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.     

Slow dynamics in colloidal glasses and porous media as probed by NMR relaxometry: assessment of solvent levy statistics in the strong adsorption regime

Mesoscopic media such as porous materials or colloidal pastes develop large specific surface area which strongly influence the dynamics of the embedded fluid. This fluid confinement can be used either to probe the interfacial geometry (frozen porous media) or the particle dynamics (paste and colloidal glass). In the strong adsorption regime, it was recently proposed that the effective surface diffusion on flat surface is anomalous and exhibits long time pathology (Lévy walks). This phenomena is directly related to the time and space properties of loop trajectories appearing in the bulk between a desorption and a readsorption step. The Lévy statistics extends the time domain of the embedded fluid dynamics toward the low frequency regime. An interesting way to probe such a slow interfacial process is to use field cycling NMR relaxometry. In the first part of this paper, we propose a simple theoretical model of NMR dispersion which only involves elementary time steps of the solvent dynamics near an interface (loops, trains, tails in relation with the confining geometry). In the second part, field cycling NMR relaxometry is used to probe the slow solvent dynamics in two type of interfacial systems: (i) a colloidal glass made of thin and flat particles (ii) two fully saturated porous media, the Vycor glass and MCM48 respectively. Experimental results are critically compared to closed-form analytical expressions and numerical simulations.     

The internal magnetic field distribution, and single exponential magnetic resonance free induction decay, in rocks

When fluid saturated porous media are subjected to an applied uniform magnetic field, an internal magnetic field, inside the pore space, is induced due to magnetic susceptibility differences between the pore-filling fluid and the solid matrix. The microscopic distribution of the internal magnetic field, and its gradients, was simulated based on the thin-section pore structure of a sedimentary rock. The simulation results were verified experimentally. We show that the 'decay due to diffusion in internal field' magnetic resonance technique may be applied to measure the pore size distribution in partially saturated porous media. For the first time, we have observed that the internal magnetic field and its gradients in porous rocks have a Lorentzian distribution, with an average gradient value of zero. The Lorentzian distribution of internal magnetic field arises from the large susceptibility contrast and an intrinsic disordered pore structure in these porous media. We confirm that the single exponential magnetic resonance free induction decay commonly observed in fluid saturated porous media arises from a Lorentzian internal field distribution. A linear relationship between the magnetic resonance linewidth, and the product of the susceptibility difference in the porous media and the applied magnetic field, is observed through simulation and experiment.     

The relationship of problems in biomedical MRI to the study of porous media.

The NMR methods that are used to characterize inanimate porous media measure relaxation times and related phenomena and material transport, fluid displacement and flow. Biological tissues are comprised of multiple small, fluid-filled compartments, such as cells, that restrict the movement of the bulk solvent water and whose constituents influence water proton relaxation times via numerous interactions with macromolecular surfaces. Several of the methods and concepts that have been developed in one field of application are also of great value in the other, and it may be expected that technical developments that have been spurred by biomedical applications of MR imaging will be used in the continuing study of porous media. Some recent specific studies from our laboratory include the development of multiple quantum coherence methods for studies of ordered water in anisotropic macromolecular assemblies, studies of the degree of restriction of water diffusion in cellular systems, multiple selective inversion imaging to depict the ratios of proton pool sizes and rates of magnetization transfer between proton populations, and diffusion tensor imaging to depict tissue anisotropies. These illustrate how approaches to obtain structural information from biological media are also relevant to porous media. For example, the recent development of oscillating gradient spin echo techniques (OGSE), an approach that extends our ability to resolve apparent diffusion changes over different time scales in tissues, has also been used to compute surface to volume measurements in assemblies of pores. Each of the new methods can be adapted to provide spatially resolved quantitative measurements of properties of interest, and these can be efficiently acquired with good accuracy using fast imaging methods such as echo planar imaging. The community of NMR scientists focused on applications to porous media should remain in close communication with those who use MRI to study problems in biomedicine, to their mutual benefits.     

