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R Kimmich

Publications and source records attributed to R Kimmich.

At least 19 recordsLinked to original sources

Rayleigh-Bénard percolation transition study of thermal convection in porous media: numerical simulation and NMR experiments.

Thermal convection was studied as a function of the porosity in random-site percolation model objects in a Rayleigh-Bénard configuration. NMR velocity mapping experiments and numerical simulations using the finite-volume method are compared. Velocity histograms were evaluated and can be described by power laws in a wide range. The maximum velocity as a function of the porosity indicates a combined percolation/Rayleigh-Bénard transition.

Journal Article↗

Flow through percolation clusters: NMR velocity mapping and numerical simulation study.

Three- and (quasi-)two-dimensional percolation objects have been fabricated based on Monte Carlo generated templates. The object size was up to 12 cm (300 lattice sites) in each dimension. Random site, semicontinuous swiss-cheese, and semicontinuous inverse swiss-cheese percolation models above the percolation threshold were considered. The water-filled pore space was investigated by nuclear magnetic resonance (NMR) imaging and, after exerting a pressure gradient, by NMR velocity mapping. The spatial resolutions of the fabrication process and the NMR experiments were 400 microm and better than 300 microm, respectively. The experimental velocity resolution was 60 microm/s. The fractal dimension, the correlation length, and the percolation probability can be evaluated both from the computer generated templates and the corresponding NMR spin density maps. Based on velocity maps, the percolation backbones were determined. The fractal dimension of the backbones turned out to be smaller than that of the complete cluster. As a further relation of interest, the volume-averaged velocity was calculated as a function of the probe volume radius. In a certain scaling window, the resulting dependence can be represented by a power law, the exponent of which was not yet considered in the theoretical literature. The experimental results favorably compare to computer simulations based on the finite-element method (FEM) or the finite-volume method (FVM). This demonstrates that NMR microimaging as well as FEM/FVM simulations reliably reflect transport features in percolation clusters.

Journal Article↗

Diffusion measurements with the aid of nutation spin echoes appearing after two inhomogeneous radiofrequency pulses in inhomogeneous magnetic fields.

Nutation echoes are generated by radiofrequency (RF) pulses with an inhomogeneous amplitude, B(1) = B(1)(r), in inhomogeneous magnetic fields, B(0) = B(0)(r). The two gradients of strengths G(1) and G(0), respectively, must be aligned in parallel for a maximum echo signal. After two RF pulses, two echoes appear at times tau(a) = 2 tau(1) + tau(2) + (G(1)/G(0))tau(1) and tau(b) = 2 tau(1) + tau(2) + 2(G(1)/G(0))tau(1), where tau(1) is the RF pulse duration and tau(2) the interpulse interval. It is shown that these echoes can favorably be employed for the determination of self-diffusion coefficients even in the poor experimental situation one often faces in low-resolution or low-field NMR. The signal intensity is comparable to that of ordinary Hahn echoes. Diffusion coefficients and spin-lattice relaxation times can be evaluated from the same experimental data set if both nutation echoes are recorded. Test experiments are in good agreement with literature data. Applications of the technique to "inside out" NMR, well logging NMR, surface coil NMR, toroid cavity NMR, etc., are suggested.

Journal Article↗

Low-frequency molecular dynamics studied by spin-lock field cycling imaging.

Spin-lock adiabatic field cycling imaging (SLOAFI) relaxometry was shown to be a useful technique for obtaining a fast study of spin-lattice relaxation dispersion in the rotating frame. The aim of the present article is to describe some technical aspects of the experiment in more detail, while showing simple examples that can be compared with laboratory frame relaxation. We also present here a general discussion of the equations for an off-resonance experiment used to analyze low-frequency molecular dynamics.

Humans↗

Diffusion measurements using the nonlinear stimulated echo.

The nonlinear stimulated echo that is generated by a sequence of three radiofrequency pulses, 90 degrees-tau(1)-90 degrees-tau(2)-45 degrees, in high magnetic fields (or at low temperatures) in the presence of pulsed or steady field gradients can be applied for measurements of the diffusion coefficient. Corresponding test experiments are reported. Steady gradients can be used without knowledge of the relaxation times. Remarkably the attenuation of the nonlinear stimulated echo by diffusion is substantially stronger than in the case of the ordinary stimulated echo.

