Nanoporous Media Research Articles

Flow prediction of heterogeneous nanoporous media based on physical information neural network

The simulation and prediction of fluid flow in porous media play a profoundly significant role in today's scientific and engineering domains, particularly in gaining a deeper understanding of phenomena such as the migration and fluid flow in underground rock formations and the enhancement of oil recovery rates. The flow of fluids in nanoscale porous media requires consideration of the effects of microscale phenomena, which are challenging to accurately describe using traditional physical models. Currently, research in deep learning for porous media predominantly focuses on conventional porous media, and there is an urgent need for investigations into heterogeneous nanoporous media. Simultaneously, there is a necessity to overcome the limitations of traditional data-driven models lacking physical prior knowledge. Therefore, the integration of physics-informed neural networks, which combine deep learning with physical principles, becomes essential for inferring relatively accurate results from sparse data. In this work, based on the heterogeneity of porous media in shale, we have introduced a deep learning model that couples physical information to predict the flow in heterogeneous nanoscale porous media. In the Physical Information Neural Network model, we utilize point clouds and couple them with deep residual networks. Discrete sampling points are used as inputs, and a multi-level residual connection, along with dimension concatenation, is employed to fuse feature information. The network, through backpropagation, takes into account the Navier-Stokes equations and wall conditions in heterogeneous nanoscale porous media. The results indicate that the apparent permeability and pressure field accuracy are over 90% and 95%, respectively. The Physical Information Neural Network demonstrates promising prospects for predicting flow in nanoscale porous media. Future work will extend to the multiphase complex flow in three-dimensional porous media.

Giant Thermoelectric Response of Confined Electrolytes with Thermally Activated Charge Carrier Generation.

The thermoelectric response of thermally activated electrolytes (TAEs) in a slit channel is studied theoretically and by numerical simulations. The term TAE refers to electrolytes whose charge carrier concentration is a function of temperature, as recently suggested for ionic liquids and highly concentrated aqueous electrolyte solutions. Two competing mechanisms driving charge transport by temperature gradients are identified. For suitable values of the activation energy that governs the generation of charge carriers, a giant thermoelectric response is found, which could help explain recent experimental results for nanoporous media infiltrated with TAEs.

Study on CO2 and CH4 Competitive Adsorption in Shale Organic and Clay Porous Media from Molecular- to Pore-Scale Simulation

Summary The elucidation of the competitive adsorption behaviors between CO2 and CH4 holds great importance in the context of improving natural gas recovery in shale reservoirs. Shale rock, as a complex porous medium, exhibits a highly interconnected multiscale pore network with pore size spanning from several to tens of nanometers. Nevertheless, accurately capturing the adsorption effects and studying the CO2/CH4 competitive adsorption within a large-scale, realistic, 3D nanoporous matrix remains a significant challenge. In this paper, we proposed a novel lattice Boltzmann method (LBM) coupled molecular simulation to investigate CO2/CH4 competitive adsorption in 3D shale nanoporous media. The initial step involves conducting Grand Canonical Monte Carlo (GCMC) simulations to simulate the competitive adsorption behaviors of CO2 and CH4 in kerogen and illite slit pores, with the aim of obtaining the atomic density distribution. Subsequently, a Shan-Chen-based lattice Boltzmann (LB) simulation is used under identical conditions. By coupling the molecular simulation results, the fluid-solid interaction parameters are determined. Finally, LB simulations are performed in designed 3D porous media, utilizing the fluid-solid interaction parameters. The effects of mineral type, CO2 concentration, and pore structure on competitive adsorption behaviors are discussed carefully. Our research offers significant contributions to the improvement of gas recovery and carbon geological sequestration through the examination of CO2/CH4 competitive adsorption in nanoporous media. Additionally, it serves as a link between molecular and pore-scale phenomena by leveraging the benefits of both molecular simulations and pore-scale simulations.

Impact of hydraulic tortuosity on microporous and nanoporous media flow.

Using two-dimensional porous structures made up of homogeneously arranged solid obstacles, we examine the effects of rarefaction on the hydraulic tortuosity in the slip and early transition flow regimes via extended lattice Boltzmann method. We observed that modification in either the obstacle's arrangement or the porosity led to a power-law relation between the porosity-tortuosity. Along with this, we also found that in the slip-flow regime, the exponent of this relation contains the effect of finite Knudsen number (Kn). In addition, we observed that on properly scaling Kn with porosity and hydraulic tortuosity, a generalized correlation can be obtained for apparent permeability.

