Estudo da blenda PBAT/PLA com cargas.

Neste trabalho compósitos foram obtidos a partir da blenda comercial 100% biodegradável Ecovio® C2224 da BASF, uma blenda formada por 55% em massa de um copoliéster biodegradável, o Ecoflex® (poli[(adipato de butileno)-co-(tereftalato de butileno)]) e 45% em massa de PLA poli(ácido láctico). Como carga, utilizaram-se dois tipos de argilas comerciais do grupo das esmectitas, ambas predominantemente montmorilonitas: Cloisite Sódica® e Cloisite 30B®. Também foi utilizado como carga a sílica coloidal comercial Aerosil 200®, com área superficial de 200 m2/g e diâmetro médio de partícula 12nm. Os compósitos estudados, ambos contendo 5% e 10% em massa de cargas, foram preparados em uma extrusora de rosca dupla, acoplada a um reômetro de torque. O estudo foi dividido em três etapas: 1ª) etapa: Obtenção e caracterização dos compósitos de Ecovio®/ argila e Ecovio® / sílica; 2ª) etapa: Avaliação da fotodegradação do Ecovio® puro e dos compósitos obtidos; 3ª) etapa: Avaliação da biodegradabilidade do Ecovio® puro e dos compósitos após exposição em câmara de UV. As propriedades mecânicas dos compósitos antes e depois de serem submetidos à exposição em câmara de UV foram avaliadas por ensaios de resistência à tração e resistência ao impacto Izod. Os resultados obtidos na 1ª etapa deste trabalho indicaram aumento nos valores de módulo de elasticidade de todos os compósitos, em relação à blenda pura. Destacam-se as composições com 5% e 10% em massa de sílica coloidal, que apresentaram aumentos de até 115% nos valores de módulo de elasticidade, sem perdas significativas em resistência à tração, alongamento e resistência ao impacto, quando comparadas à fase matriz. Na 2ª etapa, a partir de 20 dias de exposição, todas as composições (blendas e compósitos) apresentam redução nas propriedades mecânicas em função do aumento do tempo de exposição à radiação UV. Na 3ª etapa, independente do tipo ou teor de carga presente na blenda, todas as composições apresentaram índices de biodegradabilidade, depois de 120 dias, de 40 a 60%, devido à prévia exposição à radiação UV.

Analysis of the zone connecting consecutive sectors in distillation columns by the Ponchon-Savarit method

McCabe-Thiele and Ponchon-Savarit methods are two classical graphical methods for the design of binary distillation columns very useful for didactical purposes and for preliminary calculations. Nevertheless, their description in the literature is not complete and not all the cases are analysed. To complete the academic literature dealing with this subject we have generalized equations for the operating lines or DP that define the change between two consecutive sectors ΔkC for any feed condition, together with the different possibilities to extract products or to add or remove heat. A consistent analysis of what may happen when changing between sectors in the column is presented.

GE models and algorithms for condensed phase equilibrium data regression in ternary systems: limitations and proposals

Phase equilibrium data regression is an unavoidable task necessary to obtain the appropriate values for any model to be used in separation equipment design for chemical process simulation and optimization. The accuracy of this process depends on different factors such as the experimental data quality, the selected model and the calculation algorithm. The present paper summarizes the results and conclusions achieved in our research on the capabilities and limitations of the existing GE models and about strategies that can be included in the correlation algorithms to improve the convergence and avoid inconsistencies. The NRTL model has been selected as a representative local composition model. New capabilities of this model, but also several relevant limitations, have been identified and some examples of the application of a modified NRTL equation have been discussed. Furthermore, a regression algorithm has been developed that allows for the advisable simultaneous regression of all the condensed phase equilibrium regions that are present in ternary systems at constant T and P. It includes specific strategies designed to avoid some of the pitfalls frequently found in commercial regression tools for phase equilibrium calculations. Most of the proposed strategies are based on the geometrical interpretation of the lowest common tangent plane equilibrium criterion, which allows an unambiguous comprehension of the behavior of the mixtures. The paper aims to show all the work as a whole in order to reveal the necessary efforts that must be devoted to overcome the difficulties that still exist in the phase equilibrium data regression problem.

