Water�CGas Shift and CO Methanation Reactions over Ni�CCeO2(111) Catalysts

X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO₂(111) surfaces. Upon adsorption on CeO₂(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500?C800 K) leads to partial reduction of the ceria substrate with the formation of Ni²⁺ species that exists as NiO and/or Ce_1?xNi_xO_2?y. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO₂(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce⁺³ cations, CO dissociates on the surface at 300 K forming NiC_x compounds that may be involved in the formation of CH₄ at higher temperatures. At medium and large Ni coverages (>0.3 ML), the Ni/CeO₂(111) surfaces are able to catalyze the production of methane from CO and H₂, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (<0.3 ML), the Ni/CeO₂(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water?Cgas shift reaction.     

An investigation into the temperature sensitivity of strained andunstrained multiple quantum-well, long wavelength lasers: new insightand methods of characterization

The magnitude of the temperature rate of change of the threshold current density (J_th) is examined with respect to J_th , for a variety of unstrained and strained, long wavelength multiple quantum-well (MQW) lasers. A strong correlation is found between these parameters, and a new relationship describing the J_th -T relationship for these lasers is arrived at in terms of two new essentially temperature and length independent constants. A third constant, T_max, also appears which estimates the theoretical maximum operating temperature of the laser. It is proposed that these constants may prove to be more useful in characterizing the temperature sensitivity of semiconductor lasers than the conventional parameters T ₀ and I₀ which exhibit both a length and temperature dependence. Furthermore, an expression is found which relates the magnitude of T_max to adjustable device structural and material parameters, such as: the cavity length, L; facet reflectivity, R; transparency current density, J_tr; and, the modal gain coefficient, β. It is revealed that a close examination of this relationship may provide new insight into the physics of semiconductor lasers as well as a means for optimizing device design to obtain a high maximum operating temperature in order to eliminate the need for thermoelectric coolers in device packaging. Finally, the measured T_max, versus L characteristics of six different strained and unstrained MQW laser structures are presented     

The measurement of gastric motor function and transit in man by echo planar magnetic resonance imaging

Echo-planar imaging (EPI) can be used to produce snapshot images of the human stomach and antro-pyloro-duodenal segment in real time as an alternative technique to intubation and exposure to ionizing radiation. The method has been further developed to monitor simultaneous gastric motility and gastric emptying of liquid and solid meals. The model has been utilized to study the effects of pharmacological agents on gastric function.Eight normal subjects were imaged in a 0.5-T superconducting magnet for up to 6 h following ingestion of 800 ml tap water, followed by 500 ml porridge test meal + 500 ml tap water. A rapid multislice technique was adopted to image adjacent transverse slices (10 mm thick) through the gastric region. In addition, three subjects were orally dosed with 20 mg of the prokinetic agent Cisapride. Gastric volumes for each slice were calculated and summed to produce a measure of total gastric volume and gastric emptying. Contractile activity at the level of the antro-pyloric segment was detected using sequential 128 ms images at 3 s intervals. Alternate measurements of gastric volume and motility were made for the duration of the study.Gastric emptyingT _1/2's (times to empty 50% of the gastric contents) of 12.9 min for water and 116 min for porridge were in agreement with results obtained by the traditional techniques of gamma scintigraphy and impedance imaging. The frequency of gastric contractions increased from 2.4 contractions per minute (cpm) to 3.2 cpm following water and from 2.9 to 3.2 cpm following porridge. The prokinetic effect of enhanced coordination of antroduodenal contractions was also observed. These studies have demonstrated that EPI can be used to detect and image gastroduodenal function in man, totally noninvasively, and can be used to study the effects of drugs acting on the gastrointestinal tract.     

Controlled immobilisation of active enzymes on the cowpea mosaic virus capsid

Immobilisation of horseradish peroxidase (HRP) and glucose oxidase (GOX) via covalent attachment of modified enzyme carbohydrate to the exterior of the cowpea mosaic virus (CPMV) capsid gave high retention of enzymatic activity. The number of enzymes bound per virus was determined to be about eleven for HRP and 2-3 for GOX. This illustrates that relatively large biomacromolecules can be readily coupled to the virus surface using simple conjugation strategies. Virus-biomacromolecule hybrids have great potential for uses in catalysis, diagnostic assays or biosensors.     

Phase equilibria studies in the CaO–SiO2–Al2O3–MgO system with CaO/SiO2 ratio of 0.9

Phase equilibria and liquidus temperatures in the CaO–SiO₂–Al₂O₃–MgO system at a CaO/SiO₂ weight ratio of 0.9 in the liquid phase have been experimentally determined employing high-temperature equilibration and quenching technique followed by electron probe X-ray microanalysis. Isotherms at 1573, 1623, 1673, and 1773 K were determined and the primary phase fields of wollastonite, melilite, olivine, periclase, spinel, and corundum have been located. Compositions of the olivine and melilite solid solutions were analyzed and discussed. Comparisons between the newly constructed diagram, existing data, and FactSage predicted phase diagrams were performed and differences were discussed. The present study will be useful for guidance of industrial practices and further development of thermodynamic modeling.     

Computer simulation of structure and properties of crosslinked polymers: application to epoxy resins

In this work, a methodology has been developed for construction of atomistic models of crosslinked polymer networks. The methodology has been applied to low molecular weight water soluble epoxy resins crosslinked with different curing agents that are being considered for use as a primer coating on steel. The simulations allowed the crosslink density and the amount of free crosslinking sites in the coatings to be predicted. Shrinkage of the resin upon curing was reproduced by the simulation. In addition, the barrier properties of the model coatings were estimated. The interface between an inorganic substrate and cured epoxy resin has been constructed and the strength and molecular mechanisms of adhesion have been revealed. The developed methodology has a potential to significantly impact on the design and development of new coatings with improved barrier and adhesion properties.     

A reduced reaction model for carbon CVD/CVI processes

Carbon-carbon composites are produced by chemical vapor deposition/chemical vapor infiltration (CVD/CVI) processes. Models of carbon-carbon composite production processes will help reduce production costs. Reliable process models must, however, include details of the gas phase kinetics in order to identify optimal conditions. We have combined detailed gas phase kinetics, surface kinetics, and a pore closure model to predict pore geometry changes with respect to time. To determine the dominant gas phase kinetics, we reduced a large set of reactions to a minimal set using a sensitivity, rate, and dimensional analysis approach. These robust and relatively fast techniques can be used under a variety of conditions, including those within the pores of the composite. The process model shows that the deposition profile depends on the kinetic model chosen. Using the more realistic reaction model, conditions for uniform, or inside-out, densification can be suggested.