Diffusion NMR methods applied to xenon gas for materials study

We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack.     

Structural and Transport Properties of Alumina Porous Membranes from Process-Based and Statistical Reconstruction Techniques

We study the structural and transport properties of two model porous membranes made by compaction of spherical monosize gamma-alumina particles. A ballistic deposition process of spherical particles has been employed as a process-based representation method for accurately simulating the pore structure of the membranes. Comparison between the computed and experimental permeability values obtained in the Knudsen regime shows very good agreement for both membranes and indicates that sufficient representation of the original pore structure is achieved with the random sphere packs. In a further step, a medium with the same porosity and autocorrelation function as the sphere pack has been stochastically reconstructed. Comparison between the structural properties of the random sphere pack system (process-based model) and the stochastically reconstructed medium (statistical model) shows nearly identical correlation functions and pore chord length distributions but widely different mass chord length distributions. This is reflected to a significant difference in the prediction of a dynamic property like the Knudsen permeability by a factor of about 4. The results suggest that matching of the porosity and the two-point correlation function alone is not always adequate when pursuing an accurate representation of the structure of a porous material. In such cases, higher order statistical properties of the material contained in the chord length distribution of both pore and solid phase should be satisfied as well. It is also found that proper account of the formation process in the reconstruction of a porous material (process-based model) leads to representations of its structure more accurate than those of statistical reconstruction models. Copyright 2000 Academic Press.     

Linking pore diffusivity with macropore structure of zeolite adsorbents. Part I: three dimensional structural representation combining scanning electron microscopy with stochastic reconstruction methods

In the present study we have employed advanced experimental and computational methods to characterize the structure of a binderless zeolite adsorbent with improved mass transfer characteristics. Hence, we have used standard and hybrid simulated annealing (SA) methods to stochastically reconstruct in three dimensions the adsorbent structure, by matching low order correlations, namely porosity and two point correlation function. These correlations are measured on two dimensional images obtained by Back-Scattered SEM micrographs taken on different samples of the adsorbent. In the standard SA method we have started from a purely random structure, while in the hybrid method we have started from a uniformly consolidated random sphere pack made by the Lubachevsky–Stillinger algorithm. It is found that the hybrid method preserves, besides low order correlations, pore and mass chord length distribution functions, which contain information on higher order correlations, while the standard SA method matches only low order correlations. This is because in the hybrid process we have initiated the SA algorithm starting from a structure that contains structural information of the sintered zeolite powder, in the form of a consolidated random sphere pack with the porosity of the final structure. Evidently, diffusion studies will enable us to further evaluate the structures developed by each method, as will be explored in a subsequent study.     

The detection of tetrahydrofuran hydrate formation and saturation using magnetic resonance imaging technique

Tetrahydrofuran (THF) hydrate was formed in bulk as well as in glass beads pack with a mean diameter of 3.0 mm by controlling the temperature under ambient pressure. Images of THF hydrate formation procedure were obtained using the magnetic resonance imaging (MRI) technique. The experiment results showed that MRI is an effective method for the detection of hydrate formation. Saturation of hydrate formed both in bulk and glass beads can be confirmed by intensity integration of MRI images.     

Particle Network Self-Assembly of Similar Size Sub-Micron Calcium Alginate and Polystyrene Particles Atop Glass

Particle-mediated self-assembly, such as nanocomposites, microstructure formation in materials, and core-shell coating of biological particles, offers precise control over the properties of biological materials for applications in drug delivery, tissue engineering, and biosensing. The assembly of similar-sized calcium alginate (CAG) and polystyrene sub-micron particles is studied in an aqueous sodium nitrate solution as a model for particle-mediated self-assembly of biological and synthetic mixed particle species. The objective is to reinforce biological matrices by incorporating synthetic particles to form hybrid particulate networks with tailored properties. By varying the ionic strength of the suspension, the authors alter the energy barriers for particle attachment to each other and to a glass substrate that result from colloidal surface forces. The particles do not show monotonic adsorption trend to glass with ionic strength. Hence, apart from DLVO theory—van der Waals and electrostatic interactions—the authors further consider solvation and bridging interactions in the analysis of the particulate adsorption-coagulation system. CAG particles, which support lower energy barriers to attachment relative to their counterpart polystyrene particles, accumulate as dense aggregates on the glass substrate. Polystyrene particles adsorb simultaneously as detached particles. At high electrolyte concentrations, where electrostatic repulsion is largely screened, the mixture of particles covers most of the glass substrate; the CAG particles form a continuous network throughout the glass substrate with pockets of polystyrene particles. The particulate structure is correlated with the adjustable energy barriers for particle attachment in the suspension.     