Drying in nanoporous media with Kelvin effect: Capillary imbibition against evaporation by smoothed particle hydrodynamics method

Understanding drying processes in nanoporous media is of great importance in many technological and industrial situations. To better understand how gas moves through clayey rocks, of interest for underground disposal of radioactive wastes, we propose using pore-scale direct numerical simulations. In this study, we use the Smoothed Particle Hydrodynamics method, which has proved to be an effective approach for simulating complex fluid dynamics within porous media at the nanoscale. Our simulations consider capillary-dominated two-phase flow with evaporation and condensation at liquid–gas interfaces, coupled to the diffusion of water vapor in the gas phase, as well as the Kelvin effect, which is a specific feature of nanopores. Our evaporation-condensation model is validated against analytical solutions. The size of the compact support of kernel function and the particle density required to obtain accurate and stable results of capillary pressure are investigated. Drying regimes, capillary-driven and evaporated-driven, are explored. A specific effort is made to highlight the influence of the Kelvin effect on desaturation and the creation of preferential paths for gas flow as well as its impact on drying rate. The role of condensation due to local vapor concentration conditions is also emphasized.

Experimental evaluation of cement integrity on exposure to supercritical CO2 using NMR: Application to geostorage

Carbon sequestration is one approach to achieve carbon dioxide reduction in the atmosphere. Underground storage of CO2 requires an understanding of geochemical and geomechanical alteration on the integrity of the injection wellbore. In this study, we investigate the reactivity of supercritical CO2 (scCO2) at 65 °C and 20.7 MPa on Portland class G cement plugs used for oil and gas well completion, for exposure of up to 5 weeks.For nanoporous media, such as cement, diffusion is believed to be the major mass transport mechanism (Perkins and Johnston, 1963) [1]. To quantify the extent of the alteration (mineralization/dissolution) on fluid diffusivity through the cement matrix, a novel approach based on Nuclear Magnetic Resonance (NMR) is employed to derive diffusional tortuosity. Comparing pre- and post-scCO2 exposure, deuterium oxide (D2O) intrusion profiles allow us to determine flow path alteration in the cement plugs. Additional characterizations include Fourier Transform Infrared Spectroscopy (FTIR) to observe the change in cement composition, micro X-ray Computed Tomography (μXCT), along with Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) to determine invasion extent and microstructure modifications, Mercury Injection Capillary Pressure (MICP) for pore throat size distribution and BET N2 isothermal adsorption for surface area and pore size distribution.The results show that exposure to scCO2 promotes both calcium carbonate precipitation and dissolution simultaneously. However, the alteration is pore size dependent. After 5 weeks of exposure, there is evidence of carbonate dissolution in smaller pores (<30 nm) and both precipitation and dissolution in larger pores (30–200 nm). The alteration of the cement plugs leads to a decrease in the storage and connectivity of the cement. The porosity decreased from 37 to 33 % in 5 weeks, while the matrix tortuosity increased by 6 and 3 times after 2 and 5 weeks of exposure, respectively. The experimental results imply that the cement carbonate precipitation can limit the migration of scCO2 through the cement matrix.This work also highlights an alternative laboratory approach to quantify the risk associated with scCO2 exposure on Portland cement using NMR-derived tortuosity.

Unveiling nanoscale fluid miscible behaviors with nanofluidic slim-tube

Fluid miscible behaviors in nanoporous media are crucial for applications such as carbon capture, utilization, and storage (CCUS), membrane separation, subsurface pollutant remediation, and geothermal extraction. Confinement effects at the...

A novel ultra-high vacuum diffusion setup to study Knudsen diffusion

An ultra-high vacuum setup was conceived to study Knudsen diffusion in channels with varied geometrical characteristics that can be modified using 3D printing. This new experimental methodology aids to gain insight into diffusion in nanoporous media.

The effect of confinement on the phase behavior of propane in nanoporous media: an experimental study probing capillary condensation, evaporation, and hysteresis at varying pore sizes and temperatures.

