Slow dynamics of embedded fluid in mesoscopic confining systems as probed by NMR relaxometry

Mesoscopic media such as porous materials or colloidal dispersions strongly influence the dynamics of the embedded fluid. In the strong-adsorption regime, it was recently proposed that the effective surface diffusion on flat surface is anomalous and exhibits long-time pathology, enlarging the time domain of the embedded-fluid dynamics towards the low-frequency regime. An interesting way to probe such a slow interfacial process is to use the field-cycling NMR relaxometry. This technique is used here to probe the fluid dynamics in two types of interfacial systems: i) a colloidal glass made of thin and flat particles; ii) a fully saturated porous media, the Vycor glass. Experimental results are critically compared to either a simple theoretical model of NMR dispersion involving elementary steps of the fluid dynamics near an interface (loops, trains, tails) or Brownian-dynamics simulations performed inside 3D reconstructions of these confined systems.Received: 1 January 2003, Published online: 14 October 2003PACS: 76.60.Es Relaxation effects - 61.43.Gt Powders, porous materials - 82.70.Dd Colloids     

Confined dynamics, forms and transitions in colloidal systems: from clay to DNA

Colloidal suspensions are a classic example of confining systems developing large specific surfaces, presenting a rich variety of shapes and exhibiting complex organization on a length scale ranging from 1 nm to several micrometers. Two distinct confined dynamics are generally considered in such systems: (1) the embedded fluid dynamics entrapped in the pore network with two main contributions, surface interaction and long-range connectivity, and (2) the dynamics of the host matrix, associated with a time evolution of the interfacial geometry. This last contribution is particularly important during dynamic and structural transitions of colloidal suspensions such as jamming, glass transition, phase separations and flocculation. It is generally believed that the characteristic time scale needed to describe colloidal movement and interfacial geometrical reorganization is much slower than the dynamics of the embedded fluid (except in the trivial situation where the fluid molecule is irreversibly adsorbed to a colloidal surface). Thus, few connections are made between these two distinct dynamics. In this presentation, we show how the slow and confined water dynamics at proximity of a colloidal surface provides an original way to probe colloidal shape and colloidal orientation dynamics. Two topics are presented. First of all, water field-cycling NMR relaxometry is used to probe the glass transition and the strong rotational slowing down of a colloidal system made of plate-like particles, a synthetic clay (laponite). Second, we analyze the case of long colloidal thin rods (either mineral or biologic such as DNA cylinders) dispersed in very diluted suspensions. At large distance and/or long time, these particles appear as a portion of a line. We discuss how the embedded fluid dynamics can be sensitive to this morphological crossover and may provide information about the particle shape. Some comparisons with recent experiments are presented.     

Lévy Walk with Multiple Internal States

Lévy walk with multiple internal states can effectively model the motion of particles that don’t immediately move back to the directions or areas which they come from. When the Lévy walk behaves superdiffusion, it is discovered that the non-immediately-repeating property, characterized by the constructed transition matrix, has no influence on the particle’s mean square displacement (MSD) or Pearson coefficient. This is a kind of stable property of Lévy walk. However, if the Lévy walk shows the dynamical behaviors of normal diffusion, then the effect of non-immediately-repeating emerges. For the Lévy walk with some particular transition matrices, it may display nonsymmetric dynamics; in these cases, the behaviors of their variances are detailedly discussed, especially some comparisons with the ones of the continuous time random walks are made (a striking difference is the changes of the exponents of the variances). The first passage time distribution and its average of Lévy walks are simulated, the results of which turn out that the first passage time can distinguish Lévy walks with different transition matrices, while the MSD can not.