On the Geometry and Topology of 3D Stochastic Porous Media

The nature of geometric and topological information contained in statistical correlation functions was investigated systematically using simulated porous media, generated by the level-cut of Gaussian random fields. Pore space partitioning techniques based on multiorientation scanning were implemented to determine the pore and neck size distributions, coordination number distribution, and genus of a number of model porous media. These results were correlated with the statistical properties (porosity and correlation function) of the microstructure, revealing for the first time the extent of morphological diversity of a broad class of stochastically reconstructed porous media. It was found that the dominant factor explaining microstructural variability among the media studied is the dimensionless length of spatial correlation. Accordingly, the resolution at which the void space is discretized during simulation was shown to affect significantly the resulting pore and neck size distributions and specific genus. It was also found that the average coordination number of simulated porous media is independent of correlation length, but decreases slightly with decreasing porosity. Copyright 2000 Academic Press.     

Kinetic studies of glucose oxidase in polyelectrolyte multilayer films by means of scanning electrochemical microscopy (SECM)

Multilayer films of glucose oxidase (GOx) and poly(dimethyl diallyl ammonium chloride) (PDDA) prepared by layer-by-layer deposition were studied using scanning electrochemical microscopy (SECM). Aminated glass slides were coated with five bilayers of poly(styrene sulfonate) (PSS) and PDDA and used as substrates onto which GOx/PDDA multilayers were deposited. UV-Vis experiments confirmed multilayer growth, scanning force microscopic images provided morphological information about the films. SECM current-distance curves enabled the determination of kinetic information about GOx in GOx/PDDA multilayers as a function of layer number, film termination, inert covering layers, and enzyme substrate concentration after fitting to numerical models. The results indicate that only the topmost layers contributed significantly to the conversion. An odd-even pattern was observed for PDDA-terminated films or GOx-terminated films that correlated with morphological changes.     

3D visualization of the microstructure of Quedius beesoni Cameron using micro-CT

The investigation of the internal morphology of insects is usually performed using classical microtomy yielding optical micrographs of stained thin sections. The achievement of high-quality cross sections for microtomy is time-consuming and the risk of damaging sections is unavoidable. Moreover, the approach is impractical, in particular when quick acquisition of 3D structural information is required. Recently, X-ray computed microtomography (micro-CT) with a high spatial resolution was considered as a potential tool for the morphological classification of insects. We used micro-CT to investigate Quedius beesoni Cameron at the cellular length scale. This method provides a new powerful and nondestructive approach to obtain 3D structural information on the biological organization of insects. The preliminary images presented in this contribution clearly reveal the endoskeleton and the muscles of the head and the thorax with a full 3D structure. We also reconstructed the 3D structure of the brain of Quedius beesoni Cameron, and this is the first reconstruction in Staphylinidae, which will be a great advancement for morphological and phylogenic research. We claim that both the spatial resolution and the contrast characteristic of micro-CT imaging may fulfill the requirements necessary for zoological insect morphology and phylogeny, in particular, when a classification of a rare and unique insect specimen is required.     

