arXiv subjects

Signe Kjelstrup

Publications and source records attributed to Signe Kjelstrup.

At least 19 recordsLinked to original sources

arXiv2025

From Interface Dynamics to Darcy Scale Description of Multiphase Flow in Porous Media

An outstanding characteristic of porous media, desired in many applications, is the large surface area, which facilitates solid-fluid interactions, making porous media an extreme case in colloid and interface science. In two-fluid systems, wetting and the balance of capillary and viscous forces control fluid displacement processes, leading to a wide range of complex flow regimes with rich spatio-temporal dynamics. Macroscopic two-phase flow is historically described through the phenomenological extensions of Darcy's law. Besides many other shortcomings and inconsistencies, it covers only connected pathway flow in the capillary-dominated flow regime in a rigorous manner while other flow regimes with moving interfaces and associated topological changes are entirely implicit. Given the lack of adequate descriptions, upscaling multiphase flow from pore to Darcy scale represents a long-standing challenge paving into the fields of thermodynamics, statistical mechanics and integral geometry. In this review, we compare novel concepts which have been largely motivated by experimental insights, enabled by significant advances in pore-scale imaging and modeling over the last decade.

physics.flu-dyn↗

arXiv2025

Fluctuation-dissipation theorems for multi-phase flow with memory in porous media

Recent works have reported on the collective behavior of multiphase systems under fractional flow. Such behavior has been linked to pressure and/or flux fluctuations under stationary flow conditions that occur over a broad range of resonance frequencies and associated relaxation times. However, there currently exists no theoretical development to deal with such phenomena. The aim of this paper is to develop a fundamental theory that can describe such behavior. Fluctuation-dissipation theorems for the case with memory are formulated, providing a new route to obtain frequency-dependent porous media permeability. We propose that multiphase flow systems can be explained by a multipeak Lorentzian memory function and provide supporting experimental data from the flow of decane and water in a porous medium made of glass beads. Our fluctuation dissipation theorems provide information on different types of relaxation phenomena and resonance frequencies that occur during fractional flow. We show, using experimental data, that Green-Kubo-like expressions can be formulated for two-phase fluid flow driven by a constant pressure drop. The resulting autocorrelation functions, or rather their Fourier transforms, exhibit multiple Lorentzian peak shapes. Resonances are similar to those of electric conductance. The analysis offers a new route to steady-state relative permeability measurements, including information on the relaxation times and resonance regimes that exist during fractional flow. Overall, the theory presented and supported by fractional flow experiments provides a rich set of possible directions for future developments that could fundamentally change the way multiphase flow systems are understood and studied.

physics.flu-dyn↗

arXiv2024

Lithium-ion battery modelling for nonisothermal conditions

A nonequilibrium thermodynamic model is presented for the nonisothermal lithium-ion battery cell. Coupling coefficients, all significant for transport of heat, mass, charge and chemical reaction, were used to model profiles of temperature, concentration and electric potential for each layer of the cell. Electrode surfaces were modelled with excess properties. Extending earlier works, we included lithium diffusion in the electrodes, and explained the cell's thermal signature due to Peltier and Soret effects. We showed that the model is consistent with the second law of thermodynamics, meaning that the entropy production computed at steady state from entropy fluxes is equal to the integral over the sum of flux-force products. The procedure is beneficial in electrochemical cell modelling as it reveals inconsistencies. The model was solved for typical lithium-ion battery materials. The coupling coefficients for transport of salts and solvents lead to significant concentration polarization. Thermal polarization is then negligible. We show that a zero-valued heat flux is not necessarily synonymous with a zero temperature gradient. Results are important for efforts that aim to avoid local hot spots. A program code is made available for testing and applications. The program is designed to solve dynamic boundary value problems posed by the electrode surfaces.

physics.chem-ph↗

arXiv2024

Fluctuation-dissipation theorems and the measurement of the Onsager coefficients for two-phase flow in porous media

