Diffusion coefficients in dense and supercritical fluids

Os coeficientes de difusão (D 12) são propriedades fundamentais na investigação e na indústria, mas a falta de dados experimentais e a inexistência de equações que os estimem com precisão e confiança em fases comprimidas ou condensadas constituem limitações importantes. Os objetivos principais deste trabalho compreendem: i) a compilação de uma grande base de dados para valores de D 12 de sistemas gasosos, líquidos e supercríticos; ii) o desenvolvimento e validação de novos modelos de coeficientes de difusão a diluição infinita, aplicáveis em amplas gamas de temperatura e densidade, para sistemas contendo componentes muito distintos em termos de polaridade, tamanho e simetria; iii) a montagem e teste de uma instalação experimental para medir coeficientes de difusão em líquidos e fluidos supercríticos. Relativamente à modelação, uma nova expressão para coeficientes de difusão a diluição infinita de esferas rígidas foi desenvolvida e validada usando dados de dinâmica molecular (desvio relativo absoluto médio, AARD = 4.44%) Foram também estudados os coeficientes de difusão binários de sistemas reais. Para tal, foi compilada uma extensa base de dados de difusividades de sistemas reais em gases e solventes densos (622 sistemas binários num total de 9407 pontos experimentais e 358 moléculas) e a mesma foi usada na validação dos novos modelos desenvolvidos nesta tese. Um conjunto de novos modelos foi proposto para o cálculo de coeficientes de difusão a diluição infinita usando diferentes abordagens: i) dois modelos de base molecular com um parâmetro específico para cada sistema, aplicáveis em sistemas gasosos, líquidos e supercríticos, em que natureza do solvente se encontra limitada a apolar ou fracamente polar (AARDs globais na gama 4.26-4.40%); ii) dois modelos de base molecular biparamétricos, aplicáveis em todos os estados físicos, para qualquer tipo de soluto diluído em qualquer solvente (apolar, fracamente polar e polar). Ambos os modelos dão origem a erros globais entre 2.74% e 3.65%; iii) uma correlação com um parâmetro, específica para coeficientes de difusão em dióxido de carbono supercrítico (SC-CO2) e água líquida (AARD = 3.56%); iv) nove correlações empíricas e semi-empíricas que envolvem dois parâmetros, dependentes apenas da temperatura e/ou densidade do solvente e/ou viscosidade do solvente. Estes últimos modelos são muito simples e exibem excelentes resultados (AARDs entre 2.78% e 4.44%) em sistemas líquidos e supercríticos; e v) duas equações preditivas para difusividades de solutos em SC-CO2, em que os erros globais de ambas são inferiores a 6.80%. No global, deve realçar-se o facto de os novos modelos abrangerem a grande variedade de sistemas e moléculas geralmente encontrados. Os resultados obtidos são consistentemente melhores do que os obtidos com os modelos e abordagens encontrados na literatura. No caso das correlações com um ou dois parâmetros, mostrou-se que estes mesmos parâmetros podem ser ajustados usando um conjunto muito pequeno de dados, e posteriormente serem utilizados na previsão de valores de D 12 longe do conjunto original de pontos. Uma nova instalação experimental para medir coeficientes de difusão binários por técnicas cromatográficas foi montada e testada. O equipamento, o procedimento experimental e os cálculos analíticos necessários à obtenção dos valores de D 12 pelo método de abertura do pico cromatográfico, foram avaliados através da medição de difusividades de tolueno e acetona em SC-CO2. Seguidamente, foram medidos coeficientes de difusão de eucaliptol em SC-CO2 nas gamas de 202 – 252 bar e 313.15 – 333.15 K. Os resultados experimentais foram analisados através de correlações e modelos preditivos para D12.

Designing and evaluating an instructional exercise as a supplement to the Fluids & Electrolytes lecture

First year nursing students repeatedly have difficulty recalling, understanding, and applying knowledge from the Fluids & Electrolytes (F&E) class. Although the traditional teaching method of lecturing is appropriate in a situation of knowledge acquisition, this situation refers to a broader context. An alternate teaching method is needed to increase students' understanding of the previously acquired knowledge and its application. This research concerns gaming as a tool for teaching with the focus on process as well as product. An instructional exercise, in the Jeopardy format, is designed to incorporate understanding (through problem-solving), group collaboration, and metacognition. Constructivist philosophy is combined with Instructional Design to construct an exercise that focuses not only on knowledge recall, but also emphasizes thinking, understanding, and the reflective nature of the exercise. The focus of this research is to design and evaluate an exercise as a supplemental teaching method to the lecture presentation of the F&E class.

Temperature modelling of an homogeneous medium using genetically selected RBF (LIC)

Temperature modelling of human tissue subjected to ultrasound for therapeutic use is essencial for an accurate instrumental assessment and calibration. In this paper punctual temperature modeling of a homogeneous medium, radiated by therapeutic ultrasound, is presented.

Production of laminar extrudates containing particles of a model drug processed by supercritical fluids

Tese de doutoramento, Farmácia (Tecnologia Farmacêutica), Universidade de Lisboa, Faculdade de Farmácia, 2015

Friction losses of Newtonian and non-Newtonian fluids flowing in laminar regime in a helical coil

This study aimed to carry out experimental work to determine, for Newtonian and non-Newtonian fluids, the friction factor (fc) with simultaneous heat transfer, at constant wall temperature as boundary condition, in fully developed laminar flow inside a vertical helical coil. The Newtonian fluids studied were aqueous solutions of glycerol, 25%, 36%, 43%, 59% and 78% (w/w). The non-Newtonian fluids were aqueous solutions of carboxymethylcellulose (CMC), a polymer, with concentrations of 0.2%, 0.3%, 0.4% and 0.6% (w/w) and aqueous solutions of xanthan gum (XG), another polymer, with concentrations of 0.1% and 0.2% (w/w). According to the rheological study done, the polymer solutions had shear-thinning behavior and different values of viscoelasticity. The helical coil used has an internal diameter, curvature ratio, length and pitch, respectively: 0.00483 m, 0.0263, 5.0 m and 11.34 mm. It was concluded that the friction factors, with simultaneous heat transfer, for Newtonian fluids can be calculated using expressions from literature for isothermal flows. The friction factors for CMC and XG solutions are similar to those for Newtonian fluids when the Dean number, based in a generalized Reynolds number, is less than 80. For Dean numbers higher than 80, the friction factors of the CMC solutions are lower those of the XG solutions and of the Newtonian fluids. In this range the friction factors decrease with the increase of the viscometric component of the solution and increase for increasing elastic component. The change of behavior at Dean number 80, for Newtonian and non-Newtonian fluids, is in accordance with the study of Ali [4]. There is a change of behavior at Dean number 80, for Newtonian and non-Newtonian fluids, which is in according to previous studies. The data also showed that the use of the bulk temperature or of the film temperature to calculate the physical properties of the fluid has a residual effect in the friction factor values.

Heat transfer coefficients from Newtonian and non-Newtonian fluids flowing in laminar regime in a helical coil

This study aimed to carry out experimental work to obtain, for Newtonian and non-Newtonian fluids, heat transfer coefficients, at constant wall temperature as boundary condition, in fully developed laminar flow inside a helical coil. The Newtonian fluids studied were aqueous solutions of glycerol, 25%, 36%, 43%, 59% and 78% (w/w) and the non-Newtonian fluids aqueous solutions of carboxymethylcellulose (CMC), a polymer, with concentrations 0.1%, 0.2%, 0.3%, 0.4% and 0.6% (w/w) and aqueous solutions of xanthan gum (XG), another polymer, with concentrations 0.1% and 0.2% (w/w). According to the rheological study performed, the polymer solutions had shear thinning behavior and different values of elasticity. The helical coil used has internal diameter, curvature ratio, length and pitch, respectively: 0.004575 m, 0.0263, 5.0 m and 11.34 mm. The Nusselt numbers for the CMC solutions are, on average, slightly higher than those for Newtonian fluids, for identical Prandtl and generalized Dean numbers. As outcome, the viscous component of the shear thinning polymer tends to potentiate the mixing effect of the Dean cells. The Nusselt numbers of the XG solutions are significant lower than those of the Newtonian solutions, for identical Prandtl and generalized Dean numbers. Therefore, the elastic component of the polymer tends to diminish the mixing effect of the Dean cells. A global correlation, for Nusselt number as a function of Péclet, generalized Dean and Weissenberg numbers for all Newtonian and non-Newtonian solutions studied, is presented.

