Probing porous media with gas diffusion NMR.

We show that gas diffusion nuclear magnetic resonance (GD-NMR) provides a powerful technique for probing the structure of porous media. In random packs of glass beads, using both laser-polarized and thermally polarized xenon gas, we find that GD-NMR can accurately measure the pore space surface-area-to-volume ratio, S/V rho, and the tortuosity, alpha (the latter quantity being directly related to the system's transport properties). We also show that GD-NMR provides a good measure of the tortuosity of sandstone and complex carbonate rocks.     

Imaging of laser-polarized solid xenon

The enhanced spin polarization produced by optical pumping of gaseous rubidium/xenon samples has made possible a number of recent experiments in nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI). Here we report MRI of laser-polarized xenon in the solid phase at low temperature. Due to the high xenon density in the solid phase and the enhanced spin polarization, it is possible to achieve high intensity and spatial resolution of the image. Signals were observed from xenon films solidified onto the glass container walls and not from an enclosed chili pepper.     

Dissolution of laser-polarized xenon in benzene

The study of the dissolution of laser-polarized xenon in degassed deuterated benzene is reported. We show that the time evolution of the xenon signal implies that a transient convective process takes place. It is characterized by velocity-encoding magnetic resonance measurements and MRI experiments.     

Direct evidence of a magnetization transfer between laser-polarized xenon and protons of a cage-molecule in water

In a dedicated experimental setup, we directly prepare liquid-state NMR samples containing laser-polarized xenon with nuclear polarization larger than 5% at pressures up to 4 bars. Coating of the NMR tube surface allows us to increase the self-relaxation time of xenon in the gaseous phase to approximately 4.5 hours. Using a modified SPINOE pulse sequence, we present the first direct detection of a regioselective proton signal enhancement of a molecule -cyclodextrin) dissolved in water resulting from cross-polarization between laser-polarized xenon and protons. Received 16 March 2000 and Received in final form 22 May 2000     

Chemical shift imaging with continuously flowing hyperpolarized xenon for the characterization of materials

In this contribution we report new approaches to the MRI of materials using continuously produced laser-polarized (129)Xe gas. This leads to vastly improved sensitivity and makes new kinds of information available. The hyperpolarized xenon is produced in a continuous flow system that conveniently delivers the xenon at low partial pressure to probes for NMR and MRI experiments. We illustrate applications to the study of micropore and other kinds of void space and show for the first time that with flowing hyperpolarized xenon it is possible to obtain chemical-shift-resolved images in a relatively short time.     

NMR study of the dissolution of laser-polarized xenon

NMR of laser-polarized xenon is used to probe the dissolution behaviour of the noble gas in different liquids. The dissolution and self-relaxation rates are extracted via a macroscopic model, and comparison of the decay rate of the xenon magnetization in deuterated and non-deuterated solvent pairs allows the determination of the pure dipole-dipole contribution to relaxation. A transient convective effect, tentatively assigned to the xenon concentration gradient, is observed and characterized by diffusion encoding MRI experiments. The flow of xenon penetrates inside the solvent near the walls of the NMR tube, the longitudinal images showing a “” shape, the transverse ones a “O” shape. This convection effect has implications for delivery conditions of laser-polarized xenon in continuous flow experiments and magnetic resonance imaging. Received 29 April 2002 / Received in final form 26 July 2002 Published online 22 October 2002 RID="a" ID="a"e-mail: hdesvaux@cea.fr RID="b" ID="b"URA CNRS/CEA 331     

Applications of controlled-flow laser-polarized xenon gas to porous and granular media study