     

Continuous Markovian model for Lévy random walks with superdiffusive and superballistic regimes

We consider a previously devised model describing Lévy random walks [I. Lubashevsky, R. Friedrich, A. Heuer, Phys. Rev. E 79, 011110 (2009); I. Lubashevsky, R. Friedrich, A. Heuer, Phys. Rev. E 80, 031148 (2009)]. It is demonstrated numerically that the given model describes Lévy random walks with superdiffusive, ballistic, as well as superballistic dynamics. Previously only the superdiffusive regime has been analyzed. In this model the walker velocity is governed by a nonlinear Langevin equation. Analyzing the crossover from small to large time scales we find the time scales on which the velocity correlations decay and the walker motion essentially exhibits Lévy statistics. Our analysis is based on the analysis of the geometric means of walker displacements and allows us to tackle probability density functions with power-law tails and, correspondingly, divergent moments.     

Quantitative evaluation of porous media wettability using NMR relaxometry

We propose a new method to determine wettability indices from NMR relaxometry. The new method uses the sensitivity of low field NMR relaxometry to the fluid distribution in oil-water saturated porous media. The model is based on the existence of a surface relaxivity for both oil and water, allowing the determination of the amount of surface wetted either by oil or by water. The proposed NMR wettability index requires the measurement of relaxation time distribution at four different saturation states. At the irreducible water saturation, we determine the dominant relaxation time of oil in the presence of a small amount of water, and at the oil residual saturation, we determine the dominant relaxation time of water in the presence of a small amount of oil. At 100% water and 100% oil saturation, we determine the surface relaxivity ratio. The interaction of oil with the surface is also evidenced by the comparison of the spin-lattice (T1) and spin-locking (T1rho) relaxation times. The new NMR index agrees with standard wettability measurements based on drainage-imbibition capillary pressure curves (USBM test) in the range [-0.3-1].     

Lévy flights and superdiffusion in the context of biological encounters and random searches

We review the general problem of random searches in the context of biological encounters. We analyze deterministic and stochastic aspects of searching in general and address the destructive and nondestructive cases specifically. We discuss the concepts of Lévy walks as adaptive strategies and explore possible examples. We also review Lévy searches in other media and spaces, including lattices and networks as opposed to continuous environments. We analyze empirical evidence supporting the Lévy flight foraging hypothesis, as well as the more general idea of superdiffusive foraging. We compare these hypothesis with alternative theories of random searches. Finally, we comment on several issues relevant to the practical application of models of Lévy and superdiffusive strategies to the general question of biological foraging.     

Truncated Lévy flights and generalized Cauchy processes

A continuous Markovian model for truncated Lévy flights is proposed. It generalizes the approach developed previously by Lubashevsky et al. [Phys. Rev. E 79, 011110 (2009); Phys. Rev. E 80, 031148 (2009), Eur. Phys. J. B 78, 207 (2010)] and allows for nonlinear friction in wandering particle motion as well as saturation of the noise intensity depending on the particle velocity. Both the effects have own reason to be considered and, as shown in the paper, individually give rise to a cutoff in the generated random walks meeting the Lévy type statistics on intermediate scales. The nonlinear Langevin equation governing the particle motion was solved numerically using an order 1.5 strong stochastic Runge-Kutta method. The obtained numerical data were employed to analyze the statistics of the particle displacement during a given time interval, namely, to calculate the geometric mean of this random variable and to construct its distribution function. It is demonstrated that the time dependence of the geometric mean comprises three fragments following one another as the time scale increases that can be categorized as the ballistic regime, the Lévy type regime (superballistic, quasiballistic, or superdiffusive one), and the standard motion of Brownian particles. For the intermediate Lévy type part the distribution of the particle displacement is found to be of the generalized Cauchy form with cutoff. Besides, the properties of the random walks at hand are shown to be determined mainly by a certain ratio of the friction coefficient and the noise intensity rather than their characteristics individually.     