Thermogravimetric analysis of the pyrolysis of several materials used in the preparation of commercial cigarettes

Comunicación presentada en forma de póster en el "12th Mediterranean Congress of Chemical Engineering", Barcelona (Spain), November 15-18, 2011

Catalytic effect of MCM-41 in the pyrolysis of tobacco and several substances used as additives in the preparation of commercial cigarettes

Comunicación presentada en forma de póster en el "12th Mediterranean Congress of Chemical Engineering", Barcelona (Spain), November 15-18, 2011.

Effect of carbon fibres on the mechanical properties and corrosion levels of reinforced portland cement mortars

The changes in mechanical properties of portland cement mortars due to the addition of carbon fibres (CF) to the mix have been studied. Compression and flexural strengths have been determined in relation to the amount of fibres added to the mix, water/binder ratio, curing time and porosity. Additionally, the corrosion level of reinforcing steel bars embedded in portland cement mortars containing CF and silica fume (SF) have also been investigated and reinforcing steel corrosion rates have been determined. As a consequence of the large concentration of oxygen groups in CF surface, a good interaction between the CF and the water of the mortar paste is to be expected. A CF content of 0.5% of cement weight implies an optimum increase in flexural strength and an increase in embedded steel corrosion.

Electrochemical performance of carbon gels with variable surface chemistry and physics

This study describes the electrochemical characterization of N-doped carbon xerogels in the form of microspheres and of carbon aerogels with varied porosities and surface oxygen complexes. The interfacial capacitance of N-doped carbon xerogels decreased with increased micropore surface area as determined by N2 adsorption at −196 °C. The interfacial capacitance showed a good correlation with the areal NXPS concentration, and the best correlation with the areal concentration of pyrrolic or pyridonic nitrogen functionalities. The gravimetric capacitance decreased with greater xerogel microsphere diameter. The interfacial capacitance of carbon aerogels increased with higher percentage of porosity as determined from particle and true densities. The interfacial capacitance showed a linear relationship with the areal oxygen concentration and with the areal concentrations of CO- and CO2-evolving groups.

Investigating the influence of surfactants on the stabilization of aqueous reduced graphene oxide dispersions and the characteristics of their composite films

The stabilization of reduced graphene oxide (RGO) sheets in aqueous dispersion using a wide range of surfactants of anionic, non-ionic and zwitterionic type has been investigated and compared under different conditions of pH, surfactant and RGO concentration, or sheet size. The observed differences in the performance of the surfactants were rationalized on the basis of their chemical structure (e.g., alkylic vs. aromatic hydrophobic tail or sulfonic vs. carboxylic polar head), thus providing a reference framework in the selection of appropriate surfactants for the processing of RGO suspensions towards particular purposes. RGO-surfactant composite paper-like films were also prepared through vacuum filtration of the corresponding mixed dispersions and their main characteristics were investigated. The composite paper-like films were also electrochemically characterized. Those prepared with two specific surfactants exhibited a high capacitance in relation to their surfactant-free counterpart.

Review and extension of the McCabe-Thiele method covering multiple feeds, products and heat transfer stages

The McCabe-Thiele method is a classical approximate graphical method for the conceptual design of binary distillation columns which is still widely used, mainly for didactical purposes, though it is also valuable for quick preliminary calculations. Nevertheless, no complete description of the method has been found and situations such as different thermal feed conditions, multiple feeds, possibilities to extract by-products or to add or remove heat, are not always considered. In the present work we provide a systematic analysis of such situations by developing the generalized equations for: a) the operating lines (OL) of each sector, and b) the changeover line that provides the connection between two consecutive trays of the corresponding sectors separated by a lateral stream of feed, product, or a heat removal or addition.

A novel hybrid simulation-optimization approach for the optimal design of multicomponent distillation columns

Póster presentado en Escape 22, European Symposium on Computer Aided Process Engineering, University College London, UK, 17-20 June 2012.

