A review of drainage and spontaneous rupture in free standing thin films with tangentially immobile interfaces

A review of spontaneous rupture in thin films with tangentially immobile interfaces is presented that emphasizes the theoretical developments of film drainage and corrugation growth through the linearization of lubrication theory in a cylindrical geometry. Spontaneous rupture occurs when corrugations from adjacent interfaces become unstable and grow to a critical thickness. A corrugated interface is composed of a number of waveforms and each waveform becomes unstable at a unique transition thickness. The onset of instability occurs at the maximum transition thickness, and it is shown that only upper and lower bounds of this thickness can be predicted from linear stability analysis. The upper bound is equivalent to the Freakel criterion and is obtained from the zeroth order approximation of the H-3 term in the evolution equation. This criterion is determined solely by the film radius, interfacial tension and Hamaker constant. The lower bound is obtained from the first order approximation of the H-3 term in the evolution equation and is dependent on the film thinning velocity A semi-empirical equation, referred to as the MTR equation, is obtained by combining the drainage theory of Manev et al. [J. Dispersion Sci. Technol., 18 (1997) 769] and the experimental measurements of Radoev et al. [J. Colloid Interface Sci. 95 (1983) 254] and is shown to provide accurate predictions of film thinning velocity near the critical thickness of rupture. The MTR equation permits the prediction of the lower bound of the maximum transition thickness based entirely on film radius, Plateau border radius, interfacial tension, temperature and Hamaker constant. The MTR equation extrapolates to Reynolds equation under conditions when the Plateau border pressure is small, which provides a lower bound for the maximum transition thickness that is equivalent to the criterion of Gumerman and Homsy [Chem. Eng. Commun. 2 (1975) 27]. The relative accuracy of either bound is thought to be dependent on the amplitude of the hydrodynamic corrugations, and a semiempirical correlation is also obtained that permits the amplitude to be calculated as a function of the upper and lower bound of the maximum transition thickness. The relationship between the evolving theoretical developments is demonstrated by three film thickness master curves, which reduce to simple analytical expressions under limiting conditions when the drainage pressure drop is controlled by either the Plateau border capillary pressure or the van der Waals disjoining pressure. The master curves simplify solution of the various theoretical predictions enormously over the entire range of the linear approximation. Finally, it is shown that when the Frenkel criterion is used to assess film stability, recent studies reach conclusions that are contrary to the relevance of spontaneous rupture as a cell-opening mechanism in foams. (C) 2003 Elsevier Science B.V. All rights reserved.

A kinetic study of the thermally initiated free radical reactions of styrene with octanedithiol as a model for the reactions of multifunctional thiols with divinylbenzene

The kinetics of chain reactions of octanedithiol with styrene, thermally initiated with TX29B50 (a 50:50 wt% solution of TX29 diperoxy initiator in a phthalate plasticizer), have been studied over a range of initiator concentrations, a range of mixture formulations and a range of temperatures. This system has been investigated as a model system for the reactions of polyfunctional thiols with divinyl benzene. The reactions have been shown to follow first-order kinetics for both the thiol and the ene species and to be characterized by a dependence on the initiator concentration to the power of one half. The kinetic rate parameters have been shown to adhere to Arrhenius behaviour. A kinetic model for the chain reactions for this system has been proposed. (C) 2003 Society of Chemical Industry.

New heterogeneous catalysts for trans-esterification of triglycerides

This paper describes preliminary work done towards the development of new metallic heterogeneous catalysts to be used in the transesterification reaction of triglycerides, which is of considerable interest in the production of biodiesel. Biodiesel, is a mixture of mono-alkyl esters of fatty acids, and is currently manufactured by transesterification of triglycerides with methanol using NaOH or KOH as liquid base catalyst. Catalysts as such are corrosive to the equipment, and as these catalysts are in liquid phase must be neutralized after the completion of the reaction, typically using HCl, thus producing salt streams. Moreover, due to the presence of free fatty acids it reacts to form soaps as unwanted by-products, hence requiring more expensive separation processes. Therefore, there is a great need on the development of industrial processes for biodiesel production using solid acid catalysts. The key benefit of using solid acid catalysts is that no polluting by-products are formed and the catalysts do not have to be removed since they do not mix with the biodiesel product.

Scaling of the elastic contribution to the surface free energy of a nematic liquid crystal on a sawtoothed substrate

We characterize the elastic contribution to the surface free energy of a nematic liquid crystal in the presence of a sawtooth substrate. Our findings are based on numerical minimization of the Landau-de Gennes model and analytical calculations on the Frank-Oseen theory. The nucleation of disclination lines (characterized by non-half-integer winding numbers) in the wedges and apexes of the substrate induces a leading order proportional to q ln q to the elastic contribution to the surface free-energy density, with q being the wave number associated with the substrate periodicity.