Effective Gradients in Porous Media Due to Susceptibility Differences

In porous media, magnetic susceptibility differences between the solid phase and the fluid filling the pore space lead to field inhomogeneities inside the pore space. In many cases, diffusion of the spins in the fluid phase through these internal inhomogeneities controls the transverse decay rate of the NMR signal. In disordered porous media such as sedimentary rocks, a detailed evaluation of this process is in practice not possible because the field inhomogeneities depend not only on the susceptibility difference but also on the details of the pore geometry. In this report, the major features of diffusion in internal gradients are analyzed with the concept of effective gradients. Effective gradients are related to the field inhomogeneities over the dephasing length, the typical length over which the spins diffuse before they dephase. For the CPMG sequence, the dependence of relaxation rate on echo spacing can be described to first order by a distribution of effective gradients. It is argued that for a given susceptibility difference, there is a maximum value for these effective gradients,g_max, that depends on only the diffusion coefficient, the Larmor frequency, and the susceptibility difference. This analysis is applied to the case of water-saturated sedimentary rocks. From a set of NMR measurements and a compilation of a large number of susceptibility measurements, we conclude that the effective gradients in carbonates are typically smaller than gradients of current NMR well logging tools, whereas in many sandstones, internal gradients can be comparable to or larger than tool gradients.     

Reconstruction of porous material geometry by stochastic optimization based on bulk NMR measurements of the dipolar field

The dependence of the bulk signal intensity from a CRAZED NMR pulse sequence on magnetic field gradient strength and direction as a method to probe the geometry of porous materials is investigated. In this article, we report on the reconstruction of three-dimensional media consisting of a void phase and an NMR-observable liquid phase using the bulk intensity of the distant dipolar field. The correlation gradient strength and direction provide the spatial encoding of the material geometry. An integral equation for the total signal intensity is then solved numerically by a simulated annealing algorithm to recover the indicator function of the fluid phase. Results show that cylindrical and spherical structures smaller than the volume contributing to the NMR signal can be resolved using three values of the correlation distance and three orthogonal gradient directions. This is done by minimizing a cost function which measures the distance between the bulk signal dependence on gradient parameters for the simulated configuration and the signal dependence for the target configuration. The algorithm can reconstruct and differentiate their spherical and cylindrical phase-inverted equivalents. It can also differentiate horizontal from vertical cylinders, demonstrating the potential for assessing structural anisotropy and other coarse geometric quantifiers in a porous material.     

Detection of the high eigenmodes of spin diffusion in porous media

The dynamics of spin diffusion in a fluid is governed by the Torrey-Bloch equations, and the solution is often expressed mathematically in an eigenmode expansion. We report an experimental demonstration of the excitation and detection of a wide range of eigenmodes in porous media by exploring the inhomogeneous internal magnetic field in the pore space. The nodal character of the eigenfunctions of the high eigenmodes was clearly observed. The methodology of excitation and detection of the high eigenmodes may be used to better characterize pore geometry.     

Time-of-flight flow imaging using NMR remote detection

A time-of-flight imaging technique is introduced to visualize fluid flow and dispersion through porous media using NMR. As the fluid flows through a sample, the nuclear spin magnetization is modulated by rf pulses and magnetic field gradients to encode the spatial coordinates of the fluid. When the fluid leaves the sample, its magnetization is recorded by a second rf coil. This scheme not only facilitates a time-dependent imaging of fluid flow, it also allows a separate optimization of encoding and detection subsystems to enhance overall sensitivity. The technique is demonstrated by imaging gas flow through a porous rock.     

管内层流充分发展段等效热边界层的构造及其场协同分析

本文采用数值计算方法分析了圆管中部分填充多孔介质时在充分发展段的流动与传热特征,并运用场协同原理分析了其强化传热机理.结果表明,采用部分填充多孔介质的方法可以在管内流动充分发展段构造等效热边界层;选择高热导率、高孔隙率的多孔介质以及合理的多孔介质填充率,可以显著强化换热而不引起流动阻力的过度增加.与传统的在流体边界区域采取传热强化措施不同,此时,主要是在流动的中心区域采取传热强化措施.计算表明,性能评价指标PEC数可达6,因此,本文方法对于高效、低阻换热器的设计有一定的借鉴意义.     

