Recent Advances in MRI Studies of Chemical Reactors: Ultrafast Imaging of Multiphase Flows

NMR has long been established as an in situ technique for studying the solid-state structure of catalysts and the chemical processes occurring during catalytic reactions. Increasingly, pulsed field gradient (PFG) NMR and magnetic resonance imaging (MRI) are being exploited in chemical reaction engineering to measure molecular diffusion, dispersion and flow hydrodynamics within reactors. By bringing together NMR spectroscopy, PFG NMR and MRI, we are now able to probe catalysts and catalytic processes from the angstrom-to-centimeter scale. This article briefly reviews current activities in the field of MRI studies applied to catalysts and catalytic reactors. State-of-the-art measurements, which can already be used in real reactor design studies, are illustrated with examples of single-phase flow with and without chemical reaction in a fixed-bed reactor. The ability to obtain high spatial resolution (< 200μm) in images of the internal structure and flow field within reactors is demonstrated, and the potential uses of these data in reactor design and understanding bed fouling phenomena are discussed. In particular, MRI has produced the first detailed measurements of the extent of heterogeneity in the flow field within fixed-bed reactors. The example of a fixed-bed esterification process is used to show how NMR spectroscopy and MRI techniques can be combined to provide spatially resolved information on both hydrodynamics and chemical conversion within a process unit. The emerging area of ultrafast MRI is then highlighted as an area of particular interest. Recent advances have demonstrated that it is possible to record 2D images over timescales of ～100ms in the magnetically heterogeneous environments typical of heterogeneous chemical reactors. These advances open up opportunities to image many unsteady state processes for the first time. Examples are given of real-time visualization of bubble-train flow in a ceramic monolith and exploring the stability of the gas–liquid distribution as a function of liquid flow rate in a trickle-bed reactor.     

An investigation of methods of pileup rejection for 2-D array detectors employed in high resolution PET

Two methods of rejecting pileup events in 2-D array detectors used in positron emission tomography (PET) are investigated. Since the methods are based on different physical properties, they were investigated separately and in combination. Method one is based on the fact that valid events in the 2-D array detector occur only in a limited pulseheight range for each detector element, and by rejecting events outside these energy ranges, many of the pileup events can be rejected. Method two is based on the fact that most pileup event pairs have a time differential, which will cause a difference in the shape of the signal which increases the rise time of an integrated signal or the crossover time of a bipolar signal from a shaping amplifier. Method two proved to be somewhat better than method one. However, the ideal system would most likely use both methods simultaneously.     

Crystal and magnetic structures of Laves phase compound NdCo2 in the temperature range between 9 and 300 K

The crystal and magnetic structures of the Laves phase compound NdCo₂ in the temperature range from 9 to 300 K are determined by Rietveld refinement technique, using high-resolution neutron powder diffraction data. The compound crystallizes in space group above the magnetic ordering temperature T_C (≈100 K), in space group I4₁/amd below T_C and in space group Imma below the tetragonal–orthorhombic structural/magnetic transitions at T_M ≈ 42 K. The assignment of the space groups to the crystal structures of NdCo₂ in different temperature ranges complies with the reported Mössbauer studies. Detailed information of the crystal and magnetic structures of NdCo₂ at different temperatures are reported.     

Ongoing verification of a multiphysics community code: FLASH

When developing a complex, multi‐authored code, daily testing on multiple platforms and under a variety of conditions is essential. It is therefore necessary to have a regression test suite that is easily administered and configured, as well as a way to easily view and interpret the test suite results. We describe the methodology for verification of FLASH, a highly capable multiphysics scientific application code with a wide user base. The methodology uses a combination of unit and regression tests and an in‐house testing software that is optimized for operation under limited resources. Although our practical implementations do not always comply with theoretical regression‐testing research, our methodology provides a comprehensive verification of a large scientific code under resource constraints.Copyright © 2013 John Wiley & Sons, Ltd.     

Up in smoke: I. Smoke-derived germination cues for postfire annual,Nicotiana attenuata torr. Ex. Watson

