Multiplicity of metastable nonergodic states of a dispersed nonwetting liquid in a disordered nanoporous medium

Three different metastable nonergodic states of a dispersed nonwetting liquid (water) in the Fluka 100 C8 and Fluka 100 C18 disordered porous media, as well as transitions between these states under variation of the temperature and the degree of filling, have been qualitatively described. It has been shown that the appearance of such states is due to spatial variations of the number of the nearest neighbors because of the broadening of the pore size distribution function f(R), fluctuations of various local configurations of neighbors in the system of pores, and fluctuations of a configuration of a pore and its environment consisting of filled and empty pores on a percolation cluster. These states and transitions are caused by the competition between the effective repulsion of the nonwetting liquid from the wall of the pore, which is responsible for the “extrusion” of the liquid from the pore, and the effective collective multiparticle attraction of the liquid cluster in the pore to clusters in the neighboring connected pores. The theoretical dependences obtained make it possible to qualitatively describe experimental data.     

气孔分布特性对含水多孔介质气体扩散的影响

本文基于多孔介质的气孔分布特性,计算了多孔介质在含水状态下的扩散性能,并且比较了采用两种方式计算相对渗透率时的相对扩散性能。其结果表明,基于气孔分布的计算结果低于与气孔分布无关的计算结果。另外,疏水性含水多孔介质的扩散性能低于亲水性含水多孔介质的扩散性能,基于气孔分布计算含水多孔介质的气体扩散性能时,Wyllie公式并不适用。     

Dispersion transition and the nonergodicity of the disordered nanoporous medium-nonwetting liquid system

The experiments in which a nonwetting liquid does not flow from a disordered nanoporous medium are described. The outflow is shown to depend on the degree of filling of the porous medium and its temperature in a critical manner. A physical mechanism is proposed where the transition of a system of liquid nanoclusters in a confinement into a metastable state in narrow filling and temperature ranges results from the appearance of a potential barrier due to the fluctuations of the collective “multiparticle” interaction of liquid nanoclusters in neighboring pores of different sizes at the shell of a percolation cluster of filled pores. The energy of a metastable state forms a potential relief with numerous maxima and minima in the space of a porous medium. The dispersed liquid volume in a metastable state is calculated with an analytical percolation theory for a ground state with an infinite percolation cluster. The outflow time distribution function of pores is calculated, and a power law is obtained for the decrease in nonwetting liquid volume retained in a porous medium with increasing time. The relaxation of the system under study is a multistage process accompanied by discontinuous equilibrium and overcoming of numerous local maxima of a potential relief. The formation of the metastable state of retained nonwetting liquid results from the nonergodicity properties of a disordered porous medium. The proposed model can describe the detected dependences of dispersed liquid volume on the degree of filling and temperature.     

Nuclear magnetic resonance cryoporometry

Nuclear Magnetic Resonance (NMR) cryoporometry is a technique for non-destructively determining pore size distributions in porous media through the observation of the depressed melting point of a confined liquid. It is suitable for measuring pore diameters in the range 2 nm–1 μm, depending on the absorbate. Whilst NMR cryoporometry is a perturbative measurement, the results are independent of spin interactions at the pore surface and so can offer direct measurements of pore volume as a function of pore diameter. Pore size distributions obtained with NMR cryoporometry have been shown to compare favourably with those from other methods such as gas adsorption, DSC thermoporosimetry, and SANS. The applications of NMR cryoporometry include studies of silica gels, bones, cements, rocks and many other porous materials. It is also possible to adapt the basic experiment to provide structural resolution in spatially-dependent pore size distributions, or behavioural information about the confined liquid.     