Fundamental understanding of the phase behavior and properties of fluids under confinement is of great significance for multiple fields of engineering and science, as well as for many practical industrial applications. In particular, unconventional geological systems, such as shale reservoirs, possess nanometer-scale pores, which impose nanoconfinement on the fluid molecules. In large pores, the bulk phase behavior of fluids can be modeled by the well-established methods, such as equation of state (EOS) approaches. However, under confinement the thermodynamic properties of fluids deviate significantly from those in the bulk, thus rendering the traditional EOS methods ineffective in predicting the phase behavior of confined fluids. Recently, the PC-SAFT/Laplace EOS has been developed to better represent the fluid phase equilibria in nanopores, which incorporates a new parameter that needs to be determined from experimental data. In this study, a new dataset is presented to reflect the phase properties of propane confined within the MCM-41 pores, with the aim to improve both the general understanding of the phase behavior of hydrocarbons under confinement and to parameterize the PC-SAFT/Laplace EOS for the nanoconfined propane. For this purpose, propane adsorption and desorption isotherms are determined experimentally for a wide range of temperatures (-27 to 20 °C) in MCM-41 of three different pore sizes (nominal pore diameters of 60, 80, and 100 Å). The effects of temperature and pore diameter on the capillary condensation and evaporation pressures are discussed in detail. Furthermore, the adsorption-desorption hysteresis behavior and its progression for different pore sizes were discussed. The experimental data are modeled using the parameterized PC-SAFT/Laplace EOS, which accurately captured the effects of confinement on the capillary condensation of propane in MCM-41. In addition, this study enriches the field of nanoconfinement research by providing a new dataset exemplifying the thermodynamic characteristics of hydrocarbons in nanopores.

Phase behavior of n-hexane confined in unconsolidated nanoporous media: an experimental investigation at varying pore sizes and temperatures.

We investigated the effect of confinement on the phase behavior of hexane in nanopores of mesoporous silica at varying pore diameters and temperatures using a patented gravimetric apparatus. The adsorption and desorption isotherms were experimentally measured, and the capillary condensation and evaporation pressures were calculated from the isotherms. The results show that, for all pore sizes and temperatures utilized here, the confinement of fluids significantly lowers the vapor-liquid phase transition pressures. However, its evaporation, i.e., liquid-vapor phase transition, occurs at a lower pressure than its capillary condensation counterpart. The experimental findings demonstrate that the confinement effect becomes weaker in wider nanopores due to the reduced solid-fluid interactions in larger spaces. Furthermore, it is evident from isotherms that hexane rapidly approaches a supercritical-like state at high temperatures when confined in smaller pores, resulting in an ambiguous vapor-liquid phase transition. In contrast, this behavior disappears in larger pores at similar temperatures. Moreover, the present study compares the fully gravimetric adsorption method against the thermogravimetric approach. The results show that the fully gravimetric method, which directly measures the mass of the adsorbed or condensed fluids, provides significant advantages over the thermogravimetric counterpart. The findings of this study are expected to be of fundamental interest to a wide range of science and engineering communities concerned about the behavior of heavier hydrocarbons in various industrial applications, and modeling the confined phase behavior of fluids and developing robust equations of state (EOS).

Two-phase imbibition of water-oil displacement in silica nanochannels

Classical imbibition theory cannot describe imbibition flow dynamics in nanoporous media in tight reservoirs and other industrial applications. In this work, the two-phase imbibition flow of water-oil displacement in silica nanochannels is studied by using molecular dynamics simulations. Interestingly, it is found that the two-phase imbibition length is shown to increase linearly with increasing time, which is inconsistent with the variation of single-phase imbibition length. The imbibition rate increases with the increase of external driving force, and the large channel height can accelerate the two-phase imbibition flow. As the increase of chain length of alkane molecules, the imbibition rate reduces gradually. The more oil-wet the silica surface is, the slower the imbibition rate is. Furthermore, we derive a theoretical model to describe the two-phase imbibition flow of water-oil displacement in nanochannels by considering the static force equilibrium of external driving forces, capillary forces, and viscous forces of the water and oil phases. The theoretical model can well describe the two-phase imbibition flow under various conditions using the pre-calculated oil-water interfacial tension, the viscosity of fluids, and the three-phase contact angle. This study will enrich the theoretical understanding of oil-water two-phase flow at nanoscale.

Evaluation of Electron Tomography Capabilities for Shale Imaging.