Some postfire annuals with dormant seeds use heat or chemical cues from charred wood to synchronize their germination with the postfire environment. We report that wood smoke and polar extracts of wood smoke, but not the ash of burned wood, contain potent cue(s) that stimulate germination in the postfire annual plant,Nicotiana attenuata. We examined the responses of seeds from six populations of plants from southwest Utah to extracts of smoke and found the proportion of viable seeds that germinated in the presence of smoke cues to vary between populations but to be consistent between generations. With the most dormant genotypes, we examine three mechanisms by which smoke-derived chemical cues may stimulate germination (chemical scarification of the seed coat and nutritive- and signal-mediated stimulation of germination) and report that the response is consistent with the signal-mediated mechanism. The germination cue(s) found in smoke are produced by the burning of hay, hardwood branches, leaves, and, to a lesser degree, cellulose. Moreover, the cues are found in the common food condiment, liquid smoke, and we find no significant differences between brands. With a bioassay-driven fractionation of liquid smoke, we identified 71 compounds in active fractions by GC-MS and AA spectrometry. However, when these compounds were tested in pure form or in combinations that mimicked the composition of active fractions over a range of concentrations, they failed to stimulate germination to the same degree that smoke fractions did. Moreover, enzymatic oxidation of some of these compounds also failed to stimulate germination. In addition, we tested 43 additional compounds also reported from smoke, 85 compounds that were structurally similar to those reported from smoke and 34 compounds reported to influence germination in other species. Of the 233 compounds tested, 16 proved to inhibit germination at the concentrations tested, and none reproduced the activity of wood smoke. By thermally desorbing smoke produced by cellulose combustions that was trapped on Chromosorb 101, we demonstrate that the cue is desorbed between 125 and 150°C. We estimate that the germination cues are active at concentrations of less than 1 pg/seed and, due to their chromatographic behavior, infer that a number of different chemical structures are active. In separate experiments, we demonstrate that cues remain active for at least 53 days in soil under greenhouse conditions and that the application of aqucous extracts of smoke to soil containing seeds results in dramatic increases in germination of artificial seed banks. Hence, although the chemical nature of the germination cue remains elusive, the stability of the germination cues, their water-solubility, and their activity in low concentrations suggest that these cues could serve as powerful tools for the examination of dormant seed banks and the selective factors thought to be important in the evolution of postfire plant communities.     

Building brains for bodies

We describe a project to capitalize on newly available levels of computational resources in order to understand human cognition. We are building an integrated physical system including vision, sound input and output, and dextrous manipulation, all controlled by a continuously operating large scale parallel MIMD computer. The resulting system will learn to think by building on its bodily experiences to accomplish progressively more abstract tasks. Past experience suggests that in attempting to build such an integrated system we will have to fundamentally change the way artificial intelligence, cognitive science, linguistics, and philosophy think about the organization of intelligence. We expect to be able to better reconcile the theories that will be developed with current work in neuroscience.     

Grain size effects on cyclic fatigue and crack-growth resistance behaviour of partially stabilized zirconia

Cyclic fatigue crack growth and crack-resistance behaviour was studied in partially stabilized zirconia (PSZ) with three different cubic-phase grain sizes following sub-eutectoid heat treatments. Raman spectroscopy was used to determine the extent of phase transformation around the cracks for both cyclic and monotonic loading conditions. All tests were on long, through thickness cracks using compact-tension specimens. Predictions of crack-tip shielding were made following determination of toughening parameters using crackresistance data. It was found that the dominant factors affecting cyclic fatigue-crack growth were the level of crack-tip shielding, as a result of phase transformation, and the intrinsic toughness of the material. Grain size did not appear to significantly affect fatigue crack-growth behaviour.     

Creation of TiN paths on titanium alloy OT4-1 by the use of a laser beam

TiN paths have been created on the surface of the titanium alloy OT4-1 by the use of a laser beam. The results of investigations of structure, phase composition, microhardness and surface roughness of the created TiN paths are given in the paper. The paths created in the work are inhomogenous two-phase mixtures of TiN and -Ti, in which the TiN phase with strong (2 0 0) texture is predominant over the other phase and presents a dendritic structure. © 1998 Chapman & Hall     

A clinical nude mouse metastatic model for highly malignant human pancreatic cancer

Pancreatic cancer is a highly aggressive and treatment-refractory cancer. A clinically-relevant animal model is necessary to develop therapy for metastatic pancreatic cancer. In this study we evaluated the efficacy of mitomycin C (MMC) and 5-FU against the human pancreatic adenocarcinoma cell line PAN-12 in an orthotopic human metastatic pancreatic cancer nude mice model. The model is constructed by surgical orthotopic implantation (SOI) of histologically intact tumor tissue in the tail portion of the pancreas near the spleen. PAN-12 grew very aggressively in the control group of nude mice with extensive local invasion and distant metastasis to various organs with a propensity for the lung but to other organs as well, including the liver, kidney and regional and distant lymph nodes. In a striking effect none of the mice in the MMC-treated group developed tumor. Although mice in the 5-FU treated group survived statistically significantly longer than those in the untreated control, the overall incidence of metastasis in these mice was equivalent to those in the control. However no liver or kidney metastases were found in the 5-FU treated animals perhaps accounting in part for their longer survival. This "clinical" nude mouse model of highly metastatic pancreatic cancer can now be used to discover new effective agents for this disease.