In this work, the ability of on-line NIR spectroscopy for the prediction of the evolution of monomer concentration, conversion and average particle diameter in acrylamide inverse miniemulsion polymerization was evaluated. The spectral ranges were chosen as those representing the decrease in concentration of monomer. An increase in the baseline shift indicated that the NIR spectra were affected by particle size. Multivariate partial least squares calibration models were developed to relate NIR spectra collected by the immersion probe with off-line conversion and polymer particle size data. The results showed good agreement between off-line data and values predicted by the NIR calibration models and these latter were also able to detect different types of operational disturbances. These results indicate that it is possible to monitor variables of interest during acrylamide inverse miniemulsion polymerizations.

A green ceramic tape micro-heat exchanger was developed using Low Temperature Co-fired Ceramics technology (LTCC). The device was designed by using Computational Aided Design software and simulations were made using a Computational Fluid Dynamics package (COMSOL Multiphysics) to evaluate the homogeneity of fluid distribution in the microchannels. Four geometries were proposed and simulated in two and three dimensions to show that geometric details directly affect the distribution of velocity in the micro-heat exchanger channels. The simulation results were quite useful for the design of the microfluidic device. The micro-heat exchanger was then constructed using the LTCC technology and is composed of five thermal exchange plates in cross-flow arrangement and two connecting plates, with all plates stacked to form a device with external dimensions of 26 x 26 x 6 mm³.

The determination of conversion during suspension polymerization reactions is not an easy task due to the heterogeneity of the reaction medium and the tendency of particles to agglomerate rapidly when stirring is stopped. Usually, bulk polymerization in ampoules is employed to study the kinetics of suspension polymerization reactions. In this work, a comparison of different techniques for the determination of conversion during suspension polymerization reactions is presented. Results showed a good agreement between the conversion obtained by gravimetry during styrene suspension polymerization and on-line conversion monitoring data using fiber-optic based Raman Spectroscopy. Nevertheless, the polymerization rate of styrene bulk polymerization carried out in ampoules was higher than the real reaction rate of styrene suspension polymerization due to slightly higher reaction temperatures. Simulation results using the experimental temperature data in a mathematical model confirmed these results.

Time optimal monomer and reactor temperature set-point profiles were computed and implemented experimentally for the control of copolymer composition and minimization of reaction time in emulsion copolymerization systems. Iterative Dynamic Programming (IDP) was used for the off-line calculation of the optimal profiles. This approach can deal with constrained optimization of systems described by complex mathematical models, as those needed for the emulsion copolymerization. The optimization procedure was applied to vinyl acetate / butyl acrylate emulsion copolymerization under industrial-like conditions, which includes safety constraints normally found in the operation of large-scale reactors. The dynamics of the reactor heat exchange system were also taken into account in the mathematical model. The optimal trajectories obtained by the IDP procedure were implemented in a jacketed reactor with automated control of temperature and monomers feed flow rates. The real-time implementation of the optimal trajectories was successfully carried out resulting in a significant reduction in reaction time and the production of homogeneous copolymer composition.

The present work describes a methodology for estimation of monomer concentration during homopolymerization reactions by Raman spectroscopy. The estimation is done using linear models based on two different approaches: a univariate approach and a multivariate approach (with principal component regression, PCR, or partial least squares regression, PLS). The linear models are fitted with data from spectra collected from synthetic samples, i.e., samples prepared by dispersing a known concentration of monomer in polymer emulsions. Homopolymerizations of butyl acrylate and of vinyl acetate were monitored by collecting samples from the reactor, and results show that the methodology is efficient for the model fitting and that Raman spectroscopy is a promising technique for on-line monitoring of the emulsion polymerization process.

This work addressed the viability of using a pulsed sieve-plate column reactor to carry out continuous vinyl acetate/butyl acrylate emulsion copolymerization reactions. A rigorous mathematical model of emulsion copolymerization reactions in a tubular reactor with axial dispersion was used for this purpose. Operational conditions were defined to attain high monomer conversions at the reactor outlet in a relatively short residence time and, at the same time, produce a copolymer with a more homogeneous composition.

This work is concerned with the coupled estimation of the heat generated by the reaction (Qr) and the overall heat transfer parameter (UA) during the terpolymerization of styrene, butyl acrylate and methyl methacrylate from temperature measurements and the reactor heat balance. By making specific assumptions about the dynamics of the evolution of UA and Q R, we propose a cascade of observers to successively estimate these two parameters without the need for additional measurements of on-line samples. One further aspect of our approach is that only the energy balance around the reactor was employed. It means that the flow rate of the cooling jacket fluid was not required.

A new reactor, the pulsed sieve plate column (PSPC), was developed to perform continuous emulsion polymerization reactions. This reactor combines the enhanced flexibility of tubular reactors with the mixing behavior provided by sieved plates and by the introduction of pulses that is important to prevent emulsion destabilization. The main objective of this work is to study the kinetics of vinyl acetate (VA) emulsion polymerization reactions performed in this PSPC. Therefore, both experimental studies and reaction simulations were performed. Results showed that it is possible to obtain high conversions with rather low residence times in the PSPC.