Despite the advantageous resolution of electron tomography (ET), reconstruction of three-dimensional (3D) images from multiple two-dimensional (2D) projections presents several challenges, including small signal-to-noise ratios, and a limited projection range. This study evaluates the capabilities of ET for thin sections of shale, a complex nanoporous medium. A numerical phantom with 1.24 nm pixel size is constructed based on the tomographic reconstruction of a Barnett shale. A dataset of 2D projection images is numerically generated from the 3D phantom and studied over a range of conditions. First, common reconstruction techniques are used to reconstruct the shale structure. The reconstruction uncertainty is quantified by comparing overall values of storage and transport metrics, as well as the misclassification of pore voxels compared to the phantom. We then select the most robust reconstruction technique and we vary the acquisition conditions to quantify the effect of artifacts. We find a strong agreement for large pores over the different acquisition workflows, while a wider variability exists for nanometer-scale features. The limited projection range and reconstruction are identified as the main experimental bottlenecks, thereby suggesting that sample thinning, advanced holders, and advanced reconstruction algorithms offer opportunities for improvement.

High-Performance Methods of Modeling the Nano-Adsorption and Diffusion with Feedback in Heterogeneous Cylindrical Multicomponent Nanoporous Media

High-Performance Methods of Modeling the Nano-Adsorption and Diffusion with Feedback in Heterogeneous Cylindrical Multicomponent Nanoporous Media

Decoding the nanoscale porosity in serpentinites from multidimensional electron microscopy and discrete element modelling

Serpentinites, widespread in Earth's lithosphere, exhibit inherent nanoporosity that may significantly impact their geochemical behaviour. This study provides a comprehensive investigation into the characteristics, scale dependence, and potential implications of nanoporosity in lizardite-dominated serpentinites. Through a combination of multidimensional imaging techniques and molecular-dynamics-based discrete element modelling, we reveal that serpentinites function as nanoporous media with pore sizes predominantly less than 100 nm. Crystallographic relationships between olivine, serpentine, and nanoporosity are explored, indicating a lack of significant correlations. Instead, stochastic growth and random packing of serpentine grains within mesh cores may result in interconnected porosity. The analysis of pore morphology suggests that the irregular pore shapes align with the crystal form of serpentine minerals. Furthermore, the nanoporosity within brucite-rich layers at the serpentine-olivine interface is attributed to delamination along weak van der Waals planes, while pore formation within larger brucite domains likely results from low-temperature alteration processes. The fractal nature of the pore size distribution and the potential interconnectivity of porosity across different scales further support the presence of a pervasive nanoporous network within serpentinites. Confinement within these nanopores may introduce unique emergent properties, potentially influencing fluid transport, mineral solubility, and chemical reactions. As such, these processes may have profound implications for the geochemical evolution of serpentinites.

Imbibition behaviors in shale nanoporous media from pore-scale perspectives

Imbibition behaviors in shale nanoporous media from pore-scale perspectives

Predictive scale-bridging simulations through active learning

Throughout computational science, there is a growing need to utilize the continual improvements in raw computational horsepower to achieve greater physical fidelity through scale-bridging over brute-force increases in the number of mesh elements. For instance, quantitative predictions of transport in nanoporous media, critical to hydrocarbon extraction from tight shale formations, are impossible without accounting for molecular-level interactions. Similarly, inertial confinement fusion simulations rely on numerical diffusion to simulate molecular effects such as non-local transport and mixing without truly accounting for molecular interactions. With these two disparate applications in mind, we develop a novel capability which uses an active learning approach to optimize the use of local fine-scale simulations for informing coarse-scale hydrodynamics. Our approach addresses three challenges: forecasting continuum coarse-scale trajectory to speculatively execute new fine-scale molecular dynamics calculations, dynamically updating coarse-scale from fine-scale calculations, and quantifying uncertainty in neural network models.

Microstructure quantification of oblique angle sputtered porous a-Si thin films as a basis for structure-property relations of solid phase microextraction coatings

Understanding processing-structure-property (PSP) linkages of solid-phase microextraction (SPME) coating materials is crucial for the rational design and advancement of these new materials. As SPME is a diffusion-based extraction technique, analyzing the morphology of its coating materials is important for optimizing its performance. In this study, we assess the morphological evolution of micro/mesoporous amorphous silicon (a-Si) thin films sputtered at an oblique angle onto silicon, which serve as models for support materials in SPME devices. The contrast of scanning transmission electron microscopy (STEM) images is enhanced via ZnO infiltration by atomic layer deposition (ALD). Various metrics, including physical descriptors and two-point statistics methods, are employed to follow the films' evolution. Analysis of the two-point correlation function reveals a simple ellipse/spherical local pore geometry in contrast to the long-range irregular arrangement of pores identified by a range of traditional and novel metrics. Additionally, analyzing the internal structure of the pores through homology metrics aligns well with the theoretical understanding of morphological evolution in oblique sputtered films. These analyses show that the “average ratio of principal moment of inertia”, “Betti numbers”, and “two-point statistics” based metrics can capture valuable information during film growth.The morphological analysis approach proposed in this study can be applied to analyze any nanoporous medium as a first step towards developing structure-property relationships that tie back to a given preparation method. Ultimately, a more extensive experimental and/or simulation-based study should confirm the correlations between these metrics and actual diffusion properties as the basis for process-structure-properties relations for improved design and optimization of this film.