Investigation of the percolation transition in a nonwetting liquid-nanoporous medium system

The flows of liquid into and out of a nanoporous medium are studied as processes leading to the fluctuation formation and the growth of fractal clusters of filled and empty pores, respectively. The conditions for stable growth of such fluctuations are analyzed as a function of the interfacial energy between the liquid and the porous medium and the surface energy of the liquid. Expressions are obtained for the pressure at which the barrier for fluctuation filling and emptying of the pores vanishes. In general, it is shown for porous media with a pore-size distribution that these processes can be interpreted as a percolation phase transition. The volume and susceptibility of a liquid-porous medium system near the transition points with inflow and outflow of the liquid are calculated. The phenomenon of nonoutflow of a nonwetting liquid from a porous medium and hysteresis of the flow of liquid into and out of a porous medium are explained on the basis of the mechanism considered. The results of an experimental investigation of these processes in the system liquid Wood’s alloy-silochrome 80 and silochrome 120 are presented. The experimental data obtained can be described on the basis of the proposed mechanism.     

Methane hydrate crystal growth in a porous medium filled with methane-saturated liquid water

The nucleation, growth and ageing of methane hydrate crystals were observed visually in a porous medium filled with liquid water presaturated with methane. The pore space dimensions of the porous medium were 1.0?×?10²?µm. The pressure?temperature conditions at which hydrate formation was initiated corresponded to system subcoolings of 3.4?K, 6.7?K, 12.3?K and 14.1?K, respectively, where the system subcooling denotes the difference of the system temperature from the triple methane?hydrate?water equilibrium temperature under a given pressure. Faceted (skeletal) hydrate crystals grew and bridged the pore spaces without intervention of a liquid water layer when the subcoolings were equal or smaller than 6.7?K. The faceted crystals may form a physical bonding with the walls of the porous medium. At the higher subcoolings, the dispersive formation of dendritic crystals and subsequent morphological change into particulate crystals were observed. The bridging of the dendritic crystals is unlikely in the absence of a large amount of additional methane supply due to the dispersive spatial distribution of the dendritic crystals that have dimensions smaller than those of the pore spaces. As a result of the interpretation of the observed variation in the crystal morphology of the methane hydrate formed in liquid water, the dependence of the crystal morphology on the magnitude of the mass transfer of methane molecules in liquid water observed in the porous medium was consistent with that previously observed in a bulk methane–water system.     

Anomalously slow relaxation of a nonwetting liquid in the disordered confinement of a nanoporous medium

The time evolution of the water–disordered nanoporous medium Libersorb 23 (L23) system has been studied after complete filling at elevated pressure followed by full release of overpressure. It is established that relaxation of the L23 rapidly flows out during the overpressure relief time, following the variation in pressure. At a temperature below that of the dispersion transition (T < T _d = 284 K), e.g., at T = 277 K, the degree of filling θ decreases from 1 to 0.8 within 10 s. The degree of filling varies with time according to the power law θ ~ t ^–α with the exponent α < 0.1 over a period of t ~ 10⁵ s. This process corresponds to slow relaxation of a metastable state of a nonwetting liquid in a porous medium. At times t > 10⁵ s, the metastable state exhibits decay, manifested as the transition to a power dependence of θ(t) with a larger exponent. The relaxation of the metastable state of nonwetting liquid in a disordered porous medium is described in the mean field approximation as a continuous sequence of metastable states with a barrier decreasing upon a decrease in the degree of filling. Using this approach, it is possible to qualitatively explain the observed relaxation process and crossover transition to the stage described by θ(t) with a larger exponent.     

Molecular dynamics simulation of decomposition and thermal conductivity of methane hydrate in porous media

The hydrate has characteristics of low thermal conductivity and temperature sensitivity. To further analysis the mechanism of thermal conductivity and provide method for the exploitation, transportation and utilization of hydrate, the effect of decomposition and thermal conductivity of methane hydrate in porous media has been studied by using the molecular dynamics simulation. In this study, the simulation is carried out under the condition of temperature 253.15 K-273.15 K and pressure 1 MPa. The results show that the thermal conductivity of methane hydrate increases with the increase of temperature and has a faster growth near freezing. With the addition of porous media, the thermal conductivity of the methane hydrate improves significantly. The methane hydrate-porous media system also has the characteristics of vitreous body.With the decrease of the pore size of the porous media, thermal conductivity of the system increases gradually at the same temperature. It can be ascertained that the porous media of different pore sizes have strengthened the role of the thermal conductivity of hydrates.     