Janus Emulsions from a One-Step Process; Optical Microscopy Images

The optical microscopy images of an emulsion are commonly distorted when viewed between a cover glass and a planar microscopy slide. An alternative method is to place the sample on a slide with a cavity, which in turn suffers from incomplete information for high internal phase ratio (HIPR) emulsions, due to the inevitable crowding of the drops. This problem is particularly acute for more complex emulsions, such as those with Janus drops, for which a detailed image of the drop is essential. A number of publications have recently described Janus emulsions prepared by a one-step high energy emulsification process with microscopy images obtained by the sample between a planar slide and a cover glass. The correlation to the morphology of emulsions in bulk of these images is critical, but, so far, a potential equivalence has not been established. Since the images are central in order to understand why Janus emulsions should form under such conditions, the need to ascertain any such association is urgent. With this contribution, we compare images from different microscopy methods to those of gently diluted HIPR emulsions. The results reveal that the images of the emulsion samples between a cover glass and a planar microscope slide actually present a realistic representation of the drop topology in bulk emulsions.     

How does column packing microstructure affect column efficiency in liquid chromatography?

Full three-dimensional computer simulations of the fluid flow and dispersion characteristics of model nonporous chromatographic packings are reported. Interstitial porosity and packing defects are varied in an attempt to understand the chromatographic consequences of the packing microstructure. The tracer zone dispersion is calculated in the form of plate height as a function of fluid velocity for seven model particle packs where particles are selectively removed from the packs in clusters of varying size and topology. In an attempt to examine the consequences of loose but random packs, the velocities and zone dispersion of seven defect-free packs are simulated over the range 0.36< or =epsilon< or =0.50, where epsilon is the interstitial porosity. The results indicate that defect-free loose packings can give good chromatographic efficiency but the efficiency can vary depending on subtle details of the pack. When the defect population increases, the zone dispersion increases accordingly. For a particle pack where 6% of the particles are removed from an epsilon=0.36 pack, approximately 33% of the column efficiency is lost. These results show that it is far more important in column packing to prevent defect sites leading to inhomogeneous packing rather than obtaining the highest density pack with the smallest interstitial void volume.     

A photosensitive material based on methyl methacrylate-acrylic acid copolymer

The possibility of recording holographic images in a photosensitive material based on methyl methacrylate-acrylic acid copolymer, which is more heat-resistant than poly(methyl methacrylate) used as a base for optical recording media, was examined. Introduction of acrylic acid units into poly(methyl methacrylate) macromolecule does not prevent recording and reconstruction of holographic images, but, at the same time, affects the dynamics of variation of the diffraction efficiency of diffraction lattices recorded in this polymer.     

The equatorial small‐angle scattering during the straining of poly(ether ester) and its analysis

A method for the quantitative analysis of two‐dimensional (2D) small‐angle X‐ray scattering (SAXS) patterns with fiber symmetry by successive information filtering is proposed and applied to a series of images recorded during a straining experiment of a two‐phase polymer sample at a synchrotron beamline. The studied equatorial scattering is similar to the frequently discussed void scattering, but originates from an ensemble of rodlike soft domains (needles) in the sample, orientated in the direction of strain. The intensity is extracted and projected onto the equatorial plane, the ideal two‐phase structure is extracted, and the 2D chord distribution is computed. This curve describes a 2D two‐phase morphology made from needle cross‐sections embedded in matrix material. Because interparticular correlation is found to be weak in the chord distribution, pure particle scattering is assumed. Modeling the needle cross‐sections by circular disks leads to a simple theory, which allows the deconvolution of a disk diameter distribution from the chord distribution. It is shown how parameters of the disk diameter distribution can be computed without deconvolution. For the selected poly(ether ester) thermoplastic elastomer the study of the soft domain needles indicates strain‐induced hardening. While for low elongation ϵ the soft needles are more compressible than the microfibrillar matrix, saturation is observed for ϵ > 2.5. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 975–981, 1999     

Three-dimensional pore structure of chromatographic adsorbents from electron tomography