From a simple liquid to a polymer melt: NMR relaxometry study of polybutadiene

We utilize NMR field cycling relaxometry to study the crossover from glassy dynamics (t approximately > tau alpha) through Rouse to reptation behavior in a series of monodisperse polybutadienes with molecular weights M=355 to 817,000 g/mol. We separate characteristic polymer dynamics from the total spectrum dominated by glassy dynamics. The polymer dynamics show typical Rouse relaxation features that grow with M and saturate at high M. Comparing to Rouse theory, we determine the Rouse unit size MR approximately = 500 and entanglement weight Me approximately = 2000; the Rouse spectrum saturates at Mmax approximately = 4000. The local order parameter S approximately 0.11 is relatively large, indicating noticeable local packing already in the Rouse regime. The M dependence of the glass transition temperature Tg, obtained from dielectric relaxation spectra, shows distinctive kinks at MR and Me.     

Porous media characterization by PFG and IMFG NMR

Fully and partially filled with tridecane quartz sand was studied by different NMR techniques. The set of NMR experiments was carried out to obtain information about porous media geometry and fluid localization in it in case of partially filled porous space. The study was done using three NMR approaches: pulse field gradient NMR (PFG NMR), DDif experiment and tau-scanning experiment. The possibility to use all three approaches to study porous media properties even at the high resonance frequency is shown together with complementarity of the given by them information. Thus, first two approaches give information about porous sizes and geometry, at the same time tau-scanning experiment allows us to obtain information about distribution of internal magnetic field gradients in the porous space and draw conclusions about fluid localization in it.     

Two competing species in super-diffusive dynamical regimes

The dynamics of two competing species within the framework of the generalized Lotka-Volterra equations, in the presence of multiplicative α-stable Lévy noise sources and a random time dependent interaction parameter, is studied. The species dynamics is characterized by two different dynamical regimes, exclusion of one species and coexistence of both, depending on the values of the interaction parameter, which obeys a Langevin equation with a periodically fluctuating bistable potential and an additive α-stable Lévy noise. The stochastic resonance phenomenon is analyzed for noise sources asymmetrically distributed. Finally, the effects of statistical dependence between multiplicative noise and additive noise on the dynamics of the two species are studied.     

Time characteristics of Lévy flights in a steep potential well

Using the method previously developed for ordinary Brownian diffusion, we derive a new formula to calculate the correlation time of stationary Lévy flights in a steep potential well. For the symmetric quartic potential, we obtain the exact expression of the correlation time of steady-state Lévy flights with index α = 1. The correlation time of stationary Lévy flights decreases with an increasing noise intensity and steepness of potential well.     

Photoluminescence decay of silicon nanocrystals and Lévy stable distributions

We incorporate the tools of Lévy processes and distributions to describe the photoluminescence of silicon nanocrystals. The method relies on two novel features: first we use exact forms of one-sided Lévy distributions to get an excellent reproduction of experimental data. Then we show that the dynamics leading to photoluminescence decay can be modelled in terms of fractional Fokker–Planck equation.     

Lévy flights and Lévy-Schrödinger semigroups

We analyze two different confining mechanisms for Lévy flights in the presence of external potentials. One of them is due to a conservative force in the corresponding Langevin equation. Another is implemented by Lévy-Schrödinger semigroups which induce so-called topological Lévy processes (Lévy flights with locally modified jump rates in the master equation). Given a stationary probability function (pdf) associated with the Langevin-based fractional Fokker-Planck equation, we demonstrate that generically there exists a topological Lévy process with the same invariant pdf and in reverse.     

Non-Gaussian noise effects in the dynamics of a short overdamped Josephson junction

The role of thermal and non-Gaussian noise on the dynamics of driven short overdamped Josephson junctions is studied. The mean escape time of the junction is investigated considering Gaussian, Cauchy-Lorentz and Lévy-Smirnov probability distributions of the noise signals. In these conditions we find resonant activation and the first evidence of noise enhanced stability in a metastable system in the presence of Lévy noise. For Cauchy-Lorentz noise source, trapping phenomena and power law dependence on the noise intensity are observed.     