We propose a new methodology for the experimental measurement of the Onsager coefficients of porous media flows by application of the fluctuation-dissipation theorem. The experimental setup consists of a steady-state flow condition in which two incompressible fluids are simultaneously injected into a modified Hele-Shaw cell. The cell is transparent and allows direct visualization of the dynamics via regular optical imaging methods. The fluctuations in the phase saturations are obtained and, by computing the temporal correlations of their time derivatives, we gain access to the Onsager coefficients. This work gives experimental grounding to recent theoretical development on the applications of the fluctuation-dissipation theorems to porous media flows.

physics.flu-dyn↗

arXiv2022

Local thermodynamic description of isothermal single-phase flow in porous media

Darcy's law for porous media transport is given a new local thermodynamic basis in terms of the grand potential of confined fluids. The local effective pressure gradient is determined using non-equilibrium molecular dynamics, and the hydraulic conductivity and permeability are investigated. The transport coefficients are determined for single-phase flow in face-centered cubic lattices of solid spheres. The porosity changed from that in the closest packing of spheres to near unity in a pure fluid, while the fluid mass density varied from that of a dilute gas to a dense liquid. The permeability varied between \SI{5.7e-20}{\meter^2} and \SI{5.5e-17}{\meter^2}, showing a porosity-dependent Klinkenberg effect. Both transport coefficients depended on the average fluid mass density and porosity but in different ways. These results set the stage for a non-equilibrium thermodynamic investigation of coupled transport of multi-phase fluids in complex media.

physics.chem-ph↗

arXiv2022

Defining the pressures of a fluid in a nanoporous, heterogeneous medium

We describe the thermodynamic state of a single-phase fluid confined to a porous medium with Hill's thermodynamics of small systems, also known as nanothermodynamics. This way of defining small system thermodynamics, with a separate set of control variables, may be useful for the study of transport in non-deformable porous media, where presently no consensus exists on pressure computations. For a confined fluid, we observe that there are two pressures, the integral and the differential pressures. We use molecular simulations to investigate and confirm the nanothermodynamic relations for a representative elementary volume (REV). For a model system of a single-phase fluid in a face-centered cubic lattice of solid spheres of varying porosity, we calculate the fluid density, fluid-solid surface tension, replica energy, integral pressure, entropy, and internal energy.

physics.chem-ph↗

arXiv2021

Legendre-Fenchel transforms capture layering transitions in porous media

We have investigated the state of a nanoconfined fluid in a slit pore in the canonical and isobaric ensembles. The systems were simulated with molecular dynamics simulations. The fluid has a transition to a close-packed structure when the height of the slit approaches the particle diameter. The Helmholtz energy is a non-convex function of the slit height if the number of particles does not exceed that of one monolayer. As a consequence, the Legendre transform cannot be applied to obtain the Gibbs energy. The Gibbs energy of a non-deformable slit pore can be transformed into the Helmholtz energy of a deformable slit pore using the Legendre-Fenchel transform. The Legendre-Fenchel transform corresponds to the Maxwell construction of equal areas.

physics.chem-ph↗

arXiv2021

Theory and simulation of shock waves: Entropyproduction and energy conversion

We have considered a shock wave as a surface of discontinuity and computed the entropy production using non-equilibrium thermodynamics for surfaces. The results from this method, which we call the "Gibbs excess method" (GEM), were compared with results from three alternative methods, all based on the entropy balance in the shock front region, but with different assumptions about local equilibrium. Non-equilibrium molecular dynamics (NEMD) simulations were used to simulate a thermal blast in a one-component gas consisting of particles interacting with the Lennard-Jones/spline potential. This provided data for the theoretical analysis. Two cases were studied, a weak shock with Mach number $M \approx 2$ and a strong shock with $M \approx 6$ and with a Prandtl number of the gas $Pr \approx 1.4$ in both cases. The four theoretical methods gave consistent results for the time-dependent surface excess entropy production for both Mach numbers. The internal energy was found to deviate only slightly from equilibrium values in the shock front. The pressure profile was found to be consistent with the Navier-Stokes equations. The entropy production in the weak and strong shocks were approximately proportional to the square of the Mach number and decayed with time at approximately the same relative rate. In both cases, some 97 \% of the total entropy production in the gas occurred in the shock wave. The GEM showed that most of the shock's kinetic energy was converted reversibly into enthalpy and entropy, and a small amount was dissipated as produced entropy. The shock waves traveled at almost constant speed and we found that the overpressure determined from NEMD simulations agreed well with the Rankine-Hugoniot conditions for steady-state shocks.