The pore structure of chromatographic adsorbents directly influences macromolecular partitioning and transport in chromatography. Quantitative structural characterization of chromatographic media has generally been performed in terms of the mean pore size or, at best, the pore size distribution (PSD), but more detailed information on, e.g., connectivity has been lacking. We have applied electron tomography, a 3D TEM technique that views a sample from multiple perspectives and allows reconstruction of the volumetric structure, to capture the internal details of microporous chromatographic media with nanometer-scale resolution. Visualization of reconstructions of three adsorbents, Toyopearl SP-650 C, SP-550 C, and CM Sepharose FF, provides thorough and direct information on the geometry and the interconnectivity of the pore network. The structures are qualitatively consistent with in situ AFM images, and quantitative data for the porosities and PSDs from the analysis of tomographic data agree reasonably well with inverse size-exclusion chromatography results. For a more straightforward representation of the networking and size features of the disordered pore space, a 3D thinning algorithm was used to derive pore skeletons and consequently quantitative data on distributions of local path lengths, widths, tortuosities, and connectivities. Such enriched structural information can be instrumental in more discriminate structural evaluation and construction of engineered pore models for the study of solute intraparticle transport.     

Drying and sintering of sol-gel derived large SiO2 monoliths

This review article summarizes the development of drying and sintering techniques for the production of sol-gel derived, large silica glass components. Gels may be synthesized using particulate or metal alkoxide precursors, or both in combination. Rapid fracture-free drying has been achieved easily with particulate gels because of their large pore size (100–6000 Å). Alkoxide gels, which generally have small pores (<200 Å), were initially difficult to dry without cracking. However, recent studies have shown that large alkoxide gel monoliths can also be dried in reasonably short times (<10 days). During subsequent heat treatment, alkoxide gels tend to have high shrinkage rates, which may cause trapping of hydroxyl ions or organic groups remaining on the gel surface. Although the removal of these species is easier for particulate gels, their large pore size necessitates heating above 1400°C to achieve full consolidation. Sintering at such temperatures was observed to deteriorate glass quality, through crystallization, warping, and/or sagging. Extensive optimization of the entire process has shown that on a laboratory scale, high-optical-quality glass can be produced from both alkoxide and particulate gels. It remains to be seen whether sol-gel process will be feasible for the manufacture of high-quality glass products on a commercial scale.     

Three-dimensional ultrasound imaging and its use in quantifying organ and pathology volumes

Although ultrasonography is an important cost-effective imaging modality, technical improvements are needed before its full potential is realized for accurate and reproducible monitoring of disease progression or regression. Two-dimensional viewing of three-dimensional anatomy, using conventional ultrasonography, limits our ability to quantify and visualize pathology and is partly responsible for the reported variability in diagnosis and monitoring of disease progression. Efforts of investigators have focused on overcoming these deficiencies by developing 3D ultrasound imaging techniques that are capable of acquiring B-mode images using existing conventional ultrasound systems, reconstructing the information into 3D images, and then allowing interactive viewing of the 3D images on inexpensive desktop computers. In addition, the availability of 3D ultrasound images has allowed the development of manual and semi-automated techniques to quantify normal and abnormal anatomical volumes. In this paper we review our semi-automated 3D segmentation approaches for segmenting the surface of the carotid arteries and plaques, and segmenting the prostate. These techniques demonstrate that efficient segmentation techniques can be used with 3D ultrasound images to quantify anatomical organ volumes and morphology.     

Urban air pollutants and their micro effects on medieval stained glass windows

Levels of urban gaseous and particulate pollutants were investigated in the Cathedral of Cologne, Germany in the framework of the EU-project “VIDRIO”. The purpose of this study was to evaluate the influence of a protective double glazing system on the preservation of ancient stained glass windows by sampling at protected and unprotected windows (indoors, in the interspace and outdoor of the Cathedral). The interspace between the ancient stained glass window and the protective glazing is flushed in the Cathedral by indoor air, hence isolating the historic glass from the outdoor air and exposing it to indoor air on both sides of the glass panels. Concentrations of aggressive gaseous pollutants such as NO₂, SO₂, O₃ and CO₂ as well as elemental concentrations of bulk particles and relative abundances of single particles were surveyed at all sampling locations. Elemental concentrations in bulk particulate matter were found to be significantly lower inside the Cathedral in comparison to the outdoor air. This result is advantageous for the stained glass windows. Single particle analysis of the samples from Cologne showed also soil dust and organic particles as well as sulphates and nitrates, from which the latter two compounds are dangerous for the stained glass windows. On the base of the obtained results, it can be concluded that the protective glazing system in the Cathedral of Cologne can be considered as predominantly advantageous from both the gases' point of view (except for NO₂-candles burning) and from the particles' point of view.     

