Determining NMR flow propagator moments in porous rocks without the influence of relaxation

Flow propagators, used for the study of advective motion of brine solution in porous carbonate and sandstone rocks, have been obtained without the influence of Nuclear Magnetic Resonance (NMR) relaxation times, T₁ and T₂. These spin relaxation mechanisms normally result in a loss of signal that varies depending on the displacement ζ of the flowing spins, thereby preventing the acquisition of quantitative propagator data. The full relaxation behaviour of the system under flow needs to be characterised to enable the implementation of a true quantitative measurement. Two-dimensional NMR correlations of ζ − T₂ and T₁ − T₂ are used in combination to provide the flow propagators without relaxation weighting. T₁ − ζ correlations cannot be used due to the loss of T₁ information during the displacement observation time Δ. Here the moments of the propagators are extracted by statistical analysis of the full propagator shape. The measured displacements (first moments) are seen to correlate with the expected mean displacements for long observation times Δ. The higher order moments of the propagators determined by this method indicate those obtained previously using a correction were overestimated.     

Recent Fourier and Laplace perspectives for multidimensional NMR in porous media

Multidimensional NMR techniques used in the measurement of molecular displacements, whether by diffusion or advection, and in the measurement of nuclear spin relaxation times are categorised. Fourier-Fourier, Fourier-Laplace and Laplace-Laplace methods are identified, and recent developments discussed in terms of the separation, correlation and exchange perspective of multidimensional NMR spectroscopy.     

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.     

On the use of 2D correlation and exchange NMR spectroscopy in organic porous materials

Two-dimensional (2D) nuclear magnetic resonance (NMR) methods for the investigation of correlation and exchange have been introduced in recent years and have been applied to a range of different systems. Here, we report on the use of 2D NMR diffusion-diffusion correlation spectroscopy for the investigation of diffusion anisotropy in cellular plant tissues and of diffusion-diffusion exchange spectroscopy for the study of the diffusive exchange of dextran in a dispersion of polyelectrolyte multilayer hollow capsules. Furthermore, diffusion-relaxation correlation spectroscopy was applied to both systems.     

Velocity autocorrelation spectra of fluid in porous media measured by the CPMG sequence and constant magnetic field gradient

Carr-Purcell-Meiboom-Gill (CPMG) train of radiofrequency pulses applied to spins in the constant magnetic field gradient is an efficient variant of the modulated magnetic field gradient spin echo method, which provides information about molecular diffusion in the frequency domain instead of in the time domain as with the two-pulse gradient spin echo. The frequency range of this novel technique is broad enough to sample the power spectrum of displacement fluctuation in water-saturated pulverized silica (SiO2) and provides comprehensive information about the molecular restricted motion as well as about the structure of the medium.     

Formation of p-cresol:piperazine complex in solution monitored by spin-lattice relaxation times and pulsed field gradient NMR diffusion measurements

A study of the nature of the anthelmintic p-cresol:piperazine complex in chloroform solution has been conducted using different NMR techniques: self-diffusion coefficients using DOSY; NOE, NULL, and double-selective T1 measurements to determine inter-molecular distances; and selective and non-selective T1 measurements to determine correlation times. The experimental results in solution and CP-MAS were compared to literature X-ray diffraction data using molecular modeling. It was shown that the p-cresol:piperazine complex exists in solution in a very similar manner as it does in the solid state, with one p-cresol molecule hydrogen bonded through the hydroxyl hydrogen to each nitrogen atom of piperazine. The close correspondence between the X-ray diffraction data and the inter-proton distances obtained by NULL and double selective excitation techniques indicate that those methodologies can be used to determine inter-molecular distances in solution.     

Measurement of multilamellar onion dimensions under shear using frequency domain pulsed gradient NMR

We present a simple method by which the dimensions of shear-induced multilamellar vesicles (MLVs), also known as onions, can be measured during the shearing process itself. This approach is based on the use of a closely spaced train of magnetic field gradient pulses applied during a CPMG echo sequence. The CPMG train compensates flow effects while the frequency-dependence of apparent diffusion can reveal the onion size. We present here a simple phenomenological model for restricted diffusion in multilamellar vesicles, which may be used to interpret the resulting diffusion spectrum. We demonstrate this approach with MLVs formed from the lamellar phase of sodium dodecyl sulfate (SDS) in water and octanol.     