Correlated Lvy flight in external force fields

The correlated Lvy flight is studied analytically in terms of the fractional Fokker-Planck equation and simulated numerically by using the Langevin equation,where the usual white Lvy noise is generalized to an Ornstein-Uhlenbeck Lvy process(OULP)with a correlation timeτc.We analyze firstly the stable behavior of OULP.The probability density function of Lvy flight particle driven by the OULP in a harmonic potential is exactly obtained,which is also a Lvy-type one withτc-dependence width;when the particle is bounded by a quartic potential,its stationary distribution has a bimodality shape and becomes noticeable with the increase of τc.     

A new probe of pore geometry: diffusive MASS NMR

NMR methods are widely used to probe the structure and fluid dynamics of porous materials, as they are uniquely suited to these studies since NMR records the correlation of changing local magnetic fields over a time scale of ns to seconds. The local magnetic fields are established by local variations in the bulk magnetic susceptibility of the sample (and so are directly tied to the sample's local structure). The fluctuation in field that a spin sees is due to molecular transport (including molecular diffusion) through these local fields, and so reports on the length scales of structures and impediments to transport. We have developed a new set of methods DIFFUSIVE-MASS to provide a means of systematically varying the effective time scale of the measurement and thus the effective length scale. This new handle permits a detailed, microscopic picture of the structure and dynamics. Diffusive MASS NMR methods will permit a systematic set of methods and analysis for characterizing the chemistry, structure and fluid dynamics of the mobile phase in porous materials. The approach will be applicable to any diamagnetic material. In particular, the industry of oil discovery depends on understanding heterogeneous porous media.     

Restricted diffusion and exchange of water in porous media: average structure determination and size distribution resolved from the effect of local field gradients on the proton NMR spectrum

NMR Pulsed field gradient measurements of the restrained diffusion of confined fluids constitute an efficient method to probe the local geometry in porous media. In most practical cases, the diffusion decay, when limited to its principal part, can be considered as Gaussian leading to an apparent diffusion coefficient. The evolution of the latter as a function of the diffusion interval yields average information on the surface/volume ratio of porosities and on the tortuosity of the network. In this paper, we investigate porous model systems of packed spheres (polystyrene and glass) with known mean diameter and polydispersity, and, in addition, a real porous polystyrene material. Applying an Inverse Laplace Transformation in the second dimension reveals an evolution of the apparent diffusion coefficient as a function of the resonance frequency. This evolution is related to a similar evolution of the transverse relaxation time T2. These results clearly show that each resonance frequency in the water proton spectrum corresponds to a particular magnetic environment produced by a given pore geometry in the porous media. This is due to the presence of local field gradients induced by magnetic susceptibility differences at the liquid/solid interface and to slow exchange rates between different pores as compared to the frequency differences in the spectrum. This interpretation is nicely confirmed by a series of two-dimensional exchange experiments.     

Superdiffusive wave front propagation in a chemical active flow

We present experiments on the propagation of a wave front in a fluid forced by Faraday waves. The vertical periodical modulation of the acceleration induces flows in the system that modifies the Belousov-Zhabotinsky (BZ) chemical reaction dynamics. Phase waves spreading through standing waves with different symmetries results in superdiffusion. The anomalous diffusion is characterized in terms of a non-integer transport exponent which is compared with exponents resulting from tracer particles trajectories undergoing rapid, distant jumps called Lévy flights.     

Stationary states in bistable system driven by Lévy noise

We study the properties of the probability density function (PDF) of a bistable system driven by heavy tailed white symmetric Lévy noise. The shape of the stationary PDF is found analytically for the particular case of the Lévy index α = 1 (Cauchy noise). For an arbitrary Lévy index we employ numerical methods based on the solution of the stochastic Langevin equation and space fractional kinetic equation. In contrast to the bistable system driven by Gaussian noise, in the Lévy case, the positions of maxima of the stationary PDF do not coincide with the positions of minima of the bistable potential. We provide a detailed study of the distance between the maxima and the minima as a function of the depth of the potential and the Lévy noise parameters.