Influential Factors of Internal Magnetic Field Gradient in Reservoir Rock and Its Effects on NMR Response

Nuclear magnetic resonance (NMR) plays a significant role in porous media analysis and petroleum exploration, but its response is significantly influenced by the internal magnetic field gradient in fluid saturated porous medium, which obviously limits the accuracy of rock core analysis and logging interpretation. The influential factors of the internal magnetic field gradient in formation and its influences on NMR response are studied in this paper, based on NMR mechanism through one- and two-dimensional core NMR experiments. The results indicate that the internal magnetic field gradient is positively correlated with the static magnetic field strength and the magnetic susceptibility difference between pore fluid and solid grains, while it presents negative correlation with pore radius. The internal magnetic field gradient produces an additional diffusion relaxation in hydrogen relaxation system and accelerates the attenuation of magnetization vector. As a result, T₂ spectrum shifts to the left and NMR porosity and diffusion coefficient of the fluid could be inaccurate. This research sets a foundation for the NMR porosity correction and fluid distribution on T₂-G maps based on the internal magnetic field gradient correction.     

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.     

Dissimilar electro-osmotic flow and ionic current recirculation patterns in porous media detected by NMR mapping experiments

Random-site percolation clusters were milled into ceramic (polar) and polystyrene (nonpolar) plates as a paradigm for porous media or complex microsystem channel networks. The pore space was filled with electrolyte solutions. Using NMR microscopy techniques, maps of the following quantities were recorded: (i) flow velocity driven by external pressure gradient, (ii) electro-osmotic flow (EOF) velocity, (iii) ionic current density in the presence of EOF, (iv) ionic current density in the absence of EOF. As far as possible, the experiments were supplemented by computational fluid dynamics simulations. It is shown that electro-osmotic flow as well as the electric current density include vortices and recirculation patterns. Remarkably, all transport patterns turned out to be dissimilar, and the occurrence and positions of vortices do not coincide in the different maps.     

Analysis of porosity in porous silicon using hyperpolarized 129Xe two-dimensional exchange experiments

The porosity in porous silicon was characterized using hyperpolarized (HP) xenon as a probe. HP xenon under conditions of continuous flow allows for the rapid acquisition of xenon NMR spectra that can be used to characterize a variety of materials. Two-dimensional exchange spectroscopy (EXSY) (129)Xe NMR experiments using HP xenon were performed to obtain exchange pathways and rates of xenon mobility between pores of different dimensions within the structure of porous silicon and to the gas phase above the sample. Pore sizes are estimated from chemical shift information and a model for pore geometry is presented.     

NMR 1D-imaging of water infiltration into mesoporous matrices

It is shown that coupling nuclear magnetic resonance (NMR) 1D-imaging with the measure of NMR relaxation times and self-diffusion coefficients can be a very powerful approach to investigate fluid infiltration into porous media. Such an experimental design was used to study the very slow seeping of pure water into hydrophobic materials. We consider here three model samples of nuclear waste conditioning matrices which consist in a dispersion of NaNO₃ (highly soluble) and/or BaSO₄ (poorly soluble) salt grains embedded in a bitumen matrix. Beyond studying the moisture progression according to the sample depth, we analyze the water NMR relaxation times and self-diffusion coefficients along its 1D-concentration profile to obtain spatially resolved information on the solution properties and on the porous structure at different scales. It is also shown that, when the relaxation or self-diffusion properties are multimodal, the 1D-profile of each water population is recovered. Three main levels of information were disclosed along the depth-profiles. They concern (i) the water uptake kinetics, (ii) the salinity and the molecular dynamics of the infiltrated solutions and (iii) the microstructure of the water-filled porosities: open networks coexisting with closed pores. All these findings were fully validated and enriched by NMR cryoporometry experiments and by performing environmental scanning electronic microscopy observations. Surprisingly, results clearly show that insoluble salts enhance the water progression and thereby increase the capability of the material to uptake water.     