physics.flu-dyn↗

arXiv2020

Nanothermodynamic description and molecular simulation of a single-phase fluid in a slit pore

We describe the thermodynamic state of a highly confined single-phase and single-component fluid in a slit pore using Hill's thermodynamics of small systems. This theory was more recently named nanothermodynamics. We start by constructing an ensemble of slit pores for controlled temperature, volume, surface area, and chemical potential. We present the integral and differential properties according to Hill, and use them to define the disjoining pressure. We identify all thermodynamic pressures by their mechanical counterparts in a consistent manner, and investigate the identification by molecular dynamics simulations. We define and compute the disjoining pressure, and show that it contains the standard definition. We compute the entropy and energy densities, and find in agreement with the literature, that the forces at the wall are of an energetic, not entropic nature. The subdivision potential is zero for this slit pore with large walls, but unequal to zero for related sets of control variables. We show how Hill's method can be used to find new Maxwell relations of a confined fluid, in addition to a scaling relation, which applies when the walls are separated far enough. By this expansion of nanothermodynamics, we set the stage for further developments of the thermodynamics of confined fluids, a field that is central in nanotechnology.

physics.chem-ph↗

arXiv2020

Nonequilibrium thermodynamics of surfaces captures the energy conversions in a shockwave

The local entropy production in a shock wave was analysed in the framework of non-equilibrium thermodynamics (NET) of surfaces. We show that the thermodynamic state variables in the shock front are equal to their equilibrium values, despite lack of global equilibrium in the dense gas. This observation was used to develop a theory for the entropy production in a shock wave using Gibbs' surface excess properties. The theoretical results were compared with a numerical evaluation of the entropy balance for the shock front and confirmed by non-equilibrium molecular dynamics (NEMD) simulations. The NET analysis shows that the dominant contribution to the entropy production is the dissipation of kinetic and compression energy. This opens the door to accurate representations of energy conversions in shock waves.

physics.flu-dyn↗

arXiv2020

Onsager-Symmetry Obeyed in Athermal Mesoscopic Systems: Two-Phase Flow in Porous Media

We compute the fluid flow time-correlation functions of incompressible, immiscible two-phase flow in porous media using a 2D network model. Given a properly chosen representative elementary volume, the flow rate distributions are Gaussian and the integrals of time correlation functions of the flows are found to converge to a finite value. The integrated cross-correlations become symmetric, obeying Onsager's reciprocal relations. These findings support the proposal of a non-equilibrium thermodynamic description for two-phase flow in porous media.

physics.flu-dyn↗

arXiv2018

Pressures inside a nano-porous medium. The case of a single phase fluid

We define the pressure of a porous medium in terms of the grand potential, and compute its value in a nano-confined or nano-porous medium, meaning a medium where thermodynamic equations need be adjusted for smallness. On the nano-scale, the pressure depends in a crucial way on the size and shape of the pores. According to Hill, two pressures are needed to characterize this situation; the integral pressure and the differential pressure. Using Hill's formalism for a nano-porous medium, we derive an expression for the difference between the integral and the differential pressures in a spherical phase $\alpha$ of radius $R$, $\hat{p}^\alpha-p^\alpha = {\gamma}/{R}$. We recover the law of Young-Laplace for the differential pressure difference across the same curved surface. We discuss the definition of a representative volume element for the nano-porous medium and show that the smallest REV is half a unit cell in the direction of the pore in the fcc lattice. We also show, for the first time, how the pressure profile through a nano-porous medium can be defined and computed away from equilibrium.

physics.comp-ph↗

arXiv2018

Non-isothermal transport of multi-phase fluids in porous media. Constitutive equations