Diffusion↗

Two-pulse nutation echoes generated by gradients of the radiofrequency amplitude and of the main magnetic field.

A two-pulse NMR nutation spectroscopy scheme is suggested that leads to a new type of spin echoes. The amplitude of the radiofrequency (RF) pulses as well as the external magnetic field are assumed to be subject to gradients G(1) and G(0), respectively, in the same but otherwise arbitrary direction. Multiple echoes are predicted and observed at times k(G(1)/G(0))tau(1) and tau -/+ k(G(1)/G(0))tau(1) (k = 1, 2, 3, ...) after the second RF pulse, where tau(1) represents the radiofrequency pulse duration, and tau is the spacing of the RF pulses. Based on these echoes, a method for diffusion measurements is proposed that simultaneously provides the spin-lattice relaxation time and the self-diffusion coefficient.

Diffusion↗

The nutation spin echo and its use for localized NMR

A suitably matched combination of unidirectional gradient pulses of the radio frequency amplitude B(1) and of the main magnetic field B(0) produces an unconventional type of spin echo, the nutation echo. The echo signal becomes volume selective if the gradients to be matched are inhomogeneously distributed in space. An example is a combination of a constant B(0) gradient and the inhomogeneous B(1) gradient of a surface coil. We suggest a method for localized NMR on this basis. Nutation echoes can also be used to map the spatial distribution of B(1) gradients of an arbitrary radio frequency coil geometry with the aid of a small probe sample. Copyright 2000 Academic Press.

Journal Article↗

Segment diffusion and flip-flop spin diffusion in entangled polyethyleneoxide melts: A field-gradient NMR diffusometry study

Chain dynamics in melts of entangled polyethyleneoxide melts has been investigated using fringe field nuclear magnetic resonance diffusometry. As already demonstrated in our previous work, intermolecular flip-flop spin diffusion strongly influences spin echo attenuation for long diffusion times and high molecular weights. The experimental data have been evaluated taking this phenomenon quantitatively into account. Predictions of the reptation model for the correspondingly modified time and molecular weight dependences of the effective segment diffusion coefficient are presented and compared with experimental results. While the ordinary Rouse model totally fails to explain the experimental data, a satisfactory qualitative description is provided on the basis of the tube/reptation model. However, the fitted parameter values turned out to be inconsistent with known properties of this polymer. This in particular refers to the mean squared chain end-to-end distance divided by the molecular weight, for which neutron-scattering values are available in the literature. Relative to those results, the value evaluated from our NMR diffusometry data on the basis of the tube/reptation model turned out to be much too large.

Journal Article↗

PRAWN: mixing sequences for selective heteronuclear J cross polarization.

In this work, we present a family of pulse sequences for selective heteronuclear J cross-polarization (JCP), which we have developed especially for indirect 13C imaging using JCP, for example in the CYCLCROP environment. The sequences are straightforward to implement and operate reliably. Results of an average Hamiltonian analysis are given for the basic sequence, which we term PRAWN (pulsed rotating frame transfer sequence with windows). It is shown experimentally that the pulse sequence, which operates efficiently with low RF duty cycles down to a few percent, has a useful tolerance range to absolute Hartmann-Hahn mismatch and generates coherence transfer spectra in close correspondence with the JCP average Hamiltonian. Computer simulation of the performance of the basic sequence on a heteronuclear spin-(1/2) AX system is also presented. The mismatch compensation of PRAWN may be markedly enhanced further by issuing a pi pulse to each spin halfway through the basic PRAWN train and in phase quadrature to it. A simple analysis of this modified sequence, PRAWN-pi, is given under conditions of mismatch and off-resonance irradiation.

Carbon Isotopes↗

Surface fractals probed by adsorbate spin-lattice relaxation dispersion.