An evaluation of the contributions of diffusion and exchange in relaxation enhancement by MRI contrast agents

Magnetic compounds are known to enhance water proton relaxation, either by diffusion or by proton exchange. An experimental procedure to distinguish both mechanisms is proposed and validated by relaxation measurements made in water-methanol solutions of Dy(3+), Ni(2+), Gd(3+), Tempo, and AMI-25. The test discriminates according to the character of the transverse relaxation in water-methanol solutions: a mono-exponential decay corresponds to diffusion, while a bi-exponential decay indicates the contribution of a proton exchange. The study of ferritin and akaganeite particle solutions confirms the occurrence of a proton exchange between protons belonging to hydroxyl groups of the particle surface and free water protons.     

Spectral characterization of diffusion in porous media by the modulated gradient spin echo with CPMG sequence

Carr-Purcell-Meiboom-Gill train of radiofrequency pulses applied to spins in the constant magnetic field gradient is an efficient variant of the modulated magnetic field gradient spin echo method, which provides information about molecular diffusion in the frequency-domain instead in the time-domain as with the two-pulse gradient spin echo. The frequency range of novel technique is broad enough to sample the power spectrum of displacement fluctuation in water-saturated pulverized silica (SiO(2)) and provides comprehensive information about the molecular restricted motion as well as about the structure of medium.     

Observation of molecular migration in porous media using 2D exchange spectroscopy in the inhomogeneous magnetic field

We present a new method for observing fluid diffusion in a porous medium. The method employs 2D exchange spectroscopy for molecules diffusing in the presence of local magnetic field inhomogeneities, in our case distilled water in various sized glass bead packs. Our experiment involves an acquisition and evolution time domain with the two Fourier domains corresponding to the spectral distribution of local fields. We show that exchange in the internal magnetic field can be seen in a 2D spectrum with a characteristic time on the order of that required to diffuse 0.15 sphere diameters with similar behavior found for computer simulations. The method is potentially useful for studying the internal migrations in more complicated systems such as sandstones or other porous media.     

Exploring the surface permeability of nanoporous particles by pulsed field gradient NMR

A new method to determine the surface permeability of nanoporous particles is proposed. It is based on the comparison of experimental data on tracer exchange and intracrystalline molecular mean square displacements as obtained by the PFG NMR tracer desorption technique with the corresponding solutions of the diffusion equation via dynamical Monte Carlo simulations. The method is found to be particularly sensitive in the "intermediate" regime, when the influence of intracrystalline diffusion and surface resistances of the nanoporous crystal on molecular transport are comparable and the conventional method fails. As an example, the surface permeabilities of two samples of zeolite NaCaA with different crystal sizes are determined with methane, as a probe molecule, at room temperature.     

Predictions of pulsed field gradient NMR echo-decays for molecules diffusing in various restrictive geometries. Simulations of diffusion propagators based on a finite element method

Pulsed field gradient NMR diffusometry is a promising tool for investigating structures of porous material through determinations of dynamic displacements of molecules in porous systems. A problem with this approach is the lack of closed analytical expressions for echo-decays in anything but idealized pore geometries. We present here an approach based on calculating the appropriate diffusion propagator by means of finite element calculations. The suggested method is quite general, and can be applied to arbitrary porous systems. The protocol for the calculations is outlined and we show results from some different cases: diffusion in confined geometries and in systems that are spatially inhomogeneous with respect to concentration.     

脉冲涡流检测瞬态涡流场的时域解析模型

应用Laplace反变换技术建立脉冲涡流检测瞬态涡流场的时域解析模型.首先,基于电磁波的反射与透射理论,应用截断区域特征函数展开式法建立瞬态涡流场的复频域模型,然后通过求解模型极点及其留数应用部分分式展开法求解复频域模型的Laplace反变换,从而建立阶跃型和指数型电流激励下瞬态涡流场的时域解析模型.所建模型具有实现简单、效率高、模型精度不受吉布斯效应影响等优点.最后应用基于Fourier反变换的探头瞬态感应电压模型对本文所建模型,实验结果验证了本文所建模型的正确性.     

