Probing short length scales with restricted diffusion in a static gradient using the CPMG sequence.

We experimentally verify a new method of extracting the surface-to-volume ratio (S/V) of porous media with diffusion NMR. In contrast to the widely used pulsed field gradient (PFG) technique, which employs the stimulated echo coherence pathway, we use here the direct Carr-Purcell-Meiboom-Gill (CPMG) path. Even for high echoes, which exhibit ample attenuation due to diffusion in the field gradient, the relevant ruler length for the direct pathway is fixed by the diffusion length during a single inter-pulse spacing. The direct path, therefore, is well suited for probing shorter length scales than is possible with the conventional approach. In our experiments in a low-field static-gradient system, the direct CPMG pathway was found to be sensitive to structure an order of magnitude smaller than accessible with the stimulated-echo pathway.

Short-time restricted diffusion in a static gradient and the attenuation of individual coherence pathways.

We experimentally explore some of the implications of a recent theoretical study [J. Magn. Reson. 64 (2003) 145] for the measurement of restricted diffusion in connected porous media in a static gradient. In particular, we examine how restriction affects the short-time attenuation of different coherence pathways, all excited with the same sequence of slice-selective radiofrequency (RF) pulses, and how the various pathways make the transition to the long-time or tortuosity regime. We confirm that every pathway contains equivalent diffusional information and, for short times, yields the surface-to-volume ratio (S/V) of the confining space. We find also, in agreement with the theoretical predictions, that different pathways are controlled by different time scales and, thus, exhibit different sensitivity to restriction. This property might be exploited when designing optimal sequences to study restricted motion.

Effect of internal gradients in the nuclear magnetic resonance measurement of the surface-to-volume ratio.

We consider a system of spins diffusing in a static inhomogeneous (nonuniform-gradient) magnetic field B in a restricted geometry and in the presence of surface relaxation. We show that the short-time diffusional decay of nuclear magnetization is controlled by the field scattering kernel F(t) identical with [B(t)-B(0)](2), which is a measure of the average field inhomogeneity sampled by the spins in time t and does not depend on the particular sequence of radio-frequency pulses used. Magnetization in arbitrary sequences can be straightforwardly computed by evaluating elementary integrals of F(t). Diffusion takes place while the field is on, so that the spins precess as they diffuse, in contrast to the simpler problem of purely classical diffusion considered in [P. P. Mitra, P. N. Sen, and L. M. Schwartz, Phys. Rev. B 47, 8565 (1993)] which is applicable only to the ideal pulsed-field gradient experiment. We compute the short-time asymptotic form of F(t) and find that it depends on the surface-to-volume ratio (S/V) of the pore space as well as on the average of the gradients over the bounding surface. In a system with nonuniform gradients that vary faster near the surface than in the bulk, as for internal susceptibility fields, this gradient surface average may be much larger than the gradients in the bulk, significantly enhancing the apparent S/V. We discuss the application of our results to the widely used Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence as well as proposing a modification of it, which we term "padded" CPMG, that may be preferable in systems with significant surface relaxation. We indicate how each sequence can be used to probe the internal fields.

Effects of finite-width pulses in the pulsed-field gradient measurement of the diffusion coefficient in connected porous media.

We analytically compute the apparent diffusion coefficient D(app) for an open restricted geometry, such as an extended porous medium, for the case of a pulsed-field gradient (PFG) experiment with finite-width pulses. In the short- and long-time limits, we give explicit, model-independent expressions that correct for the finite duration of the pulses and can be used to extract the pore surface-to-volume (S/V) ratio as well as the tortuosity. For all times, we compute D(app) using a well-established model form of the actual time-dependent diffusion coefficient D(t) that can be obtained from an ideal narrow-pulse PFG. We compare D(app) and D(t) and find that, regardless of pulse widths and geometry-dependent parameters, the two quantities deviate by less than 20%. These results are in sharp contrast with the studies on closed geometries [J. Magn. Reson. A 117 (1995) 209], where the effects of finite gradient-pulse widths are large. The analytical results presented here can be easily adapted for different pulse protocols and time sequences.

Restricted diffusion in grossly inhomogeneous fields.

We analyze the effects of geometrical restriction on the nuclear magnetization of spins diffusing in grossly inhomogeneous fields where radio-frequency (RF) pulses are weak relative to the total field inhomogeneity, making the rotation angle space-dependent and thus exciting multiple coherence pathways. We show how to separate the effects of restricted diffusion from the effects of the pulses in the case when the change in the field experienced by a diffusing spin in the course of the experiment is small compared to the RF magnitude. We then derive explicit formulas for the contribution of individual coherence pathways to the total magnetization in arbitrary pulse sequences. We find that, for long diffusion times, restriction can dramatically alter the spectrum and the shape of a particular echo, while for short times, the correction will be proportional to the pore space surface-to-volume ratio. We demonstrate these results on the example of the early echoes of the Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence.