A Fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO₂ and CO₂/H₂ on a silica-supported caesium-doped copper catalyst. Adsorption of CO₂ on a “caesium”/silica surface resulted in the formation of CO₂ ⁻ and complexed CO species. Exposure of CO₂ to a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm⁻¹. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and H₂, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.     

On-line studies and computer simulation of the melt spinning of nylon-66 filaments

A mathematical model was developed to describe the high-speed melt-spinning behavior crystallizable polymers. This model included the effects of acceleration, gravity, and air friction on the kinematics of the process; temperature and molecular orientation on the crystallization kinetics of the polymer; and temperature, molecular weight, and crystallinity on the elongational viscosity of the material. Experimental on-line diameter, birefringence, and temperature profiles were obtained for a 12,000 Mn nylon-66 at 2.5 g/min spun at take-up speeds ranging from 2800 to 6600 m/min. These profiles were qualitatively and reasonably quantitatively in agreement with the predicted profiles. They indicated that orientation induced crystallization occurs at spinning speeds greater than 4000 m/min. The experimental diameter and birefringence profiles were compared to those predicted by the model using Avrami indices of 3, 2, and 1. There was a small increase in the crystalline index at the lower speeds with decreasing index. The effect of the strain hardening was more significant at the higher speeds, this being shown by decreasing the exponent in the relationship for the crystallinity on the elongational viscosity. The model developed in this study indicates that high spinning speeds provide the high stress environment that increases the molecular orientation within the fiber. It is this higher molecular orientation that is the driving force for rapid crystallization on the spinline. This rapid crystallization causes a strain hardening, preventing any further drawdown in the fiber diameter and an abrupt rise in the birefringence. This behavior closely corresponds to the observed spinline profiles.     

The effect of stabilizing agents on the hydration rate of β-C2S

Small quantities (<2%) of various metal oxides are incorporated into the lattice of β-C₂S during the high temperature preparation. The effect which these stabilizers have on the hydration rate is examined. A model involving the charge/radius ratio of the metal ion is developed to explain altered hydration rates. This charge/ radius ratio model also proves useful in describing the crystal-chemical stabilization of β-C₂S. In addition, the solubility of Cr₂O₃ in β-C₂S is determined by a novel differential thermal analysis technique.     

Theoretical examination of the mechanism of aldose-ketose isomerization

Two mechanisms for an aldose–ketose isomerization havebeen examined using high level ab initio and semiempirical molecularorbital methods. The proton transfer pathway via an enediolintermediate is shown to be favored in the absence of a metalion, while the hydride transfer pathway becomes favored in thepresence of a metal ion. Our calculations explain why the protontransfer pathway is operative in most aldose–ketose isomerizationreactions. These calculations also provide further support forthe previously proposed metal ion-mediated hydride transfermechanism for xylose isomerase.     

Non-Isothermal crystallization of isotactic polypropylene in dotriacontane. II: Effects of dilution,cooling rate,and nucleating agent addition on growth rate

Non-isothermal crystallization growth rates of nucleated and non-nucleated isotactic polypropylene (iPP) in dotriacontane were determined experimentally by thermal optical microscopy. Adipic acid was used as the nucleating agent. The non-isothermal growth rates of the nucleated and non-nucleated systems were compared with experimentally determined isothermal growth rates. The Lauritzen and Hoffman growth rate equation, originally developed for isothermal crystallization, was modified to describe the non-isothermal growth. The modified Lauritzen-Hoffman equation was used to predict isothermal growth rates from non-isothermal crystallization for the nucleated and non-nucleated polymer-diluent mixtures. This study is the first to deal with polymer-diluent-nucleating agent systems vital to membrane production.     

Towards an Environmentally Acceptable Heterogeneous Catalytic Method of Producing Adipic Acid by the Oxidation of Hydrocarbons in Air

A survey is given of the catalytic methods potentially available for the production of adipic acid by the oxidation of readily available hydrocarbon precursors under environmentally benign conditions. Encouraging results are reported using H₂O₂ as oxidant and microporous FeAlPO-5 as catalyst at moderate temperatures.     