Structure and dynamics of poly(carbosilane) dendrimers as revealed by pulsed field gradient NMR technique

The self-diffusion of poly(carbosilane) dendrimer macromolecules solutions in the high-concentration region starting from the polymer block was investigated by pulsed field gradient nuclear magnetic resonance techniques. A restriction of diffusion was observed for the concentration region of 50–95 wt% of dendrimer in tetrachloride CCl₄ solutions. This phenomenon has been explained by the formation of solutions at a thermodynamical nonequilibrium. A theoretical approach on the basis of thermodynamics and statistical mechanics was developed.     

Combination of schlieren and pulsed TV holography in the study of a high-speed flame jet

This paper presents studies of the propagation of a high-speed turbulent flame jet of an air/hydrogen gas mixture. The experimental results are recorded with the schlieren and the pulsed TV holography method. These methods are compared and combined to benefit from the advantages of each of them. Abel inversion has been used to achieve three-dimensional information i.e. refractive index distributions. Evaluation, calibration and Abel inversion algorithms are described together with experimental results. The results obtained from the different techniques show remarkable similarities concerning both qualitative and quantitative aspects.     

Determination of pore space shape and size in porous systems using NMR diffusometry. Beyond the short gradient pulse approximation

The influence of finite length gradient pulses on NMR diffusion experiments on liquids confined to diffuse between two parallel planes is investigated. It is experimentally verified that the pore size decreases when determined using finite gradient pulses if the results are analyzed within the short gradient pulse approximation. The results are analyzed using the matrix formulation. The observed minima in the echo decay profiles are considerably less sharp than theoretical analysis would indicate and we suggest that this is due to the presence of a distribution of pore sizes in the sample. In addition, effects due to the presence of background gradients are discussed. It is argued that effects due to the finite length gradient pulses are relatively minor and in realistic applications the effects due to inhomogeneities in pore sizes and effects due to background gradients will constitute more serious problems in pore size determinations by means of NMR diffusometry.     

NMR relaxation of protons in tissues and other macromolecular water solutions

Nuclear magnetic resonance (NMR) longitudinal (T₁) and transverse (T₂) relaxation parameters have been evaluated for protein solutions, cellular suspensions and tissues using both data from our laboratory and the extensive literature. It is found that this data can be generalized and explained in terms of three water phases: free water, hydration water, and crystalline water. The proposed model which we refer to as the FPD model differs from similar models in that it assumes that free and hydration water are two phases with distinct relaxation times but that T₁ = T₂ in each phase. In addition there is a single correlation time for each rather than a distribution as assumed in most other models. Longitudinal decay is predicted to be single exponent in character resulting from a fast exchange between the free and hydration compartments. Transverse decay is predicted to be multiphasic with crystalline (T₂ 10 μsec), hydration (T₂ 10 sec) and free (T₂ 100 sec) water normally visible. The observed or effective transverse relaxation times for both the hydration and free water phases are greatly affected by the crystalline phase and are much shorter than the inherent relaxation times.     

Investigations of polymer dynamics in nanoporous media by field cycling NMR relaxometry and the dipolar correlation effect

The chain dynamics of short-chain perfluoropolyether melts confined in Vycor nanoporous media has been characterized by field cycling nuclear magnetic resonance relaxometry and the dipolar correlation effect. The slowdown of motions under confinement, leading to larger residual dipolar couplings, has been probed by looking at the quotient of stimulated and primary echoes. Using field cycling relaxometry, it has been shown that there is strong evidence of reptation-like motion, even for such short-chain polymers as shown by the frequency and molecular weight dependences of the spin-lattice relaxation time.     

Polarization and transmission of microwaves in the magnetic suspension in the applied magnetic field

The production method of magnetic suspension consisting of ferromagnetic particles dispersed in cedarwood oil is presented at the beginning of this article. Next, the set-up for microwaves generation using a klystron is described. The main part of this paper concerning microwave transmission and polarization during its passage in samples of the produced magnetic suspension placed in a magnetic field is based on the following parameters: induction of this field, filling factor of magnetic suspension by ferromagnetic particles, dimensions of particles, viscosity of liquid carrier, and ratio of the magnetic field changes. Conducted investigations show that microwaves are damped and polarized in these magnetic suspensions. Obtained results are discussed and observed effects are explained by ordering of ferromagnetic particles in magnetic suspension by applied magnetic field.