Multidimensionally resolved pore size distributions

A novel method of determining median pore size and pore size distributions as a function of spatial position inside a porous sample is described. Pore sizes have been measured with 1-, 2- and 3-dimensional spatial resolution, using NMR cryoporometry in conjunction with magnetic resonance imaging techniques. The method is suitable for pore diameters in the range of 30 Å to over 2000 Å pore diameter, and is based on the technique of freezing a liquid in the pores and measuring the melting temperature by nuclear magnetic resonance. Since the melting point is depressed for crystals of small size, the melting point depression gives a measurement of pore size.     

Correlation effects during liquid infiltration into hydrophobic nanoporous media

To explain the thermal effects observed during the infiltration of a nonwetting liquid into a disordered nanoporous medium, we have constructed a model that includes correlation effects in a disordered medium. It is based on analytical methods of the percolation theory. The infiltration of a porous medium is considered as the infiltration of pores in an infinite cluster of interconnected pores. Using the model of randomly situated spheres (RSS), we have been able to take into account the correlation effect of the spatial arrangement and connectivity of pores in the medium. The other correlation effect of the mutual arrangement of filled and empty pores on the shell of an infinite percolation cluster of filled pores determines the infiltration fluctuation probability. This probability has been calculated analytically. Allowance for these correlation effects during infiltration and defiltration makes it possible to suggest a physical mechanism of the contact angle hysteresis and to calculate the dependences of the contact angles on the degree of infiltration, porosity of the medium, and temperature. Based on the suggested model, we have managed to describe the temperature dependences of the infiltration and defiltration pressures and the thermal effects that accompany the absorption of energy by disordered porous medium-nonwetting liquid systems with various porosities in a unified way.     

A stochastic theory for deep bed filtration accounting for dispersion and size distributions

We develop a stochastic theory for filtration of suspensions in porous media. The theory takes into account particle and pore size distributions, as well as the random character of the particle motion, which is described in the framework of the theory of continuous-time random walks (CTRW). In the limit of the infinitely many small walk steps we derive a system of governing equations for the evolution of the particle and pore size distributions. We consider the case of concentrated suspensions, where plugging the pores by particles may change porosity and other parameters of the porous medium. A procedure for averaging of the derived system of equations is developed for polydisperse suspensions with several distinctive particle sizes. A numerical method for solution of the flow equations is proposed. Sample calculations are applied to compare the roles of the particle size distribution and of the particle flight dispersion on the deposition profiles. It is demonstrated that the temporal flight dispersion is the most likely mechanism forming the experimentally observed hyperexponential character of the deposition profiles.     

Xenon porometry: a novel method for the derivation of pore size distributions

Xenon porometry is a novel method used for characterizing porous materials by the (129)Xe nuclear magnetic resonance of xenon gas. With the method, the diffusion of gas is slowed down by immersing the material in a medium, which can be in liquid or solid state during measurements. Because of slow diffusion, the signal of a xenon atom is characteristic of the properties of only one pore, and the composite signal of all atoms represents the distribution of properties. The method is especially applicable for determining pore size distribution because the chemical shifts of two different xenon signals (one from liquid and the other from gas pockets in solid) are dependent on pore size. Therefore, the shapes of these signals represent pore size distribution function. In addition, the porosity of the material can be determined by comparing the intensities of two signals. This article focuses on describing xenon signals observed from gas pockets in a solid medium, which has turned out to be most convenient for pore size determination.     