Spin-lattice relaxation of strong adsorbates confined in disordered structures such as porous silica glass is treated on the basis of a relaxation mechanism due to "reorientation mediated by translational displacements." In such a situation the low-frequency spin-lattice relaxation dispersion beyond the regime where local reorientations dominate reflects molecular dynamics as well as the surface geometry on a length scale longer than 1 nm. It is shown that the power law frequently observed for the spin-lattice relaxation dispersion in porous media can be traced back to surface fractality. The fractal properties of rough surfaces and the statistics governing surface displacements enter explicitly in the expression for the dipolar correlation function. The surface fractal dimension can thus be evaluated from the low-frequency spin-lattice relaxation dispersion accessible by field-cycling NMR relaxometry.

Journal Article↗

Propagator representation of anomalous diffusion: the orientational structure factor formalism in NMR.

The radial Fourier transform for the isotropic space with a fractal dimension is discussed. The moments of diffusive displacements with non-Gaussian propagators arising as solutions of fractional diffusion equations are calculated. The Fourier propagator is applied to NMR correlation and spectral density functions in context with the orientational structure factor formalism. It is shown that the low-frequency molecular fluctuations of liquids in porous media with strong or forced adsorption at surfaces are due to reorientations mediated by translational displacements caused by surface diffusion of the adsorbate molecules. In terms of this formalism, field-cycling NMR experiments provide information on the static and dynamic fractal dimensions related to surface diffusion. The experimental results for liquids in porous silica glass can be explained by a surface fractal dimension df=2.5, where the mean squared displacement scales as proportional, variantt(2/dw) with dw=1 (ballistic transport), if the surface population can exchange with the bulklike phase in the pores, and with dw=2, if the bulklike phase is frozen. The former dynamics is interpreted in terms of bulk-mediated surface diffusion.

Journal Article↗

A new formalism for the evaluation of order-fluctuation modes in liquid crystals from field-cycling NMR-relaxometry data.

A numerical procedure is presented which permits one to derive a formal distribution of collective fluctuation modes from experimental field-cycling NMR-relaxometry data of an ordered system. The purpose is to distinguish true order-fluctuation modes from local reorientation mechanisms. The evaluation scheme is demonstrated using simulated as well as experimental data. Applications serving the elucidation and characterization of modified or limited director fluctuation modes as they occur with liquid crystals in pores or with lyotropic systems are discussed. Test experiments have been carried out with a potassium laurate system.

Crystallization↗

Multiple nonlinear stimulated echoes.

Three-pulse sequences in the presence of magnetic field gradients at high magnetic fields produce multiple nonlinear stimulated echoes (NOSE) at times ntau1 after the third pulse, where n is an integer and tau1 the interval between the first two pulses. These phenomena are due to the demagnetizing field produced by the spatial modulation of the nuclear magnetization arising in the sample after the first two pulses. The theory is presented and compared with experiments. The dependence of the NOSE amplitudes on the flip angles and on the pulse intervals is described. Implications for multidimensional NMR experiments based on sequences of three or more pulses in the presence of field gradients are discussed.

Dimethylpolysiloxanes↗

Detection of Anisotropic Pulsating Flow and Its Velocity-Fluctuation Rate in Fertilized Bird Eggs by NMR Microimaging

Coherent and incoherent flows in fertilized quail and bantam eggs have been studied with the aid of NMR microimaging techniques in the course of incubation until the end of the sixth day. The methods employed were multiplane tagging NMR imaging and a NMR gradient-echo imaging pulse sequence supplemented by bipolar gradient pulses in the coherence-evolution interval. The latter technique is suited for recording of velocity maps as well as for localizing of regions with enhanced echo attenuation by incoherent motions. Slight coherent displacements in the middle of the upper part of the egg white were found after the fourth day of incubation with the aid of both pulse schemes. The maximum velocity was estimated to be 1 mmsoliduss. More pronounced effects revealed themselves in the examination of incoherent motions. After the same time of incubation and in a somewhat more restricted area of the upper part of the egg white, distinct motions could be localized consistently with either technique. It is shown that these motions are directed to and from the yolk. Furthermore, the analysis of the time fluctuations of the local signals with the aid of a Fourier transformation showed that the flow is largely of a pulsating nature. The pulsation frequency was found to be 0.4 Hz.

Journal Article↗

NMR imaging of thermal convection patterns.