Morphological and tissue characterization of the medicinal fungus Hericium coralloides by a structural and molecular imaging platform

In this study the potential of new imaging techniques such as Magnetic Resonance Imaging (MRI), Matrix-Assisted Laser Desorption/Ionization (MALDI) profiling mass spectrometry ("MALDI Profiling") and Fourier Transform Infrared (FTIR) spectroscopic imaging was evaluated to study morphological and molecular patterns of the potential medicinal fungus Hericium coralloides. For interpretation, the MALDI profiling, FTIR imaging and MRI results were correlated with histological information gained from Scanning Electron Microscopy (SEM) and Light Microscopy (LM). Additionally we tested several evaluation processes and optimized the methodology for use of complex FTIR images to monitor molecular patterns. It is demonstrated that the combination of these spectroscopic methods enables to gain a more distinct picture concerning morphology and distribution of active ingredients. We were able to obtain high quality FTIR imaging and MALDI-profiling results and to distinguish different tissue types with their chemical ingredients. Beside this, we have created a 3-D reconstruction of a mature Hericium basidioma, based on the MRI dataset: analyses allowed, for the first time, a realistic approximation of the "evolutionary effectiveness" of this bizarrely formed basidioma type, concerning the investment of sterile tissue and its reproductive output (production of basidiospores).     

Linking pore diffusivity with macropore structure of zeolite adsorbents. Part II: simulation of pore diffusion and mercury intrusion in stochastically reconstructed zeolite adsorbents

In the present study we complete the evaluation of three dimensional digitized reconstructions of a binderless zeolite adsorbent with improved mass transfer rates, by performing simulations of pore diffusion and Hg-intrusion porosimetry in these structures. It is seen that an excellent agreement with the experimental diffusivity is achieved (relative error of 1.2 %) for a pore structure that matches, besides low order correlations, chord length distribution functions that account for higher order correlations. Furthermore, simulations on a variety of reconstructed samples indicate that matching chord length distribution functions is a necessary (though probably not sufficient) condition for accurate structural representation. The average tortuosity factor is 2.68 and is nearly constant over a broad spectrum of pressures, when properly normalized. Hg-intrusion porosimetry simulations, performed with a pure morphology method, show a good agreement with the experimental curve for normalized cumulative intrusion volumes in the range of 50–88 %, but cannot make a distinction between structures with differences in higher order correlations. It is believed that SEM micrographs, properly obtained to represent realistic 2D sections of the material, contain sufficient structural information that can distinguish among pore structures with different mass transfer rates, when combined with stochastic reconstruction methods. Evidently, the direct link between these structural parameters and pore diffusivity will provide the necessary route to improve the mass transfer rate of porous adsorbents.     

Remotely detected MRI velocimetry in microporous bead packs

Many NMR and MRI methods probe fluid dynamics within macro- and mesoporous materials, but with few exceptions, they report on its macroscopically averaged properties. MRI methods are generally unable to localize microscopic features of flow within macroscopic samples because the fraction of the enclosing detector volume occupied by these features is so small. We have recently overcome this problem using remotely detected MRI velocimetry, a technique in which spatial, chemical, and velocity information about elements of the flow is encoded with a conventional NMR coil and detected sensitively at the sample outflow by a volume-matched microdetector. Here, we apply this method to microporous model systems, recording MRI images that correlate local velocity, spin relaxation, and time-of-flight in microscopic resolution and three spatial dimensions. Our results illustrate that remotely detected MRI is an effective approach to elucidate flow dynamics in porous materials including bead pack microreactors and chromatography columns.