Resumo em Inglês:

Related momentum and energy equations describing the heat and fluid flow of Herschel-Bulkley fluids within concentric annular ducts are analytically solved using the classical integral transform technique, which permits accurate determination of parameters of practical interest in engineering such as friction factors and Nusselt numbers for the duct length. In analyzing the problem, thermally developing flow is assumed and the duct walls are subjected to boundary conditions of first kind. Results are computed for the velocity and temperature fields as well as for the parameters cited above with different power-law indices, yield numbers and aspect ratios. Comparisons are also made with previous work available in the literature, providing direct validation of the results and showing that they are consistent.

Resumo em Inglês:

The aim of this work was to prepare tungsten oxycarbides by Temperature Programmed Reaction (TPR), starting with previously molded macroporous tungsten oxide (WO3). The tungsten oxycarbides were prepared by one of two different methods: direct carburization with CH4/H2 to obtain WC or preliminary formation of nitrides with NH3 to obtain W2N, followed by carburization to W2C and WC with CH4/H2. Results suggested that the carburization of the W2N was incomplete, resulting in an oxycarbonitride, or did not occur at all, with the end material being W2N. From among the materials prepared, two catalysts were selected as a function of their mechanical properties, and their performances were compared with a 2 N microthruster using the Shell 405 commercial catalyst in the reaction of hydrazine decomposition.

Resumo em Inglês:

The Vrentas/Duda proposal for the diffusion of polymer-solvent systems, which is based on the free-volume theory, was employed in correlating and predicting mutual diffusion coefficients in highly concentrated polymer solutions. It has been observed that the predictive version of the model is capable of qualitatively representing the experimental data, while the use of an adjustable parameter greatly improves the performance of the model. The systems studied were poly(vinyl) acetate-toluene and Neoprene-acetone, and a comparison between experimental data and calculated values from the Vrentas/Duda model is reported. A new experimental apparatus based on the sorption technique was built to provide reliable diffusivity data on the Neoprene-acetone system.

Resumo em Inglês:

The effect of surface topography upon the adsorption of dimer molecules is analyzed by means of grand canonical ensemble Monte Carlo simulations. Heterogeneous surfaces were assumed to consist of a square lattice containing active sites with two different energies. These were distributed in three different configurations: a random distribution of isolated sites; a random distribution of grains with four high-energy sites; and a random distribution of grains with nine high-energy sites. For the random distribution of isolated sites, the results are in good agreement with the molecular simulations performed by Nitta et al. (1997). In general, the comparison with theoretical models shows that the Nitta et al. (1984) isotherm presents good predictions of dimer adsorption both on homogeneous and heterogeneous surfaces with sites having small differences in characteristic energies. The molecular simulation results also show that the energy topology of the solid surfaces plays an important role in the adsorption of dimers on solids with large differences in site energies. For these cases, the Nitta et al. model does not describe well the data on dimer adsorption on random heterogeneous surfaces (grains with one acid site), but does describe reasonably well the adsorption of dimers on more patchwise heterogeneous surfaces (grains with nine acid sites).

Resumo em Inglês:

TiCxNy coatings deposited on high-speed steel substrates have been used to enhance the tribological properties of cutting tools (hardness, wear resistance, etc.) as well as their corrosion resistance in an aggressive environment. These layers are usually produced by plasma deposition techniques (PVD or CVD), and different coating properties can be obtained with each method. In this work, TiCxNy films were deposited on AISI M2 high-speed steel substrates by the reactive magnetron sputtering technique. A series of samples with a variety of reactive gas mixtures (nitrogen and methane), substrate biases, and deposition temperatures was produced. As a result, coatings with different chemical compositions were deposited for each group of deposition parameters. Gas mixture composition and substrate bias directly affected the chemical composition of the coating, while deposition temperature influenced the chemical composition of TiCxNy layers to a very low extent.

Resumo em Inglês:

Some years ago the authors proposed a model for the non-ideality of the solid phase, based on the Predictive Local Composition concept. This was first applied to the Wilson equation and latter extended to NRTL and UNIQUAC models. Predictive UNIQUAC proved to be extraordinarily successful in predicting the behaviour of both model and real hydrocarbon fluids at low temperatures. This work illustrates the ability of Predictive UNIQUAC in the description of the low temperature behaviour of petroleum fluids. It will be shown that using Predictive UNIQUAC in the description of the solid phase non-ideality a complete prediction of the low temperature behaviour of synthetic paraffin solutions, fuels and crude oils is achieved. The composition of both liquid and solid phases, the amount of crystals formed and the cloud points are predicted within the accuracy of the experimental data. The extension of Predictive UNIQUAC to high pressures, by coupling it with an EOS/G E model based on the SRK EOS used with the LCVM mixing rule, is proposed and predictions of phase envelopes for live oils are compared with experimental data.