The percolation transition in filling a nanoporous body by a nonwetting liquid

The paper presents the results of an experimental study of the percolation transition in filling by nonwetting liquids of nanoporous bodies of various natures with different specific surface areas and mean pore and granule sizes. The liquid that we used was an aqueous solution of ethylene glycol. The hysteresis and non-outflow phenomena observed in this transition at various (known) surface energies of liquids were studied by varying the concentration of ethylene glycol. This helped us explain the mechanism of the percolation transition in filling nanoporous bodies with nonwetting liquids. It was shown that, to quantitatively describe the observed dependences in terms of percolation theory taking into account energy barriers to filling, we must use a non-scaling distribution function of clusters of accessible and filled pores that admits the formation of pore clusters of arbitrary dimensions.     

考虑弥散效应的多孔介质中超绝热燃烧的数值模拟

研究多孔介质内往复流动下的超绝热燃烧。一维模型包括气体输运、多孔介质固体的辐射、导热和气固两相间的对流换热。通过数值计算研究超绝热燃烧的形成、以及弥散效应、当量比和多孔介质材料本身对超绝热燃烧特性的影响。计算结果的有效性通过实验进行了验证并取得了相同的趋势。结果表明,组分弥散效应对气体温度分布和反应热影响很小;同一工况下,不考虑气体混合物的热弥散效应,会导致过高的气体温度计算值。同时,计算结果表明小孔径的多孔介质更有利于贫可燃极限的扩展,对30 ppi的多孔介质燃烧器,得到了当量比为0．092的可燃极限。     

MRI studies of the evaporation of a single liquid droplet from porous surfaces

A combination of in situ one-dimensional profiling and two-dimensional 1H magnetic resonance imaging has been applied to study the shape and subsequent dynamic evaporation behavior of a single liquid droplet after impact onto a porous surface in a carefully controlled atmosphere. Aspects of the porous media permeability and particle shape are shown to affect considerably the observed drying regime. Variation in the shape, spread ratio, and penetration depth of the liquid droplet following impact are attributed to the different types of porous media used. A comparison of numerical simulations with the MRI data for the droplet shape, spread factor, and penetration depth show good agreement though larger deviations between simulated and experimental results occur in certain cases where the surface of the porous medium is disrupted by the impact of the liquid droplet. Initial results examining the effect of a reduced liquid surface tension show a significantly increased evaporation rate.     

Characterization of Porous Materials by Magnetic Relaxometry in the Earth’s Field

In this paper, it is shown how free induction decay signals recorded in the Earth’s magnetic field from water protons confined in porous media can be used to derive transversal relaxation times (T ₂) and their distributions. After T ₂ determination of six sintered glass samples with various pore sizes, the common theoretical model can be fitted to the data set. The T ₂ distribution of water protons in a bimodal porous system is analyzed and compared to mercury porosimetry results. The implications for the calculation of pore sizes and pore size distributions of porous media by this method are discussed.     

岩心孔隙介质中流体的核磁共振弛豫

弛豫时间是核磁共振研究中的一个重要参数,岩心孔隙介质流体的弛豫过程是自由流体弛豫机制、表面弛豫机制和流体的扩散弛豫机制共同作用的结果,它包含了丰富的孔隙和流体本身的信息. 弛豫时间和自扩散系数的测量及对弛豫时间的分析是核磁共振技术应用于岩心分析和石油勘测的重要内容.     

Effect of heat treatment on pore structure in nanocrystalline NiO: A small angle neutron scattering study

Nanocrystalline nickel oxide powders were calcined at 300, 600 and 900°C and pore structure evolution was followed by small angle neutron scattering (SANS). Pore size distributions at two widely separated size ranges have been revealed. Shrinkage of larger-sized pore with reduction in polydispersity has been observed with increasing heat treatment temperature. The pore structures at various heat treatment temperatures do not scale. This has been attributed to the grain boundary diffusion leading to an asymmetric shrinkage of the pores.