Constructing good deals in discrete time arbitrage-free dynamic pricing models

Recent literature has proved that many classical pricing models (Black and Scholes, Heston, etc.) and risk measures (V aR, CV aR, etc.) may lead to “pathological meaningless situations”, since traders can build sequences of portfolios whose risk leveltends to −infinity and whose expected return tends to +infinity, i.e., (risk = −infinity, return = +infinity). Such a sequence of strategies may be called “good deal”. This paper focuses on the risk measures V aR and CV aR and analyzes this caveat in a discrete time complete pricing model. Under quite general conditions the explicit expression of a good deal is given, and its sensitivity with respect to some possible measurement errors is provided too. We point out that a critical property is the absence of short sales. In such a case we first construct a “shadow riskless asset” (SRA) without short sales and then the good deal is given by borrowing more and more money so as to invest in the SRA. It is also shown that the SRA is interested by itself, even if there are short selling restrictions.

Incidence rate and spatio-temporal clustering of type 1 diabetes in Santiago, Chile, from 1997 to 1998

OBJECTIVE: To estimate the incidence rate of type 1 diabetes in the urban area of Santiago, Chile, from March 21, 1997 to March 20, 1998, and to assess the spatio-temporal clustering of cases during that period. METHODS: All sixty-one incident cases were located temporally (day of diagnosis) and spatially (place of residence) in the area of study. Knox's method was used to assess spatio-temporal clustering of incident cases. RESULTS: The overall incidence rate of type 1 diabetes was 4.11 cases per 100,000 children aged less than 15 years per year (95% confidence interval: 3.06--5.14). The incidence rate seems to have increased since the last estimate of the incidence calculated for the years 1986--1992 in the metropolitan region of Santiago. Different combinations of space-time intervals have been evaluated to assess spatio-temporal clustering. The smallest p-value was found for the combination of critical distances of 750 meters and 60 days (uncorrected p-value = 0.048). CONCLUSIONS: Although these are preliminary results regarding space-time clustering in Santiago, exploratory analysis of the data method would suggest a possible aggregation of incident cases in space-time coordinates.

Effect of the number of shells on the pressure and energy of two-dimensional free bubble clusters

We have performed Surface Evolver simulations of two-dimensional hexagonal bubble clusters consisting of a central bubble of area lambda surrounded by s shells or layers of bubbles of unit area. Clusters of up to twenty layers have been simulated, with lambda varying between 0.01 and 100. In monodisperse clusters (i.e., for lambda = 1) [M.A. Fortes, F Morgan, M. Fatima Vaz, Philos. Mag. Lett. 87 (2007) 561] both the average pressure of the entire Cluster and the pressure in the central bubble are decreasing functions of s and approach 0.9306 for very large s, which is the pressure in a bubble of an infinite monodisperse honeycomb foam. Here we address the effect of changing the central bubble area lambda. For small lambda the pressure in the central bubble and the average pressure were both found to decrease with s, as in monodisperse clusters. However, for large,, the pressure in the central bubble and the average pressure increase with s. The average pressure of large clusters was found to be independent of lambda and to approach 0.9306 asymptotically. We have also determined the cluster surface energies given by the equation of equilibrium for the total energy in terms of the area and the pressure in each bubble. When the pressures in the bubbles are not available, an approximate equation derived by Vaz et al. [M. Fatima Vaz, M.A. Fortes, F. Graner, Philos. Mag. Lett. 82 (2002) 575] was shown to provide good estimations for the cluster energy provided the bubble area distribution is narrow. This approach does not take cluster topology into account. Using this approximate equation, we find a good correlation between Surface Evolver Simulations and the estimated Values of energies and pressures. (C) 2008 Elsevier B.V. All rights reserved.

Improving management skills through business simulation

A survey was conducted among students of the Accounting and Administration undergraduate degree at ISCAP – IPP (School of Accounting and Administration of Polytechnic Institute of Porto) in order to understand their perception value of their course Business Simulation (BS). This course is provided in a business environment where students can learn by doing through the management of a company as they were in the real life, but risk-free. The learning tasks are provided in an action-oriented format to maximize the learning process. Students learn by doing a set of tasks every session and have also to produce reports and presentations during the course. BS is part of the undergraduate degree of Accounting and Administration at ISCAP – IPP since the beginning of 2003. The questionnaire we used captured the students’ perception about general and specific skills and competencies considered important for managers and accountants in the real life, about the methodology used in the course, which is totally different from the traditional form, and also about the adequacy of the course included as part of the undergraduate degree. The results showed that students’ perception is highly positive and almost all of them think they improve the skills needed for a job during the course. These results are consistent with [1] Adler and Milne’s research in which the authors found that students agree with the use of action-oriented learning tasks in order to provide them the needed attitudes, skills, and knowledge. The improvement of group skills is the most important issue for students, which can be understandable as BS is the only course from the degree in Accounting and Administration they really have to work in groups.

