Regeneration of zinc particles for zinc–air fuel cells in a spouted-bed electrode

Fuel cells wherein zinc particles form a negative electrode and a gas-diffusion electrode (air electrode) is the positive electrode, are under development. Such cells are dependent on the regeneration of the zinc particles (and electrolyte). This paper describes experiments on electrolytic cells equipped with spouted bed cathodes for use in this application. Experiments have been carried out on laboratory scale cells to determine the operability of cells for growing 'seed particles in the range from 0.4 to 1 mm to measure cell voltage and current efficiency (and thereby energy consumption rate), and to identify a suitable material that could be used as a diaphragm (separating the spouted bed from the oxygen evolving anode). A larger cell, capable of producing up to 10 kg Zn per day, was designed and built. The larger cell was run successfully fifteen times and showed cell voltages and energy consumption rates comparable with those of smaller cells.     

Gold nanoparticles on ceria: importance of O vacancies in the activation of gold

Synchrotron-based techniques (high-resolution photoemission, in-situ X-ray absorption spectroscopy, and time-resolved X-ray diffraction) have been used to study the destruction of SO₂ and the water-gas shift (WGS, CO + H₂O → H₂ + CO₂) reaction on a series of gold/ceria systems. The adsorption and chemistry of SO₂ was investigated on Au/CeO₂(111) and AuO _x /CeO₂ surfaces. The heat of adsorption of the molecule on Au nanoparticles supported on stoichiometric CeO₂(111) was 4–7 kcal/mol larger than on Au(111). However, there was negligible dissociation of SO₂ on the Au/CeO₂(111) surfaces. The full decomposition of SO₂ was observed only after introducing O vacancies in the ceria support. AuO _x /CeO₂ surfaces were found to be much less chemically active than Au/CeO₂(111) or Au/CeO_2−x (111) surfaces. In a separate set of experiments, in-situ time-resolved X-ray diffraction and X-ray absorption spectroscopy were used to monitor the behavior of nanostructured {Au + AuO _x }–CeO₂ catalysts under the WGS reaction. At temperatures above 250 °C, a complete AuO _x → Au transformation was observed with high catalytic activity. Photoemission results for the oxidation and reduction of Au nanoparticles supported on rough ceria films or a CeO₂(111) single crystal corroborate that cationic Au^δ+ species cannot be the key sites responsible for the WGS activity at high temperatures. The active sites in {Au + AuO _x }/ceria catalysts should involve pure gold nanoparticles in contact with O vacancies of the oxide.     

Shape memory polymers based on uniform aliphatic urethane networks

Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, to form amorphous networks with very uniform supermolecular structures, which can be used as photo‐thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N′,N′‐tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3‐butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34–153°C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T_g. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Edible oil evaluation by room odor tests: A preliminary report

Room odors developed on heating edible fats in open vessels were evaluated and characterized by a 20 member odor panel. Edible fats tested were: special soybean salad and cooking oils, hydrogenated soybean oil and some commercial salad and cooking oils. Factors were investigated that affect reliability and reproducibility of the test and the acuity of the panel members. The effects of fry temperature and size of sample were investigated. The method has been applied to a study of hydrogenated and unhydrogenated soybean oil samples. Presented at the AOCS Meeting, Chicago, September 1970. No. Market. Nutr. Res. Div., ARS, USDA.     

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.     

Damage Mechanisms and the Mechanical Properties of a Laminated 0/90 Ceramic/Matrix Composite

The tensile properties of a 0/90 laminated CAS matrix composite reinforced with Nicalon fibers have been measured. Some effects of notches have also been explored. Changes in modulus and permanent strain caused by matrix cracking have been measured and compared with available models. For this comparison, independent measurements have been made of the constituent properties and the residual stress. The ultimate tensile strength has also been measured and compared with a global load-sharing model. It is concluded that lower-bound matrix cracking models provide good predictability of the stresses at which various matrix cracking mechanisms first operate. Also, the ultimate tensile strength is found to be consistent with a global load-sharing model, based on the in situ strength properties of the fibers. Conversely, the evolution of matrix cracks at stresses above the lower bound has yet to be adequately modeled. In addition, a need is identified for improved models relating elastic properties and permanent strains to matrix crack spacing.     

