sensitive to the transport models than the flow, and the transport coefficients computed by the Gupta-Yos model are more suitable for predicting the double cone flow at the high enthalpy. On the other hand, the flow field of the high enthalpy double cone is more sensitive to the thermochemical models than the heat transfer on the wall excluding the peak position. Behind the detached shock, chemical reactions are found to enhance thermal or vibrational out-of-equilibrium effects. However, vibrational non-equilibrium effects are revealed to weaken the degree of molecule dissociation reactions. Two flow separations occur in the flow field computed by using the thermal non-equilibrium gas models, but the flows of thermal equilibrium gas models separate only once. The maximum values of wall parameters without chemical reactions are found to deviate greatly from the experimental measurements. The thermochemical out-of-equilibrium gas model can predict the separation region size closer to the experiment than the two reported numerical results. The wall static pressure and heat flux are also shown to well match the experimental results. The present work should shed lights on better understanding thermochemical non-equilibrium effects of complex flow phenomenon like the shock wave/boundary layer interaction in hypersonic propulsion with high enthalpy surroundings.