Two special magnetic resonance imaging techniques were applied to the Rayleigh/Bénard problem of thermal convection for the first time. The methods were tested using a water cell with horizontal bottom and top covers kept at different temperatures with a downward gradient. Using Fourier encoding velocity imaging (FEVI) a five-dimensional image data set was recorded referring to two space dimensions of slice-selective images and all three components of the local velocity vector. On this basis, the fields of the velocity components or of the velocity magnitude were evaluated quantitatively and rendered as gray shade images. Furthermore the convection rolls were visualized with the aid of two- or three-dimensional multistripe/multiplane tagging imaging pulse sequences based on two or three DANTE combs for the space directions to be probed. Movies illustrating the fluid motions by convection in all three space dimensions were produced. It is demonstrated that the full spatial information of the convection rolls is accessible with microscopic resolution of typically 100 x 100 x 100 microns3. This resolution is effectively limited by flow displacements in the echo time, which should be well within the voxel dimension. The main perspective of this work is that the combined application of FEVI and multistripe/multiplane tagging imaging permits quantitative examinations of thermal convection for arbitrary boundary conditions and with imposed through-flow apart from the direct visualization of convective flow in the form of movies.

Convection↗

Magic echoes and NMR imaging of solids.

Solid state NMR imaging techniques based on magic echoes are reviewed. The theoretical background of magic echoes in general and their spatial encoding in particular is treated. The magic-echo imaging pulse sequences presently in use are described and discussed. Particular emphasis is devoted to those techniques, which allow the incorporation of spectroscopic or parameter-selective information. The applicability of these methods for the investigation of materials is demonstrated and perspectives for materials science are outlined.

Image Enhancement↗

Visualization of anisotropic pulsations in extraembryonic compartments of incubated quail eggs by NMR microimaging.

Multi-plane tagging time-of-flight and bipolar gradient phase-encoding and amplitude-weighting NMR microimaging techniques have been employed to study transport in extraembryonic compartments of fertilized quail eggs during the first seven days of incubation. After the fourth day coherent and incoherent motions became visible in certain regions, in particular in the upper part of the albumen. Coherent motions as visualized by deformations of multiplane tagging grids were specified by local velocities less than 1 mm/s at most. On the other hand, incoherent motions led to much more pronounced phenomena. The multiplane tagging grid completely faded in a region comprising the upper third of the albumen after 4.5 incubation days. Images weighted by signal attenuation owing to incoherent displacements indicate motions in the same region. The fact that a reproducible localization of the motions is only possible when signals from different transients are averaged indicates that the incoherence at least partly is temporal in nature. The signal intensity of a volume selected in the incoherent-motion region consequently fluctuates with time. The Fourier analysis of these fluctuations revealed a distinct pulsation with a frequency of 0.4 Hz.

Animals↗

Self-diffusion in fluids in porous glass: confinement by pores and liquid adsorption layers.

Diffusion coefficients of 10 different polar and nonpolar liquids filled in porous glasses with mean pore diameters of 4 or 30 nm were determined with the aid of the NMR field-gradient technique. In the time scale of these experiments (0.3 to 500 ms) diffusion coefficients were found to be time independent. Within the experimental error, no influence of the polarity of the adsorbate can be stated. The diffusion coefficients of all investigated fluids in glass with 4 and 30 nm pores were reduced by factors of 0.17 and 0.63, respectively, relative to the bulk values. This relatively weak reduction can be explained by considering the known porosities of the adsorbents. The second objective of this study was to examine the diffusion behaviour below the melting point of adsorbates in porous glass. Fluids confined in pores do not freeze at the bulk freezing temperatures. In this respect, two phases must be distinguished. A maximal two monolayer thick film adsorbed on the inner surfaces does not crystallize at all, whereas the "free" fraction of the fluid in the pores freezes at reduced temperatures according to the Gibbs-Thompson relation. The nonfrozen surface layers form a network in which self-diffusion can be investigated. Experiments have been carried out with cyclohexane. A reduction factor of 0.06 was found relative to the extrapolated values of the entirely unfrozen fluid in porous glass with a mean pore diameter of 30 nm. It is, thus, demonstrated that molecules in adsorption layers virtually retain their translational degrees of freedom along the surfaces. The lowering of the diffusivity is mainly due to the geometric restriction rather than to the interaction with the surface.

Diffusion↗