Corner flow effect on the relative permeability of two-phase flow in nano-confined porous media

Relative permeability is a critical factor clarifying the multiphase flow behavior in nano-porous media. However, most studies have focus on the circle flow, neglecting the corner flow effect. Therefore, in this work, a comprehensive relative permeability model considering the corner flow effect is proposed. We integrated the corner flow with the immiscible flow model and the confined liquid-gas phase equilibrium with the near-miscible flow model. Then it was validated against the experimental measured data, indicating the proposed model can well describe the two-phase flow in the confined space. Subsequently, sensitivity analysis of corner number, fractal dimension, minimum radius, and viscosity ratio were conducted. Results show that the corner flow effect is noticeable when corner number is less than 8. Under the optimal pore radius of 2 × 10−5 m, the gas relative permeability increases from 0.4909 to 0.9274 with corner number raising from 4 to 10. Under critical oil phase saturation of 0.175, increase of fraction dimension, minimum radius, and viscosity ratio leads to the significant decrease of oil relative permeability and increase of gas relative permeability. In addition, nano-confinement effect and CO2 injection will reduce the interfacial tension and increase the near-miscible relative permeability. When CO2 injection increase to 100% under oil saturation of 0.4084, the increment of oil relative permeability is nearly 67.2%. Interfacial intension-based interpolation method indicates that the confined fluid is more likely to be miscible than the bulk fluid. This relative permeability model provides deeper understandings of two-phase flow in the nano-porous media, which is benefit for the better development of unconventional reservoirs.

Effect of Ion Size on Pressure-Induced Infiltration of a Zeolite-Based Nanofluidic System.

A nanofluidic system consists of a nano-porous medium and functional liquid, which demonstrates a higher energy absorption density compared to conventional systems for energy absorption. Alterations in the composition of the functional liquid can significantly impact the properties of a nanofluidic system. In this paper, the widely used zeolite ZSM-5 was chosen as the porous medium to establish a nanofluidic system. Three distinct electrolyte solutions, namely KCl aqueous solutions, NaCl aqueous solutions and MgCl2 aqueous solutions were employed as functional liquids while pure water served as the reference condition for configuring four kinds of nanofluidic systems. Pressure-induced percolation experiments were performed on the four zeolite-based systems. The difference in the infiltration process between the electrolyte solution systems and the deionized water system has been ascertained. The effect of the ion size on the infiltration and defiltration process has been determined. The results show that the introduction of ions induces a hydration effect, resulting in a higher critical infiltration pressure of the electrolyte solution system compared to an aqueous solution system. The magnitude of cation charge directly correlates with the strength of the hydration effect and the corresponding increase in critical infiltration pressure. Upon entering the nanochannel, the liquid infiltrates primarily in the form of ions rather than a cation hydration form. The larger the ion size, the shallower the penetration depth after entering the nanopore channel and the larger the corresponding relative outflow rate. The present work will provide valuable theoretical complementary and experimental data support for nanofluidic system applications.

Ultrasonic study of water adsorbed in nanoporous glasses.

Thermodynamic properties of fluids confined in nanopores differ from those observed in the bulk. To investigate the effect of nanoconfinement on water compressibility, we perform water sorption experiments on two nanoporous glass samples while concomitantly measuring the speed of longitudinal and shear ultrasonic waves in these samples. These measurements yield the longitudinal and shear moduli of the water-laden nanoporous glass as a function of relative humidity that we utilize in the Gassmann theory to infer the bulk modulus of the confined water. This analysis shows that the bulk modulus (inverse of compressibility) of confined water is noticeably higher than that of the bulk water at the same temperature. Moreover, the modulus exhibits a linear dependence on the Laplace pressure. The results for water, which is a polar fluid, agree with previous experimental and numerical data reported for nonpolar fluids. This similarity suggests that irrespective of intermolecular forces, confined fluids are stiffer than bulk fluids. Accounting for fluid stiffening in nanopores may be important for accurate interpretation of wave propagation measurements in fluid-filled nanoporous media, including in petrophysics, catalysis, and other applications, such as in porous materials characterization.