Transverse Vibrations in Beams Supported by a Piece-Wise Homogeneous Visco- Elastic Foundation

Transversal vibrations induced by a load moving uniformly along an infinite beam resting on a piece-wise homogeneous visco-elastic foundation are studied. Special attention is paid to the additional vibrations, conventionally referred to as transition radiations, which arise as the point load traverses the place of foundation discontinuity. The governing equations of the problem are solved by the normalmode analysis. The solution is expressed in a form of infinite sum of orthogonal natural modes multiplied by the generalized coordinate of displacement. The natural frequencies are obtained numerically exploiting the concept of the global dynamic stiffness matrix. This ensures that the frequencies obtained are exact. The methodology has restrictions neither on velocity nor on damping. The approach looks simple, though, the numerical expression of the results is not straightforward. A general procedure for numerical implementation is presented and verified. To illustrate the utility of the methodology parametric optimization is presented and influence of the load mass is studied. The results obtained have direct application in analysis of railway track vibrations induced by high-speed trains when passing regions with significantly different foundation stiffness.

Rapid high-performance liquid chromatographic determination with fluorescence detection of furosemide in human body fluids and its confirmation by gas chromatography-mass spectrometry.

Furosemide (FD: Lasix) is a loop diuretic which strongly increases both urine flow and electrolyte urinary excretion. Healthy volunteers were administered 40 mg orally (dissolved in water) and concentrations of FD were determined in serum and urine for up to 6 h for eight subjects, who absorbed water at a rate of 400 ml/h. Quantification was performed by HPLC with fluorescence detection (excitation at 233 nm, emission at 389 nm) with a limit of detection of 5 ng/ml for a 300-microliters sample. The elution of FD was completed within 4 min using a gradient of acetonitrile concentration rising from 30 to 50% in 0.08 M phosphoric acid. The delay to the peak serum concentration ranged from 60 to 120 min. FD was still easily measurable in the sera from all subjects 6 h after administration. In urine, the excretion rates reached their maximum between 1 and 3 h. The total amount of FD excreted in the urine averaged 11.2 mg (range 7.6-14.0 mg), with a mean urine volume of 3024 ml (range 2620-3596 ml). Moreover, the urine density was lower than 1.010 (recommended as an upper limit in doping analysis to screen diuretics) only for 2 h. An additional volunteer was administered 40 mg of FD and his urine was collected over a longer period. FD was still detectable 48 h after intake. Gas chromatography-mass spectrometry with different types of ionization was used to confirm the occurrence of FD after permethylation of the extract. Negative-ion chemical ionization, with ammonia as reactant gas, was found to be the most sensitive method of detection.

Unveiling Shi’i Religious Identities: Case Studies of Hijab in Culturally Homogeneous Canadian Schools

This qualitative case study explored 10 young female Shi’i Muslim Arabic-Canadian students’ experiences associated with wearing the Hijab (headscarf) within their home, community, and predominantly White Canadian public elementary school environments. The study integrated several bodies of scholarly theories in order to examine the data under a set of comprehensive lenses that more fully articulates and theorizes on the diversity of female Shi’i Muslim Canadian students’ experiences. These theories are: identity theories with a focus on religious identity and negative stereotypes associated with Muslims; feminism and the Hijab discourses; research pertaining to Muslims in school settings; and critical race theory. In order to readdress the dearth of information about Shi’is’ experiences in schools, this study provides an in-depth case study analysis in which the methodology strategies included 10 semi-structured in-depth interviews, 2 focus-group meetings, and the incorporation of the researcher’s fieldnotes. Data analysis revealed the following themes corresponding to participants’ experiences and values in their social worlds of home, community, and schools: (a) martyrdom and self-sacrifice as a means for social justice; (b) transformational meaning of the Hijab; (c) intersectionality between culture, religion, and gender; and (d) effects of visits “back home” on participants’ religious identities. Additional themes related to participants’ school experiences included: (a) “us versus them” mentality; (b) religious and complex secular dialogues; (c) absence of Muslim representations in monocultural schools; (d) discrimination; (e) remaining silent versus speaking out; and (f) participants’ strategies for preserving their identities. Recommendations are made to integrate Shi’i Muslim females’ identity within the context of Islam and the West, most notably in relation to: (a) the role of Muslim community in nondiverse settings as a space that advances and nurtures Shi’i Muslim identity; and (b) holistic and culturally responsive teaching that fosters respect of others’ religiosity and spirituality. This study makes new inroads into feminist theorizing by drawing conceptual links between these previously unknown connections such as the impact of the historical female exemplary role model and the ritual stories on the experiences of Muslim females wearing the Hijab.