We report initial NMR studies of continuous flow laser-polarized xenon gas, both in unrestricted tubing, and in a model porous media. The study uses Pulsed Gradient Spin Echo-based techniques in the gas-phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients. Pulsed Gradient Echo studies of continuous flow laser-polarized xenon gas in unrestricted tubing indicate clear diffraction minima resulting from a wide distribution of velocities in the flow field. The maximum velocity experienced in the flow can be calculated from this minimum, and is seen to agree with the information from the complete velocity spectrum, or motion propagator, as well as previously published images. The susceptibility of gas flows to parameters such as gas mixture content, and hence viscosity, are observed in experiments aimed at identifying clear structural features from echo attenuation plots of gas flow in porous media. Gas-phase NMR scattering, or position correlation flow-diffraction, previously clearly seen in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack is not so clear in experiments using a different gas mixture. A propagator analysis shows most gas in the sample remains close to static, while a small portion moves through a presumably near-unimpeded path at high velocities.     

Investigation of non-acoustical parameters of compressed melamine foam materials

A series of careful non-acoustical parameters measurements using 5 ‘Illtec’ melamine foam and 10 ‘Basotect TG’ melamine foam samples have been made. Flow resistivity, tortuosity, porosity, viscous characteristic length and thermal characteristic length of two types of compressed melamine foam materials with different foam magnifications have been investigated. It has been found that a relationship between the flow resistivity, fibre equivalent diameter and bulk density exists for each of the compressed melamine foam materials.This paper also discusses relationships between the non-acoustical parameters and compression rates in the compressed melamine foam media.     

Deduction of tortuosity and porosity from acoustic reflection and transmission measurements on thick samples of rigid-porous materials

An acoustic method for obtaining the tortuosity, and porosity of thick samples of rigid porous materials consisting of large (>1 mm) grains or fibres is proposed. The method uses pulses with central frequencies close to 12 kHz and an approximate bandwidth of between 3 and 20 kHz. In this frequency range, inertial rather than viscous or scattering effects dominate sound propagation in large pores. This allows application of the high frequency limit of the “equivalent fluid” model. Both reflected and transmitted signals are used in the measurements. Tortuosity is deduced from the high frequency limit of the phase speed (obtained from transmission data) and porosity is obtained from the high frequency limit of the reflection coefficient once the tortuosity is known. The method is shown to give good results in the cases where significant scattering does not occur until frequencies much higher than the upper limit of the pulse bandwidth. Apart from its applicability to samples with several centimetres thickness, the method needs only one set of measurements with the sample to deduce both tortuosity and porosity. In principle the method can be used also to estimate characteristic lengths. However, the errors are found to be larger and the results less consistent than for tortuosity.     

Novel MRI applications of laser-polarized noble gases

Gas-phase nuclear magnetic resonance (NMR) has great potential as a probe for a variety of interesting physical and biomedical problems that are not amenable to study by water or similar liquid. However, NMR of gases was largely neglected due to the low signal obtained from the thermally polarized gases with very low sample density. The advent of optical pumping techniques for enhancing the polarization of the noble gases³He and¹²⁹Xe has bought new life to this field, especially in medical imaging where³He lung inhalation imaging is approaching a clinical application. However, there are numerous applications in materials science that also benefit from the use of these gases. We review primarily nonmedical applications of laser-polarized noble gases for both NMR imaging and spectroscopy and highlight progress with examples from our laboratory including high-resolution imaging at millitesla applied field strength and velocity imaging of convective flow. Porous media microstucture has been probed with both thermal and laser-polarized xenon, as xenon is an ideal probe due to low surface interaction with the grains of the porous media.     

Magnetic resonance imaging of convection in laser-polarized xenon

We demonstrate nuclear magnetic resonance (NMR) imaging of the flow and diffusion of laser-polarized xenon (129Xe) gas undergoing convection above evaporating laser-polarized liquid xenon. The large xenon NMR signal provided by the laser-polarization technique allows more rapid imaging than one can achieve with thermally polarized gas-liquid systems, permitting shorter time-scale events such as rapid gas flow and gas-liquid dynamics to be observed. Two-dimensional velocity-encoded imaging shows convective gas flow above the evaporating liquid xenon, and also permits the measurement of enhanced gas diffusion near regions of large velocity variation.     