The synthesis and characterization of the molecular sieve SAPO-16 as well as other SAPO and CoAPO phases using bis(cyclopentadienyl) cobalt(III) hydroxide as a structure directing agent

The clathrate type molecular sieve SAPO-16 was prepared via a hydrothermal synthesis using bis(cyclopentadienyl)cobalt(III) hydroxide, Cp₂CoOH, as a template and characterized by XRD, FT-IR, UV-Vis and SEM. Additionally, the preparation and characterization of possibly new isostructural SAPO-UTD-3 and CoAPO-UTD-3 materials is reported.NSF Presidential Young Investigator 1991–1996.     

Preparation and Characterization of Mordenite Thin Films via Pulsed Laser Deposition

Zeolite thin films are interesting for their potential application in membrane based separations, catalysis, and molecular sensing. Mordenite is a one-dimensional channel type zeolite that has been used in alcohol/water separations. Pulsed-laser deposition has been used to prepare partially oriented, crystalline mordenite thin films on stainless steel foil, and frits as well as carbon fibers and DAM-1 particles. Preliminary results for pervaporation of isopropanol/H₂O mixtures using mordenite membranes indicate separation factors of 133 and 459 at room temperature and 76°C, respectively.     

Viscoelastic properties and morphology of sulfonated poly(styrene-b-ethylene/butylene-b-styrene) block copolymers (sBCP), and sBCP/[silicate] nanostructured materials

Self-assembled organic/inorganic hybrid materials were created via domain targeted sol-gel reactions of tetraethylorthosilicate in solution with sulfonated poly(styrene-b-[ethylene-co-butylene]-b-styrene) (sSEBS) copolymers. Dynamic mechanical analyses (DMA) of these hybrid materials suggest that the silicate component preferentially incorporates within the sulfonated polystyrene (PS) domains. An irreversible order-order transition (OOT) for unmodified SEBS, sSEBS, and the organic/inorganic hybrids was identified using DMA in shear mode. The OOT temperature increases with sulfonation as well as by adding a silicate phase by the sol-gel process. The DMA results imply a morphological shift with sulfonation, and reflect modified interactions within and between phases. Atomic force microscopy (AFM) indicated a shift from hexagonally packed cylinders in unmodified SEBS to a lamellar morphology in the sulfonated materials, but silicate incorporation did not affect the morphology or domain dimensions. The latter result is evidence for sol-gel polymerization templating in a self-assembly process. The phase-separated morphology is stable up to the degradation temperature of the polymer and thermogravimetric analysis revealed that the degradation temperature is unaffected by silicate incorporation. Small angle X-ray scattering data are in harmony with the structures revealed by AFM in terms of degree of order and scale of features. These results are largely rationalized in terms of chain mobility restrictions due to hydrogen-bonding interactions between different sulfonated PS blocks, an increase in the PS-ethylene/butylene block mixing parameter, increased interfacial surface tension and chain restrictions posed by inserted silicate nanostructures in the case of the hybrid materials.     

Effects of dietary casein and soy protein on metabolism of radiolabelled low density apolipoprotein B in rabbits

Rabbits fed semipurified diets containing casein have elevated plasma cholesterol levels compared to those fed soy protein. As part of continuing studies on the mechanism of casein-induced hypercholesterolemia, two groups of six rabbits were fed these diets for 14 to 16 weeks. Animals fed the casein diet were found to have significantly higher plasma concentrations of protein, cholesterol, triacylglycerol, phospholipid and apolipoprotein B (apo B) associated with low density lipoprotein (LDL) than those fed the soy protein diet. Kinetic studies showed that the fractional catabolic rate of LDL-apo B was significantly lower in animals fed casein than in those fed soy protein regardless of whether the tracer LDL was obtained from donors fed casein or soy protein. The production rate of LDL-apo B was higher in casein-fed animals but this was not statistically significant. These results show that the efficiency of removal of LDL is significantly reduced in animals fed casein compared to those fed soy protein, and that the source of LDL did not affect the efficiency of its subsequent removal. The acumulation of LDL in casein-fed animals is consistent with down-regulation of the LDL receptor.