Some perspectives on dispersion and the use of ensemble-averaged PGSE NMR

Magnetic resonance methodology has made a significant impact in helping us understand the physics of porous media. Among an important class of experiments is that set of techniques designed to measure fluid dispersion. This paper provides some background on some of the underlying physics of dispersion, and outlines some of the NMR approaches that have proven successful. The local and nonlocal dispersion tensors are described and the prospects for future NMR advances considered.     

应用粒子图像测试技术测量球床多孔介质单相流动的流场

多孔介质在生产生活以及科技发展中的应用十分广泛, 随着能源、化工、冶金和原子能等领域技术的发展, 以及近代工农业生产技术的进步, 大量多孔介质的传热传质问题逐渐出现, 进一步促进了多孔介质学科的形成和发展, 使其成为当今科学技术中令人瞩目的研究热点之一. 通过实验获得准确的实验图像和数据, 并使用相应软件对实验所得数据和流体流动图像进行深度分析, 这样既有真实可靠的实际数据, 又有直观的理论的支持, 使对多孔介质的研究更为完善. 实验结合粒子图像测试技术和折射率匹配技术对叉排排列玻璃球多孔介质填充床内的流体流动转变过程进行流场测试, 并提取数据, 采用Tecplot软件对提取数据进行处理, 得出流体流动机理的转变过程. 实验固相为由直径25 mm水晶玻璃球叉排堆积而成的填充床, 液相为65%苯甲醇和35% 无水乙醇配制的匹配液. 液相与固相的折射率都为1.477, 成功消除由于折射率不匹配引起的激光光线偏折. 实验得到雷诺数为 4.7 ≤ Re ≤ 1000时球床内流场图, 对比不同雷诺数时流场和流线变化得出: 随着雷诺数的增加, 流线变得越来越紊乱; 当雷诺数在220以上时, 球床内漩涡在尺寸变化上出现突跃, 在位置和形态变化表现出随机特征, 预示进入了稳定的湍流.     

多孔介质内溶解与沉淀过程的格子Boltzmann方法模拟

本文采用格子Boltzmann方法模拟了多孔介质内的溶解和沉淀现象, 并分析了雷诺数、施密特数、达姆科勒数对多孔介质孔隙结构及浓度分布的影响. 结果表明: 对于多孔介质内的溶解(沉淀)过程, 当雷诺数越大时, 孔隙率越大(小), 平均浓度值越小(大); 当达姆科勒数或施密特数较小时, 溶解和沉淀过程均受反应控制, 此时反应在多孔介质的固体表面较为均匀的发生; 当达姆科勒数或施密特数较大时, 溶解和沉淀过程均受扩散控制, 此时反应主要发生在上游及大孔隙区域.     

Effects of hydrophobic treatments of stone on pore water studied by continuous distribution analysis of NMR relaxation times.

The effects of protective hydrophobic products applied to porous media such as stone or mortar vary greatly with the product, the porous medium, and the mode of application. Nuclear Magnetic Resonance (NMR) measurements on fluids in the pore spaces of both treated and untreated samples can give information on the contact of the fluid with the internal surfaces, which is affected by all the above factors. Continuous distributions of relaxation times T(1) and T(2) of water in the pores of both synthetic and natural porous media were obtained before and after hydrophobic treatment. The synthetic porous media are ceramic filter materials characterized by narrow distributions of pore dimensions and show that the treatment does not produce large changes in the relaxation times of the water. For three travertine samples most of a long relaxation time component, presumably from the largest pores, remains after treatment, while the amplitude of an intermediate component is greatly reduced. For three pudding-stone samples, treatment leads to a substantial loss from the long component and an even greater loss from the intermediate component.     

DTI of trabecular bone marrow

The development of NMR diffusion imaging and diffusion tensor imaging (DTI) has offered the possibility of studying the porous structures beyond anatomical imaging. In fact, random molecular motions, within tissue components, probe tissue microstructures. Up to now, the DTI method was mainly used to investigate cerebral morphology and study white matter diseases. In this study, it has been applied to trabecular bone marrow analysis to obtain structural information on spongy bone tissue. Our first results show that DTI could represent an important tool in studying the microstructural architecture of the trabecular bone as well as the microarchitecture of porous media.