Carbon fiber recovery using subcritical and supercritical fluids for chemical recycling of thermoset composite materials.

Tesis (Doctor en Ingeniería de Materiales) UANL, 2014.

Synthese und Charakterisierung neuer Stärkederivate für die klinische Anwendung

Ein neuartiges, mehrstufiges Syntheseverfahren wurde zur Darstellung von unterschiedlichen Stärkederivaten (Ether und Ester) entwickelt, die hinsichtlich ihres Eigenschaftsprofils und ihrer Reinheit für die klinische Anwendung als Blutvolumenersatzmittel geeignet sind. Die Synthesen wurden dahingehend gestaltet, dass Produkte mit einer hohen Regioselektivität resultierten. Dabei konnten sämtliche Reaktionsschritte, die zur Modifikation der ursprünglich eingesetzten Wachsmais- und Kartoffelstärken notwendig waren, in einem homogenen, wäss-rigen System ohne zwischenzeitliche Aufarbeitung in einem Eintopfverfahren durchgeführt werden. Die auf diese Weise bevorzugt synthetisierten Carboxymethylstärken wurden mit NMR-spektroskopischen Methoden und GPC-MALLS strukturell eingehend charakterisiert. Mit eigens entwickelten Enzym-Assays konnten essentielle Informationen über die physiolo-gische Wirksamkeit der verschiedenen Stärkederivate in vitro gewonnen werden. Die Ergebnisse konnten mit Untersuchungen an Humanblut verifiziert werden.

The Inertio-Elastic Planar Entry Flow of Low-Viscosity Elastic Fluids in Micro-fabricated Geometries

The non-Newtonian flow of dilute aqueous polyethylene oxide (PEO) solutions through microfabricated planar abrupt contraction-expansions is investigated. The contraction geometries are fabricated from a high-resolution chrome mask and cross-linked PDMS gels using the tools of soft-lithography. The small length scales and high deformation rates in the contraction throat lead to significant extensional flow effects even with dilute polymer solutions having time constants on the order of milliseconds. The dimensionless extra pressure drop across the contraction increases by more than 200% and is accompanied by significant upstream vortex growth. Streak photography and videomicroscopy using epifluorescent particles shows that the flow ultimately becomes unstable and three-dimensional. The moderate Reynolds numbers (0.03 ≤ Re ≤ 44) associated with these high Deborah number (0 ≤ De ≤ 600) microfluidic flows results in the exploration of new regions of the Re-De parameter space in which the effects of both elasticity and inertia can be observed. Understanding such interactions will be increasingly important in microfluidic applications involving complex fluids and can best be interpreted in terms of the elasticity number, El = De/Re, which is independent of the flow kinematics and depends only on the fluid rheology and the characteristic size of the device.

Estudi i simulació aerodinàmica amb programari de dinàmica de fluids computacional (CFD) en un model bàsic de vehicle de competició de la categoria CM (curses de muntanya)

Aquest projecte té com a objectiu la simulació numérica de la carrosseria d’ un vehicle de curses de muntanya de categoria CM

A Homogeneous Set-Theoretical Frame for Clustering Fuzzy Relational Data

Our purpose is to provide a set-theoretical frame to clustering fuzzy relational data basically based on cardinality of the fuzzy subsets that represent objects and their complementaries, without applying any crisp property. From this perspective we define a family of fuzzy similarity indexes which includes a set of fuzzy indexes introduced by Tolias et al, and we analyze under which conditions it is defined a fuzzy proximity relation. Following an original idea due to S. Miyamoto we evaluate the similarity between objects and features by means the same mathematical procedure. Joining these concepts and methods we establish an algorithm to clustering fuzzy relational data. Finally, we present an example to make clear all the process