Over-production of 5-enolpyruvylshikimate-3-phosphate synthase in Escherichia coli: use of the T7 promoter

5-Enolpyruvylshikimate-3-phosphate (EPSP) synthase, the productof the Escherichia coli aroA gene, has been overproduced inE.coli BL21(DE3) under the control of the T7 gene 10 promoterand ribosome binding site, to a level of {small tilde}50% oftotal cell protein. EPSP synthase is the primary target of thepost-emergence herbicide, glyphosate, commonly known as Roundup^TM.A simple two step purification is described, which results in99% pure homogeneous protein (as determined by PAGE). The integrityof the protein has been compared with previously characterizedprotein from .E.coli AB2829(pKD501) by determination of itskinetic parameters, N-terminal protein and DNA sequences, aminoacid analysis and ¹³C-NMR spectroscopy. This new overproducingstrain readily provides the gram quantities of highly pure proteinrequired for NMR studies of the active site and the developmentof novel time-resolved solid-state NMR techniques currentlyunderway in this laboratory.     

X-ray Photoelectron Spectroscopy of Cadmium Tin Oxide Ceramics in As-Fired and Electrochemically Reduced Forms

X-ray photoelectron spectroscopy (XPS) has been employed to investigate the chemical nature of samples of dicadmium stannate (Cd₂SnO₄) in the as-fired, electrochemically reduced, and reoxidized states. The reduction of Cd₂SnO₄ was found to be associated with a dramatic color change from bright yellow to dark green, a phenomenon commonly known as the electrochromic effect. Both quantitative XPS results and binding energy measurements proved that, upon exposure of the reduced ceramic bodies to air, the Sn²⁺ to Sn⁴⁺ transition readily took place to produce the intermediate compound, Cd₂SnO₃ with divalent tin. Prolonged exposure to the atmosphere did not result in further progress of reoxidation extending to monovalent cadmium. However, complete reoxidation of the reduced samples was possible by annealing in air at 350°C for a short period of time, e.g., 3 h, by which the original features of the as-fired state such as color and electrical conductivity were restored. The results also showed that reoxidized samples at high temperature assume the same XPS characteristics as those of as-fired ceramics.     

Analyses of lipids and oxidation products by partition chromatography: Hydroxy fatty acids and esters

A liquid-partition chromatographic procedure was used to separate hydroxy fatty acids, their methyl esters, and reduced fatty ester hydroperoxides. Mixtures of methyl stearate, mono- and dihydroxystearate, and mixtures of the corresponding free fatty acids were easily separated. Chromatographic determinations for ricinoleate in castor oils compared favorably with the chemical and infrared analyses. The chromatographic procedure was used to separate hydroxy fatty acids inDimorphotheca andStrophanthus seed oils. The methyl ester of dimorphecolic acid, the principal hydroxy fatty ester ofDimorphotheca oil, behaved like reduced methyl linoleate hydroperoxide and showed a polarity intermediate between methyl 12-hydroxystearate and methyl 9,10-dihydroxystearate. The 9-hydroxy-12-octadecenoic ester ofStrophanthus oil had a larger retention volume than methyl ous hydroxy fatty esters isolated chromatographically. The diene content of the reduced hydroperoxides agrees well with values reported in the literature (1,5,16). The diene content of the chromatographed methyl dimorphecolate is higher than reported by Smithet al. (20) for their preparations but agrees well with the value reported by Chipault and Hawkins (6) for puretrans-trans conjugated methyl linoleate. The extinction coefficient of methyl 12-hydroxystearate at 2.8 μ is higher than that reported for ricinoleate and the absorption band is much sharper. Because of these two conditions no association of the hydroxyl groups is indicated. These results also confirm the purity of the hydroxy fatty esters obtained by LPC. This method has been a valuable adjunct to the study of various oxygen-containing fatty acid and esters and was used to characterize the hydroxy esters obtained from the hydrogenation of methyl linolenate hydroperoxides (9). This work offers a basis for the development of analytical methods to determine the hydroxy and other polar acid content of fatty glycerides and their derivatives.     

Chemistry of mandibular and Dufour's gland secretions of ants in genusMyrmecocystus

Males of several species ofMyrmecocystus produce mandibular gland secretions that contain 2,4-dimethyl-2-hexenoic acid and a variety of monoterpenes that include neral, geranial, citronellol, limonene, and 2,6-dimethyl-5-hepten-1-ol. Other components identified include methyl anthranilate, octanal, octanol, octyl octanoate, and 2-hexyl-2-decenal. Methyl salicylate has been identified as a mandibular gland constituent of workers of several species in addition to mellein and monoterpenes such as cymene, limonene, and the isomers of citral. The Dufour's gland secretions of workers and females of 14 species contain typical formicine alkanes (e.g., undecane), 2-alkanols (e.g., 2-tridecanol), and 2-alkanones (e.g., 2-tridecanone). Two species in the subgenusEremnocystus produce secretions that are distinguished by the presence of significant quantities of tridecyl esters. The functions of these compounds as well as their possible chemosystematic significance in the genusMyrmecocystus are discussed.