Pore-Size Distributions and Tortuosity in Heterogeneous Porous Media

The diffusion coefficient, measured at long observation times by pulsed-held-gradient NMR, can in principle be used to estimate the tortuosity of a porous medium. This method is useful for glass-sphere packs, but we find that it does not generally work for porous sedimentary rock. Natural sedimentary rocks are characterized by complex microgeometries and broad distributions of pore sizes, which cannot be adequately sampled by diffusing molecules in experimentally accessible observation times. The time-dependent diffusion coefficient D(t) can be distinctly irregular for rocks with very large pores. In heterogeneous porous media, determination of pore-size distribution by relaxation-time measurements and tortuosity by PFG diffusion measurements are mutually exclusive.     

Study of NMR porosity for terrestrial formation in China

NMR logging is an effective method for porosity measurement. NMR-derived porosity only comes from the pore fluid and is, in principle, not affected by rock matrix. However, it is found that the difference between NMR-derived and conventional log-derived porosities is often between 2 to 6 pu, which is unacceptable, in terrestrial formation in China. In the paper, the theory of NMR porosity was reviewed. The influence factors on NMR porosity error were analyzed based on NMR core measurements. More than 30 core samples with a wide range of porosities including sandstone, limestone and artificial ceramic were chosen for the conventional and NMR porosity measurements. The current NMR data acquisition method was studied based on laboratory NMR core measurements and found to be not good for terrestrial formation. A new NMR data acquisition method suiting for terrestrial formation in China was proposed and much improved the accuracy of NMR porosity measurement. It is suggested that the analysis of core samples from different regions should be carried out before logging in order to obtain accurate NMR porosity.     

Spatially resolved measurement of rock core porosity

Density weighted, centric scan, Conical SPRITE MRI techniques are applied in the current work for local porosity measurements in fluid saturated porous media. The methodology is tested on a series of sandstone core samples. These samples vary in both porosity and degree of local heterogeneity due to bedding plane structure. The MRI porosity measurement is in good agreement with traditional gravimetric measurements of porosity. Spatially resolved porosity measurements reveal significant porosity variation in some samples. This novel MRI technique should have applications to the characterization of local porosity in a wide variety of porous media.     

Measurements of tortuosity in stereolithographical bone replicas using audiofrequency pulses

The tortuosity of five air-filled stereolithographical cancellous bone replicas has been obtained from measurements using audiofrequency pulses in a rectangular waveguide. The data obtained from the replicas yields information about anisotropy with respect to orthogonal axes of the passages that would be marrow filled in vivo. A strong relationship has been found between the acoustically measured tortuosity and the independently measured porosity. Use of stereolithographical bone replicas has the potential to simulate perforation and thinning of cancellous bone and hence evaluate the dependence of acoustic properties on cancellous bone microstructure. As an "extreme" illustration of such use, "inverses" of the original replicas have been manufactured and acoustic measurements have been made on them. The data reveal significantly greater tortuosity of the passages that are geometrically equivalent to the original solid bone structures.     

Première détection d'un transfert d'aimantation entre du xénon polarisé par laser et des protons d'une protéine

The conditions of observation and characterization of magnetization transfert between laser-polarized xenon 129 and protein protons are addressed. This is experimentally illustrated by its first detection obtained on the wheat non-specific lipid transfer protein.     

Analysis of permeability for the fractal-like tree network by parallel and series models

This work investigates the hydraulic conductivity properties in the fractal-like tree networks between one point and a straight line. The expression for the effective permeability of the networks is derived based on the parallel and series models and the relationship between the effective permeability and the geometry structures of the network is analyzed. It is found the effective permeability after including tortuosity is about 20% lower than that without considering the tortuosity, and the tortuosity effect should be included in analysis of hydraulic conductivity properties in the networks; the effective permeability is very sensitive to the geometrical structures of the network. A comparison of the fractal-like tree network with the traditional parallel net indicates that the fractal-like tree network can provide much higher permeability than that of the traditional parallel net.     