Direct multisearch for multiobjective optimization

In practical applications of optimization it is common to have several conflicting objective functions to optimize. Frequently, these functions are subject to noise or can be of black-box type, preventing the use of derivative-based techniques. We propose a novel multiobjective derivative-free methodology, calling it direct multisearch (DMS), which does not aggregate any of the objective functions. Our framework is inspired by the search/poll paradigm of direct-search methods of directional type and uses the concept of Pareto dominance to maintain a list of nondominated points (from which the new iterates or poll centers are chosen). The aim of our method is to generate as many points in the Pareto front as possible from the polling procedure itself, while keeping the whole framework general enough to accommodate other disseminating strategies, in particular, when using the (here also) optional search step. DMS generalizes to multiobjective optimization (MOO) all direct-search methods of directional type. We prove under the common assumptions used in direct search for single objective optimization that at least one limit point of the sequence of iterates generated by DMS lies in (a stationary form of) the Pareto front. However, extensive computational experience has shown that our methodology has an impressive capability of generating the whole Pareto front, even without using a search step. Two by-products of this paper are (i) the development of a collection of test problems for MOO and (ii) the extension of performance and data profiles to MOO, allowing a comparison of several solvers on a large set of test problems, in terms of their efficiency and robustness to determine Pareto fronts.

Otimização de um sistema de "Free-Cooling" de uma instalação de climatização: incluindo a definição de um algoritmo de controlo de funcionamento

A utilização de equipamentos de climatização é cada vez mais frequente, e surgem novas tecnologias para aumentar a eficiência do processo, e neste caso, a opção da instalação de um sistema de Unidade de Tratamento de Ar com Economizador é a fundamental temática deste trabalho de dissertação. O “Free-Cooling” baseia-se na utilização total ou parcial do ar exterior para proceder à climatização de um espaço, quando se verificam as condições ótimas para o processo, e quando o sistema apresenta um controlador que permita gerir a abertura dos registos face à temperatura exterior e interior medida. A análise das condições exteriores e interiores é fundamental para dimensionar um Economizador. É necessário determinar o tipo de clima do local para fazer a seleção do tipo de controlo do processo, e recolher também, o perfil de temperaturas exterior para justificar a utilização de “Free-Cooling” no local. A determinação das condições interiores como a quantificação da utilização da iluminação, ocupação e equipamentos, é necessária para determinar a potência das baterias de arrefecimento ou aquecimento, e no caso de ser utilizado “Free-Cooling”, determinar o caudal de ar exterior a insuflar. O balanço térmico das instalações explicita todas as cargas influentes no edifício, e permite quantificar a potência necessária para climatização. Depois, adicionando o Economizador no sistema e comparando os dois sistemas, verifica-se a redução dos custos de utilização da bateria de arrefecimento. O desenvolvimento de um algoritmo de controlo é fundamental para garantir a eficiência do Economizador, onde o controlo dos registos de admissão e retorno de ar é obrigatoriamente relacionado com a leitura dos sensores de temperatura exterior e interior. A quantidade de ar novo insuflado no espaço depende, por fim, da relação entre a carga sensível do local e a diferença de temperatura lida entre os dois sensores.

Data mining contributions to characterize MV consumers and to improve the suppliers-consumers settlements

This paper deals with the establishment of a characterization methodology of electric power profiles of medium voltage (MV) consumers. The characterization is supported on the data base knowledge discovery process (KDD). Data Mining techniques are used with the purpose of obtaining typical load profiles of MV customers and specific knowledge of their customers’ consumption habits. In order to form the different customers’ classes and to find a set of representative consumption patterns, a hierarchical clustering algorithm and a clustering ensemble combination approach (WEACS) are used. Taking into account the typical consumption profile of the class to which the customers belong, new tariff options were defined and new energy coefficients prices were proposed. Finally, and with the results obtained, the consequences that these will have in the interaction between customer and electric power suppliers are analyzed.

Typical load profiles in the smart grid context – a clustering methods comparison

The present research paper presents five different clustering methods to identify typical load profiles of medium voltage (MV) electricity consumers. These methods are intended to be used in a smart grid environment to extract useful knowledge about customer’s behaviour. The obtained knowledge can be used to support a decision tool, not only for utilities but also for consumers. Load profiles can be used by the utilities to identify the aspects that cause system load peaks and enable the development of specific contracts with their customers. The framework presented throughout the paper consists in several steps, namely the pre-processing data phase, clustering algorithms application and the evaluation of the quality of the partition, which is supported by cluster validity indices. The process ends with the analysis of the discovered knowledge. To validate the proposed framework, a case study with a real database of 208 MV consumers is used.