Investigation of the dynamics of a percolation transition under rapid compression of a nanoporous body-nonwetting liquid system

The dynamics of infiltration of a nanoporous body with a nonwetting liquid under rapid compression is studied experimentally and theoretically. Experiments are carried out on systems formed by a hydrophobic nanoporous body Libersorb 23, water, and an aqueous solution of CaCl₂ at a compression rate of \(\dot p\) ≥ 10⁴ atm/s. It is found that the infiltration begins and occurs at a new constant pressure independent of the compression energy and viscosity of the liquid. The time of infiltration and the filled volume increase with the compression energy. A model of infiltration of a nanoporous body with a nonwetting liquid is constructed; using this model, infiltration is described as a spatially nonuniform process with the help of distribution functions for clusters formed by pores accessible to infiltration and filled ones. On the basis of the proposed system of kinetic equations for these distribution functions, it is shown that under rapid compression, the infiltration process must occur at a constant pressure p _c whose value is controlled by a new infiltration threshold θ _c = 0.28 for the fraction of accessible pores, which is higher than percolation threshold θ _c0 = 0.18. Quantity θ _c is a universal characteristic of porous bodies. In the range θ _c0 < θ < θ _c , infiltration of the porous body should not be observed. It is shown that the solution to the system of kinetic equations leads to a nonlinear response by the medium to an external action (rapid compression), which means the compensation of this action by percolation of the liquid from clusters of filled pores of finite size to an infinitely large cluster of accessible but unfilled pores. As a result of such compensation, infiltration is independent of the viscosity of the liquid. It is found that all experimental results can be described quantitatively in the proposed model.     

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.     

First-order transition in a three-dimensional disordered system

We present the first detailed numerical study in three dimensions of a first-order phase transition that remains first order in the presence of quenched disorder (specifically, the ferromagnetic-paramagnetic transition of the site-diluted four states Potts model). A tricritical point, which lies surprisingly near the pure-system limit and is studied by means of finite-size scaling, separates the first-order and second-order parts of the critical line. This investigation has been made possible by a new definition of the disorder average that avoids the diverging-variance probability distributions that plague the standard approach. Entropy, rather than free energy, is the basic object in this approach that exploits a recently introduced microcanonical Monte Carlo method.     

Observation of a dispersion transition and the stability of a liquid in a nanoporous medium

It has been found that the removal of overpressure is accompanied by a transition of some nonwetting-liquid nanoclusters to the stable state in narrow ranges of the filling factor and temperature. This means that the nonwetting liquid becomes ??wetting.??     

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.     

Phase transition in an occupationally disordered sulfate system

We have investigated the behavior of the Li_1.43Cs_0.57SO₄ single-crystal Raman spectra and dielectric permittivity as a function of temperature. It was observed that the crystal, which is an occupationally disordered system, with orthorhombic C_2v² structure at room temperature, undergoes a phase transition at 230 K. In the new phase the SO₄ tetrahedra remain in two non-equivalent sites and there is no evidence of the doubling of the unit cell.     

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.     

Freezing of fluids confined in a disordered nanoporous structure

Freezing of a simple fluid in a disordered nanoporous carbon is studied using molecular simulations. Only partial crystallization occurs, and the confined phase is composed of crystalline and amorphous nanodomains. This freezing behavior departs strongly from that for nanopores of simple geometry. We present a method for analyzing the freezing in such disordered materials in terms of a transition in the average size and number of crystalline clusters. The results provide a basis for the interpretation of experiments on freezing in such materials, particularly 1H-NMR and scattering experiments.     

Fluctuations of the number of neighboring pores and appearance of multiple nonergodic states of a nonwetting liquid confined in a disordered nanoporous medium

Multiple nonergodic states have been observed for nonwetting liquid in the Fluka100 C18 and Fluka100 C8 porous media with broad pore size distributions having different widths. The dispersion transition where the volume of confined liquid depends critically on the degree of filling of the porous medium and temperature is observed in the temperature range 293–343 K under study for the Fluka100 C18 porous medium and is not observed for the Fluka100 C8 porous medium. A mechanism of the appearance of multiple nonergodic states has been proposed. It has been shown that fluctuations of the number of the nearest neighbors in the disordered system are mainly responsible for the features of confinement of nonwetting liquid and nonergodic states of nonwetting liquid in the nanoporous media under investigation with wide pore size distributions.     