We develop constitutive equations for multi-component, multi-phase, macro-scale flow in a porous medium exposed to temperature-, composition-, and pressure -gradients. The porous medium is non-deformable. We define the pressure and the composition of the representative elementary volume (REV) in terms of the volume and surface averaged pressure and the saturation, and the respective driving forces from these variables. New contributions due to varying porosity or surface tension offer explanations for non-Darcy behavior. The interaction of a thermal and mechanical driving forces give thermal osmosis. An experimental program is suggested to verify Onsager symmetry in the transport coefficients.

physics.flu-dyn↗

arXiv2018

Hill's nano-thermodynamics is equivalent with Gibbs' thermodynamics for curved surfaces

We review first how properties of curved surfaces can be studied using Hill's thermodynamics, also called nano-thermodynamics. We proceed to show for the first time that Hill's analysis is equivalent to Gibbs for curved surfaces. This simplifies the study of surfaces that are curved on the nano-scale, and opens up a possibility to study non-equilibrium systems in a systematic manner.

physics.chem-ph↗

arXiv2018

Non-isothermal transport of multi-phase fluids in porous media. The entropy production

We derive the entropy production for transport of multi-phase fluids in a non-deformable, porous medium exposed to differences in pressure, temperature, and chemical potentials. Thermodynamic extensive variables on the macro-scale are obtained by integrating over a representative elementary volume (REV). Using Euler homogeneity of the first order, we obtain the Gibbs equation for the REV. From this we define the intensive variables, the temperature, pressure and chemical potentials and, using the balance equations, derive the entropy production for the REV. The entropy production defines sets of independent conjugate thermodynamic fluxes and forces in the standard way. The transport of two-phase flow of immiscible components is used to illustrate the equations.

physics.flu-dyn↗

arXiv2018

Stable and efficient time integration of a dynamic pore network model for two-phase flow in porous media

We study three different time integration methods for a dynamic pore network model for immiscible two-phase flow in porous media. Considered are two explicit methods, the forward Euler and midpoint methods, and a new semi-implicit method developed herein. The explicit methods are known to suffer from numerical instabilities at low capillary numbers. A new time-step criterion is suggested in order to stabilize them. Numerical experiments, including a Haines jump case, are performed and these demonstrate that stabilization is achieved. Further, the results from the Haines jump case are consistent with experimental observations. A performance analysis reveals that the semi-implicit method is able to perform stable simulations with much less computational effort than the explicit methods at low capillary numbers. The relative benefit of using the semi-implicit method increases with decreasing capillary number $\mathrm{Ca}$, and at $\mathrm{Ca} \sim 10^{-8}$ the computational time needed is reduced by three orders of magnitude. This increased efficiency enables simulations in the low-capillary number regime that are unfeasible with explicit methods and the range of capillary numbers for which the pore network model is a tractable modeling alternative is thus greatly extended by the semi-implicit method.

physics.comp-ph↗

arXiv2017

Relations between Seepage Velocities in Immiscible, Incompressible Two-Phase Flow in Porous Media

Based on thermodynamic considerations we derive a set of equations relating the seepage velocities of the fluid components in immiscible and incompressible two-phase flow in porous media. They necessitate the introduction of a new velocity function, the co-moving velocity. This velocity function is a characteristic of the porous medium. Together with a constitutive relation between the velocities and the driving forces, such as the pressure gradient, these equations form a closed set. We solve four versions of the capillary tube model analytically using this theory. We test the theory numerically on a network model.

physics.flu-dyn↗

arXiv2016

A Monte Carlo Algorithm for Immiscible Two-Phase Flow in Porous Media

We present a Markov Chain Monte Carlo algorithm based on the Metropolis algorithm for simulation of the flow of two immiscible fluids in a porous medium under macroscopic steady-state conditions using a dynamical pore network model that tracks the motion of the fluid interfaces. The Monte Carlo algorithm is based on the configuration probability, where a configuration is defined by the positions of all fluid interfaces. We show that the configuration probability is proportional to the inverse of the flow rate. Using a two-dimensional network, advancing the interfaces using time integration the computational time scales as the linear system size to the fourth power, whereas the Monte Carlo computational time scales as the linear size to the second power. We discuss the strengths and the weaknesses of the algorithm.

physics.flu-dyn↗