Mechanical, thermal and colorimetric properties of LLDPE coloured with a blue nanopigment and conventional blue pigments

Purpose – This research deals with a new kind of nanopigment, obtained from the combination of organic dyes and layered nanoclays, that the authors call nanoclay-colorant pigment (NCP). Whilst they have already been employed in inks and coatings, to date these nanopigments have not been used as pigments for polymers. The existing lack of knowledge surrounding them must be redressed in order to bridge the gap between current academic studies and commercial exploitation. Therefore, the main purpose of this paper is to examine the hitherto unknown aspects of the NCP, which relate specifically to their applicability as a new type of colorant for polymers. Design/methodology/approach – A blue NCP has been prepared at the laboratory according to the patented method of synthesis (patent WO0104216), using methylene blue and montmorillonite nanoclay. It has then been applied to a thermoplastic polymer (linear low-density polyethylene – LLDPE) to obtain a coloured sample. Furthermore, samples with the same polymer but using conventional blue colorants have been prepared under the same processing conditions. The mechanical, thermal and colorimetric properties of these materials have been compared. Findings – The thermal stability of the sample coloured with NCP is reduced to some extent, while the mechanical strength is slightly increased. Moreover, this sample has better colour performance than the conventionally pigmented samples. Originality/value – In this paper, a blue NCP has been synthesised and successfully employed with polyethylene and the obtained sample shows better colour performance than polyethylene with conventional pigments.

Combined simulation-optimization methodology for the design of environmental conscious absorption systems

This work addresses the optimization of ammonia–water absorption cycles for cooling and refrigeration applications with economic and environmental concerns. Our approach combines the capabilities of process simulation, multi-objective optimization (MOO), cost analysis and life cycle assessment (LCA). The optimization task is posed in mathematical terms as a multi-objective mixed-integer nonlinear program (moMINLP) that seeks to minimize the total annualized cost and environmental impact of the cycle. This moMINLP is solved by an outer-approximation strategy that iterates between primal nonlinear programming (NLP) subproblems with fixed binaries and a tailored mixed-integer linear programming (MILP) model. The capabilities of our approach are illustrated through its application to an ammonia–water absorption cycle used in cooling and refrigeration applications.

Vapor-liquid equilibria using the Gibbs energy and the common tangent plane criterion

Phase thermodynamics is often perceived as a difficult subject that many students never become fully comfortable with. The Gibbsian geometrical framework can help students to gain a better understanding of phase equilibria. An exercise to interpret the vapor-liquid equilibrium of a binary azeotropic mixture, using the equilibrium condition based on the common tangent plane criterion (the Gibbs stability test), is presented in this paper. From a T-composition phase diagram for the mixture, the temperature is set at different values: above, intermediate to, and below the boiling temperatures of the pure components, to intersect different regions of the system. Students prepare an Excel spreadsheet where the Gibbs energy of mixing of the vapor and liquid mixtures are calculated and represented over the whole range of compositions and then, apply the Gibbs stability test to ascertain the aggregation state of the system and to calculate the VL phase equilibrium compositions. Finally, Matlab is used to generate the 3D Gibbs energy of mixing surfaces for both phases over the whole range of temperatures which facilitates the geometrical interpretation of the vapor-liquid equilibrium.

Correlation of the liquid–liquid equilibrium data for specific ternary systems with one or two partially miscible binary subsystems

This paper presents the results of a liquid–liquid equilibrium data correlation for 11 ternary systems which have not been previously fitted using the NRTL model or, when they have, the results presented in the literature are inconsistent with the experimental behavior of the system. These ternary systems include mixtures with one or two partially miscible pairs. During the correlation process, new restrictions were imposed on the values for the NRTL binary parameters to ensure correct prediction of the total or partial miscibility for the binary pairs involved. In addition, topological concepts related to the Gibbs stability test have been applied in order to validate the results in the whole range of compositions.

Modelling liquid–liquid equilibria for island type ternary systems

Closed miscibility gaps in ternary liquid mixtures, at constant temperature and pressure, are obtained if phase separations occur only in the ternary region, whilst all binary mixtures involved in the system are completely miscible. This type of behaviour, although not very frequent, has been observed for a certain number of systems. Nevertheless, we have found no information about the applicability of the common activity coefficient models, as NRTL and UNIQUAC, for these types of ternary systems. Moreover, any of the island type systems published in the most common liquid–liquid equilibrium data collections, are correlated with any model. In this paper, the applicability of the NRTL equation to model the LLE of island type systems is assessed using topological concepts related to the Gibbs stability test. A first attempt to correlate experimental LLE data for two island type ternary systems is also presented.