Spin-glass transition in disordered terbium

While crystalline Tb is a helix antiferromagnet with a Néel temperature of 229 K which becomes ferromagnetic at 222 K, disordered Tb exhibits a spin-glass transition. The spin-glass freezing temperature ranges from 183 to 53 K, the lowest temperatures corresponding to the greatest degree of atomic disorder. These experiments constitute the first evidence for an elemental spin-glass.     

Low-temperature metal-insuslator transition and magnetic properties in the VxMn1−x S disordered system

A study of the structure and electrical and magnetic properties of the V_xMn_1−x S disordered system is reported. The existence of a low-temperature metal-insulator transition for Fermi-glass 0.4<x<0.5 compositions in paramagnetic phase, which is accompanied by a change in the structure and magnetic properties, has been established. An analysis of the magnetic properties permits a conjecture that current carriers become delocalized in these solid solutions at the metal-insulator transition temperature to form small ferromagnetically ordered regions (ferrons). Fiz. Tverd. Tela (St. Petersburg) 39, 1428–1431 (August 1997)     

ε-expansion for the density of states of a disordered system near an Anderson transition

The density of states for the Schrödinger equation with a Gaussian random potential is calculated in a space of dimension d=4?ε in the entire energy range, including the vicinity of an Anderson transition.     

Ferromagnetism and metal-insulator transition in the disordered Hubbard model

A detailed study of the paramagnetic to ferromagnetic phase transition in the one-band Hubbard model in the presence of binary-alloy disorder is presented. The influence of the disorder (with concentrations x and 1-x of the two alloy ions) on the Curie temperature T(c) is found to depend strongly on electron density n. While at high densities, n>x, the disorder always reduces T(c); at low densities, n相似文献   

无序度对一维长程关联无序系统中局域化-退局域化转变的影响

对长程幂律关联能量序列进行了修正,使其能体现出无序度在一维长程关联无序系统中的影响,并利用重正化群方法,计算了能反映该系统局域化-退局域化转变的Lyapunov指数.结果表明,在由于关联指数p的影响而在系统中出现的局域化向退局域化的转变中,无序度起着相反的作用.当关联指数p一定而无序度W增大时,系统中心能区范围内由于长程关联而引起的扩展态逐渐向局域态转变.当无序度W增大到某一临界值W_c时,系统中所有本征态均转变为局 关键词： 长程关联 Lyapunov指数 无序度 局域化-退局域化转变     

T c of disordered superconductors near the Anderson transition

According to the Anderson theorem, the critical temperature T _c of a disordered superconductor is determined by the average density of states and does not change at the localization threshold. This statement is valid under assumption of a self-averaging order parameter, which can be violated in the strong localization region. Stimulating by statements on the essential increase of T _c near the Anderson transition, we carried out the systematic investigation of possible violations of self-averaging. Strong deviations from the Anderson theorem are possible due to resonances at the quasi-discrete levels, resulting in localization of the order parameter at the atomic scale. This effect is determined by the properties of individual impurities and has no direct relation to the Anderson transition. In particular, we do not see any reasons to say on “fractal superconductivity” near the localization threshold.     

Short range order and the metal-insulator transition in disordered systems

The effect of short range order on the electronic density of states, the conductivity, and localization is calculated for a model binary alloy in the simple cubic configuration using a cluster extension of CPA. In the presence of short range order a metal insulator transition takes place as the concentration passes through a critical range.     

Influence of the stick-slip transition on the electrokinetic behavior of nanoporous material

Electrokinetic phenomena exhibiting discontinuities are described in terms of a stick-slip transition. The flux-force equations are partially linear and in the linear regimes the coefficients satisfy Onsager's reciprocal relations. From an interpretation of existing data on ion exchange membranes we find a linear dependence of the slip length with the surface potential. We conclude that slippage offers an alternative explanation for the so-called anomalous surface conduction, as often found in electrokinetic phenomena. This would imply an enhancement of electrokinetic effects in nanopores.