Silicon Nitride Derived from an Organometallic Polymeric Precursor: Preparation and Characterization

Partially crystalline Si₃N₄, with nanosized crystals and a specific surface area greater than 200 m²/g, is obtained by pyrolysis of a commercially available vinylic polysilane in a stream of anhydrous NH₃ to 1000°C. This polymer does not contain N initially. Crystallization to high-purity α-Si₃N₄ proceeds with additional heating above 1400°C under N₂. The changes in crystallinity, powder morphology, infrared spectra, and elemental compositions, for samples annealed from 1000° to 1600°C under N₂, are consistent with an amorphous-to-crystalline transformation. Although macroscopic consolidation and local densification occur at 1400°C, volatilization and accompanying weight loss limit bulk densification. The effect of temperature on specific surface area is examined and related to the sintering process. These results are applicable to pyrolysis, decomposition, and crystallization studies of ceramics synthesized by polymeric precursor routes.     

Flow patterns and mass transfer rates in fluidized bed ion exchange equipment

The axial mixing of ion exchange resin and liquid in fluidized beds is modelled by a series of well-mixed cells for the resin and an equal or larger number of mixed cells for the liquid. Concentration breakthrough curves are calculated using this mixing model, assuming finite mass transfer kinetics and irreversible equilibrium. The model is used to describe mixing patterns and kinetics in static fluidized beds (no resin flow); the information so obtained can be used to design continuous and periodic flow counter-current fluidized bed ion exchange systems.     

Rice husk ash filled natural rubber. I. Overall rate constant determination for the vulcanization process from rheometric data

Black rice husk ash (BRHA) and white rice husk ash (WRHA) were incorporated into natural rubber (NR) using a laboratory‐size two‐roll mill. A conventional vulcanization system (CV) was chosen and cure studies were carried out on a TI‐100 Curometer. The torque curves were obtained at 150, 160, 170, and 180°C. The overall rate and the apparent activation energy for the vulcanization process were calculated for each compound assuming that vulcanization follows first‐order kinetics. For comparison purposes, two commercial fillers, precipitated silica (Zeosil‐175) and carbon black (N762), were also used. It was observed that addition of WRHA to NR compounds increased the cross‐linking rate and lowered the apparent activation energy more markedly than the other fillers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1194–1203, 2003     

Evaluation of the thermal and mechanical properties of poly(ε‐caprolactone), low‐density polyethylene,and their blends

The thermal and mechanical properties of low‐density polyethylene (LDPE), poly(ε‐caprolactone) (PCL), and their blends were evaluated. Differential scanning calorimetry showed that increasing the PCL content of the blend did not change the LDPE melting temperature, but reduced the crystallinity by up to 16.8%. This behavior was related to interactions between the PCL chains and the crystalline phase of LDPE. Tensile strength and elongation at break values for the blends were lower than those for the pure polymers, which suggested an incompatibility between the polymers. The values for Young's modulus under tensile increased when PCL was added to LDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3909–3914, 2004     

Use of renewables for the production of chemicals: Glycerol oxidation over carbon supported gold catalysts

As a renewable feedstock and due to its high functionality glycerol is an attractive reactant for the production of a large number of valuable compounds. We report on an environmentally friendly alternative to produce chemicals from the glycerol oxidation, which are currently produced either by stoichiometric oxidation processes or by enzymatic routes. We investigate the heterogeneously catalyzed liquid-phase oxidation of glycerol with carbon supported gold catalysts. The prepared nanosized gold catalysts are highly active, so that the reaction could be performed under atmospheric pressure. The influence of the preparation method of the catalysts has been investigated. Moreover, the support effect on the catalytic process has been studied and discussed in terms of pore structure of the investigated carbon materials. The promotor effect of platinum on Au/C catalysts was examined and it could be shown that the presence of Pt increases not only the catalyst activity but also the selectivity. By promoting the gold catalysts with platinum the selectivity to dihydroxyacetone could be increased from 26% (Au/C) to 36% (Au–Pt/C).     

Modeling of solid—liquid adsorption: Effects of adsorbent loads on model parameters

The adsorption of cobalt phthalocyanine dye onto activated carbon in a continuous stirred tank adsorber was studied. The variables investigated were: adsorbent mass, adsorbent particle size and fluid flowrate. Several models based on film, pore and surface diffusion were constructed and fitted to the experimental data. Experimental results showed: (i) the increasing importance of the film mass transfer resistance for increasing adsorbent loads; (ii) the increasing importance of the surface diffusion mechanism for increasing adsorbent loads; and (iii) the better discrimination among different models for higher adsorbent loads and lower flowrate.     

Li influx and binding, and li/mg competition in bovine chromaffin cell suspensions as studied by li NMR and fluorescence spectroscopy

Li(+) influx by bovine chromaffin cells, obtained from bovine adrenal medulla, was studied in intact cell suspensions using (7)Li NMR spectroscopy with the shift reagent [Tm(HDOTP)](4-). The influx rate constants, k(i), were determined in the absence and in the presence of two Na(+) membrane transport inhibitors. The values obtained indicate that both voltage sensitive Na(+) channels and (Na(+)/K(+))-ATPase play an important role in Li(+) uptake by these cells. (7)Li NMR T(1) and T(2) relaxation times for intracellular Li(+) in bovine chromaffin cells provided a T(1)/T(2) ratio of 305, showing that Li(+) is highly, immobilized due to strong binding to intracellular structures. Using fluorescence spectroscopy and the Mg(2+) fluorescent probe, furaptra, the free intracellular Mg(2+) concentration in the bovine chromaffin cells incubated with 15 mM LiCl was found to increase by about mM after the intracellular Li(+) concentration reached a steady state. Therefore, once inside the cell, Li(+) is able to displace Mg(2+) from its binding sites.     

Digestibility and nutritional value of crude oil from three amaranth species

Oils from a selection ofAmaranthus caudatus, A. hypochondriacus andA. cruentus were extracted with hexane. The crude oils were analyzed for acid value, saponification and iodine number, and were included in basal casein diets for rat studies at 5 and 10% levels to replace equal amounts of refined cottonseed oil. The oils fromA. cruentus andA. hypochondriacus were similar in the oil properties studied and different fromA. caudatus. At either 5 or 10% food intake levels, weight gain and PER were not statistically different from values reported for cottonseed oil. True digestibility of amaranth oil was lower than that of cottonseed oil.A. cruentus oil gave the lowest digestibility. Oil levels induced statistical differences in food intake and digestibility. Oils fromA. caudatus, A. hypochondriacus and cottonseed induced similar serum cholesterol levels, while oil fromA. cruentus gave statistically higher values. Hemoglobin, hematocrit and serum proteins were similar among all groups. Microscopic analysis of the organs of the rats revealed some changes that were also found in cottonseed oil-fed rats. It was concluded that crude amaranth oil has lower digestibility than cottonseed oil, but that it is not responsible for growth-depressing effects when the seed is fed raw as compared to processed materials.     

Zeolites as catalysts in organic reactions. Claisen-Schmidt condensation of acetophenone with benzaldehyde

HY zeolites catalyze the crossed aldol condensation of acetophenone with benzaldehyde, in benzene at 80 °C, to give trans- and cis-chalcones. Together with these expected products, 3,3-diphenylpropiophenone is also produced. In the analogous basic condensation, using phase transfer catalysis, the Michael adduct was not detected, and besides chalcone a small percentage of the Cannizzaro reaction product was observed.