Resumo em Inglês:

Crystallization and precipitation from solutions are responsible for 70% of all solid materials produced by the chemical industry. Competing with distillation as a separation and purification technique, their use is widespread. They operate at low temperatures with low energy consumption and yield with high purifications in one single step. Operational conditions largely determine product quality in terms of purity, filterability, flowability and reactivity. Producing a material with the desired quality often requires a sound knowledge of the elementary steps involved in the process: creation of supersaturation, nucleation, crystal growth, aggregation and other secondary processes. Mathematical models coupling these elementary processes to all particles in a crystallizer have been developed to design and optimize crystallizer operation. For precipitation, the spatial distribution of reactants and particles in the reactor is important; thus the tools of computational fluid dynamics are becoming increasingly important. For crystallization of organic chemicals, where incorporation of impurities and crystal shape are critical, molecular modeling has recently appeared as a useful tool. These theoretical developments must be coupled to experimental data specific to each material. Theories and experimental techniques of industrial crystallization and precipitation from solutions are reviewed, and recent developments are highlighted.

Resumo em Inglês:

Tertiary alkylamines in solution with organic diluents are attractive extractants for the recovery of carboxylic acids from dilute aqueous phases. The aim of this study was to investigate the mechanism for extraction of organic acids from water by a long-chain aliphatic tertiary amine. In order to attain this objective, we studied the liquid-liquid equilibria between the triisooctylamine + 1-octanol + n-heptane system as solvent and an aqueous solution of an individual carboxylic acid such as citric, lactic and malic acids. The experiments showed that the partition coefficient for a particular organic acid depends on the kind of solute, notably when the acid concentration in the aqueous phase is low. A mathematical model, where both chemical association and physical distribution are taken into consideration, is proposed. The model suggests that the various complexes obtained between amine and organic acids contribute to the distribution of the solute between the coexisting phases in equilibrium.

Resumo em Inglês:

Aqueous two-phase systems (ATPSs) have found wide application in the separation of biological molecules such as amino acids, peptides and proteins. Most of the research in this area has been dedicated to experimental determination and less effort has been devoted to the proper thermodynamic modeling of these systems. This work presents a new model for ATPS that accounts for solvation effects between polymer and water molecules, which are commonly reported to be responsible for phase separation. The model uses the Flory-Huggins equation as a starting point and modifies the combinatorial term by considering the presence of a hydration shell. The modified equation parameters were fit to a number of isotherms of poly(ethylene glycol) - dextran systems, and the results obtained are reported herein. These results show that the adopted modification leads to remarkable improvements in the performance of the model.

Resumo em Inglês:

A large number of advantages are obtained from the use of highly concentrated worts during the production of beer in a process referred to as "high-gravity". However, problems related to slow or stuck fermentations, which cause the lower productivity and possibility of contamination, are encountered. This study examines the influence of factors pH, percentage of corn syrup, initial wort concentration and fermentation temperature on the fermentation parameters, namely productivity, wort attenuation and the yield coefficient for sugar-to-ethanol conversion. The results show that productivity increased when the higher temperature, the higher wort concentration and the lower syrup percentage were used, while wort attenuation increased when lower wort concentration and no syrup were used. The yield coefficient for sugar-to-ethanol conversion was not influenced by any of the factors studied.

Resumo em Inglês:

In one of the stages of the gelatin production process, a highly concentrated solution of gel is cooled and extruded to form gelatin noodles, which are then laid on a drying belt. Gelatin is a molecular colloid that is not porous under these drying conditions, and as a consequence, water migration occurs solely by diffusive processes. To achieve a commercial standard of dryness, the dependence of the diffusion coefficient as a function of temperature is used. This set of circumstances favors the appearance of sharp concentration gradients inside the gel. In a numerical simulation of the drying process these characteristics create difficult conditions for use of the traditional methods for solution of time-dependent partial differential equation models. This paper evaluates an implementation of the boundary element method to determine surface conditions of the gelatin particle.