Estimation of Permeability by Integrating Nuclear Magnetic Resonance (NMR) Logs with Mercury Injection Capillary Pressure (MICP) Data in Tight Gas Sands

It has been a great challenge to determine permeability in tight gas sands due to the generally poor correlation between porosity and permeability. The Schlumberger Doll Research (SDR) and Timur–Coates permeability models, which have been derived for use with nuclear magnetic resonance (NMR) data, also lose their roles. In this study, based on the analysis of the mercury injection experiment data for 20 core plugs, which were drilled from tight gas sands in the Xujiahe Formation of central Sichuan basin, Southwest China, two empirical correlations between the pore structure index ( $ \sqrt {{K \mathord{\left/ {\vphantom {K \varphi }} \right. \kern-0em} \varphi }} $ , defined by the square root of the ratio of rock permeability and porosity) and the R ₃₅ (the pore throat radius corresponding to 35.0 % of mercury injection saturation), the pore structure index and the Swanson parameter have been developed. To consecutively estimate permeability in field applications, based on the study of experimental NMR measurements for 36 core samples, two effective statistical models, which can be used to derive the Swanson parameter and R ₃₅ from the NMR T ₂ logarithmic mean value, have been established. These procedures carried out on the experimental data set can be extended to reservoir conditions to estimate consecutive formation permeability along the intervals with which NMR logs were acquired. The processing results of several field examples using the proposed technique show that the classification scale models are effective only in tight gas reservoirs, whereas the SDR and Timur–Coates models are inapplicable. The R ₃₅-based model is of significance in thin sands with high porosity and high permeability, but the predicted permeability curves in tight gas sands are slightly lower. In tight gas and thin sands, the Swanson parameter model is all credible.     

岩心核磁共振实验对低孔低渗碳酸盐岩储层的适应性研究

低孔低渗碳酸盐岩储层矿物成分复杂、岩石骨架参数难以确定、储集空间类型多样、孔隙结构及孔渗关系复杂、常规测井曲线响应特征不明显,使其测井评价极其困难．本文利用核磁共振测井定量评价低孔低渗碳酸盐岩储层岩心的孔隙结构、计算储层参数．利用T₂谱分布曲线分析孔隙结构、计算T₂截止值;在此基础上计算岩心总孔隙度、有效孔隙度、束缚水孔隙度、渗透率等储层参数,并与常规岩心实验结果进行对比分析;最后,总结出核磁共振测井在低孔低渗储层中的应用优势与局限,为核磁共振测井评价模型的建立提供基础数据．     

Time-of-flight remote detection MRI of thermally modified wood

We demonstrate that time-of-flight (TOF) remote detection (RD) magnetic resonance imaging (MRI) provides detailed information about physical changes in wood due to thermal modification that is not available with conventional nuclear magnetic resonance (NMR) based techniques. In the experiments, xenon gas was forced to flow through Pinus sylvestris pine wood samples, and the flow paths and dispersion of gas atoms were observed by measuring ¹²⁹Xe TOF RD MRI images from the samples. MRI sensitivity of xenon was boosted by the spin exchange optical pumping (SEOP) method. Two different samples were studied: a reference sample, dried at low temperature, and a modified sample, which was thermally modified at 240 °C after the drying. The samples were taken next to each other from the same wood plank in order to ensure the comparability of the results. The most important conclusion is that both the smaller dispersion observed in all the TOF RD experiments independent of each other and the decreased amount of flow paths shown by the time projection of z-encoded TOF RD MRI experiment imply that a large amount of pits connecting tracheid cells are closed in thermal modification. Closed pits may be one reason for reduced moisture content and improved dimensional stability of wood achieved in thermal modification. This is the first time biological samples have been investigated by TOF RD MRI.