Dynamic mathematical models are developed to simulate styrene emulsion polymerization reactions carried out in pulsed tubular reactors. Two different modeling approaches, the tanks-in-series model and the axial dispersion model, are compared. The models developed were validated with experimental data from the literature and used to study the dynamics during transient periods, e.g., the start-up of the reactor and the response to disturbances. The effect of the Peclet number on process variables such as conversion and particle concentration was also verified.

Experimental results of fixed-bed heat-transfer experiments with no chemical reaction are presented and discussed. The runs were carried out in a tubular integral reactor heated by an electrical furnace at temperatures in the range of 100 to 500°C. Experimental temperature profiles were determined for the electrical furnace, for the reactor wall, and for the fixed bed center. Industrial catalyst for the prereforming of hydrocarbons was employed as the packing material. The effects of process conditions (furnace temperature, gas flow rate) on the heat-transfer coefficients were evaluated. The experimental results were analyzed in terms of the external, wall, and internal thermal resistances, associated in series, and compared with model predictions. Under the conditions studied, the overall coefficient was mostly a function of the external effective heat-transfer coefficient. An alternative data treatment was proposed to determine the internal heat-transfer coefficient in fixed beds when wall temperature is not constant.

INTRODUÇÃO: O enfisema lobar congênito é doença rara, cuja patogênese permanece desconhecida. O interesse acadêmico reside na falta de uniformidade dos achados anatomopatológicos. Em cerca de 50%, não se consegue definir a lesão anatomopatológica. A teoria mais recente relaciona esta doença com um número aumentado de alvéolos dentro de cada ácino pulmonar. OBJETIVO: O objetivo deste trabalho é efetuar uma revisão do estudo anatomopatológico original de 12 crianças com diagnóstico de enfisema lobar congênito, procurando, mediante método quantitativo, pesquisar a presença do aumento do número de alvéolos no ácino pulmonar. MÉTODO: Os autores realizaram um estudo caso-controle pareado pela idade. O número de alvéolos em cada ácino pulmonar foi pesquisado pela técnica da contagem radial de alvéolos. Para comparar as medidas obtidas nos casos e seus respectivos controles, utilizaram a prova U de Mann-Whitney. Regressão linear avaliou a influência da idade sobre as medidas. RESULTADOS: Encontraram um número elevado de alvéolos nos portadores de enfisema lobar congênito operados com idade inferior a 3 anos, um número semelhante entre as idades de 3 e 7 anos e um número diminuído a partir dessa idade. Na criança normal, ocorre um aumento no número de alvéolos com o aumento da idade. No enfisema lobar congênito, esse número se mantém praticamente constante, independente da idade. CONCLUSÃO: Os achados permitiram concluir que: o lobo polialveolar pode ser diagnosticado por um método simples e prático como a contagem radial de alvéolos, colaborando para diminuir a freqüência de casos de etiologia desconhecida, um número de alvéolos maior que o esperado para idade encontra-se associado ao enfisema lobar congênito no paciente (operado) antes dos 3 anos de idade e que, ao contrário do que ocorre no pulmão normal, no lobo acometido por enfisema lobar congênito não ocorre aumento no número de alvéolos com o aumento na idade.

BACKGROUND: Congenital lobar emphysema is an unusual condition and its pathogenesis remains unknown. The variety of findings in pathology studies of the ressected specimens led to increasing academic interest. About 50 per cent of the cases have no definitive diagnosis in pathology. The most recent theory proposes an increased number of alveoli within each acinus (polyalveolar lobe). PURPOSE: The aim of this paper is to report the morphometric measures of surgical specimens of 12 patients with congenital lobar emphysema, using the Emery and Mithal technique (radial alveolar count). METHODS: We made a case-control study, classifying the cases by age. Mann-Whitney´s U test and linear regression techniques were used in data analysis: Mann-Whitney´s U in comparing the cases and respective controls and linear regression to evaluate the influence of age in the measures found. RESULTS: The results revealed a significantly higher radial alveolar count than expected for the age group under 3 years; no difference was observed in the age group between 3 and 7 years and in children older than 7, the radial alveolar count was lower than expected. The normal development of the lung consists in an increasing number of alveoli increase from birth until adulthood, but this number remains constant, independent of age in congenital lobar emphysema. CONCLUSIONS: Such findings allow us to conclude that polyalveolar lobe can and must be diagnosed by a simple and practical method, such as the radial alveolar count, which decreases the incidence of the unknown etiology. The findings of an increased number of alveoli on patients younger than 3 is related to congenital lobar emphysema, since the number of alveoli does not increase in congenital lobar emphysema, just the opposite to what one would expect in the normal development of the lung.