996 resultados para Associating fluid theory
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Surfactant monolayers are of interest in a variety of phenomena, including thin film dynamics and the formation and dynamics of foams. Measurement of surface properties has received a continuous attention and requires good theoretical models to extract the relevant physico- chemical information from experimental data. A common experimental set up consists in a shallow liquid layer whose free surface is slowly com- pressed/expanded in periodic fashion by moving two slightly immersed solid barriers, which varies the free surface area and thus the surfactant concentration. The simplest theory ignores the fluid dynamics in the bulk fluid, assuming spatially uniform surfactant concentration, which requires quite small forcing frequencies and provides reversible dynamics in the compression/expansion cycles. Sometimes, it is not clear whether depar- ture from reversibility is due to non-equilibrium effects or to the ignored fluid dynamics. Here we present a long wave theory that takes the fluid dynamics and the symmetries of the problem into account. In particular, the validity of the spatially-uniform-surfactant-concentration assumption is established and a nonlinear diffusion equation is derived. This allows for calculating spatially nonuniform monolayer dynamics and uncovering the physical mechanisms involved in the surfactant behavior. Also, this analysis can be considered a good means for extracting more relevant information from each experimental run.
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El entorno alpino de los Grisones ha sido un laboratorio donde experimentar un método arquitectónico procedente de diversas fuentes durante los años 70 en la ETHZ. Este método ha producido durante las últimas tres décadas un discurso teórico propiamente suizo alemán. La tradición continúa siendo un valor cultural para la comunidad alpina de los Grisones, que apuesta por seguir relacionando la arquitectura con su historia y su paisaje. La especificidad de cada entorno suizo alemán es un hecho obvio pero, por encima de sus rasgos característicos, hay un denominador común que les da unidad en silencio: se trata de una idea de la construcción. El fenómeno de los Grisones es territorial en su localización concreta, pero comparte el trasfondo teórico del resto de la arquitectura suizo alemana reciente. La tesis recorre transversalmente las condiciones que han dado lugar a esa trayectoria común hasta la actualidad, en que la arquitectura suizo alemana se halla precisamente en un momento de cambio generacional. La obra de Peter Märkli constituye en esta tesis un paradigma de la voluntad suizo alemana por formar parte de la continuidad cultural de la arquitectura, como una actitud de resistencia compartida frente al mundo globalizado. La tesis se articula a partir de ocho proyectos recientes, realizados por arquitectos suizo alemanes en el entorno del territorio alpino de los Grisones. Estos proyectos condensan la trayectoria arquitectónica suizo alemana durante el siglo XX, así como el fenómeno arquitectónico que ha tenido lugar en el entorno de los Grisones durante las últimas tres décadas. La tesis analiza a través de cada pareja de proyectos los episodios teóricos, artísticos y filosóficos más relevantes que se sintetizan en estas obras, así como sus referentes arquitectónicos y la dimensión trascendente de los materiales en los que la cultura suiza hunde sus raíces: la madera, la piedra y el hormigón. Las vanguardias pictóricas, el Movimiento Moderno y las corrientes humanistas y regionalistas que se fueron sucediendo durante el pasado siglo, configuran el escenario en el que tomó cuerpo la sensibilidad arquitectónica suizo alemana reciente, que emerge a través de la compleja red de relaciones establecidas entre el panorama suizo y el internacional. El mismo bagaje teórico subyace al territorio suizo alemán a nivel general, por lo que asociarlo a través de esta tesis a proyectos realizados en un entorno característico, permite acceder a una realización concreta de ese debate en un entorno tan particular como son los Grisones. La aproximación a los proyectos es de carácter fenomenológico: la experiencia directa de los mismos ha sido el sustrato fundamental del enfoque de la tesis. El trabajo de campo no se limitó a visitar los proyectos que vertebran la tesis, sino que trató de abarcar las obras más relevantes de la producción suizo alemana reciente en los Grisones, con el fin de adquirir cierto grado de sensibilidad perceptiva hacia la singularidad de su identidad territorial. La tesis hace especial hincapié en las obras de Peter Märkli y Peter Zumthor, representantes de los dos extremos del discurso suizo alemán reciente, respecto a la materialidad y al carácter de la secuencia espacial, sistemático o fluido respectivamente, pero que asimismo comparten el clasicismo formalista que subyace al fenómeno suizo alemán. Los dos proyectos que establecen el periodo 1992-2004 explorado por esta investigación constituyen dos hitos fundamentales. El Museo de La Congiunta en Giornico de Peter Märkli se construyó en 1992 y se erige a partir de entonces como un icono arquitectónico de la condensación típicamente suizo alemana de base reductiva. Este paradigma de síntesis conceptual y constructiva comenzó a forjarse en la década de 1930 de la mano del Konkrete Kunst formulado por Max Bill, que es la única manifestación artística genuinamente suiza del siglo XX y que desarrolló pictóricamente los valores de precisión, rigor, racionalismo y abstracción afines a la sensibilidad suizo alemana. En segundo lugar, el proyecto para la rehabilitación de la Villa Garbald y la construcción de la Torre Roccolo en Castasegna llevado a cabo por Miller & Maranta en 2004, supuso la consumación de la Analoge Architektur, que fue la primera corriente arquitectónica propiamente suiza, desarrollada durante la década de 1980 por Miroslav Sik. La Deutscher Tendenza es un periodo de la trayectoria suizo alemana reciente poco conocido, representado por una figura tan relevante como es Peter Zumthor. Las obras que proyectó Zumthor entre 1979 y 1985 forman parte de un periodo en que el arquitecto se encontraba profundamente influido por el neorracionalismo italiano, como ilustra la escuela de Churwalden de 1983. La arquitectura suizo alemana reciente exploró sistemáticamente los sistemas compositivos de las vanguardias pictóricas y del Movimiento Moderno, por encima de su formalismo concreto. La segunda fase de la obra de Zumthor entre 1985 y 1996 se caracteriza por la transfiguración del plano libre del sistema compositivo neoplasticista desarrollado por De Stijl, plano que adquirió grosor hasta convertirse en la caja articuladora de la fluidez de la secuencia espacial. El formalismo de Zumthor en esta fase implica la prioridad del esquema compositivo, compuesto por un perímetro regular en el que se reúnen las cajas que, como las superficies de color de las composiciones de Mondrian, articulan el espacio a su alrededor. La Residencia de Masans de Zumthor de 1993 es un proyecto canónico de este sistema compositivo, que culmina en el esquema radial de las Termas de Vals de 1996. La imagen poética se convirtió en el lenguaje propio del pensamiento de la arquitectura suizo alemana, que permitía una reflexión no verbal, a partir de unos pocos arquetipos fundamentales. Los arquitectos del Ticino buscaron en la Tendenza italiana durante la década de 1970 una alternativa al insostenible modelo territorial que estaba destruyendo su paisaje cultural. Algunos de estos arquitectos comenzaron a dar clase durante esa década en la ETHZ, por lo que transmitieron sus inquietudes al alumnado e introdujeron a Aldo Rossi en la facultad, que era uno de los máximos representantes de la Tendenza. El método analógico de Rossi, basado en la psicología analítica de Carl Jung, fue una influencia fundamental en la ETHZ durante los años 70. Rossi partía de una teoría afín al colectivo intelectual suizo que los arquitectos de la ETHZ pronto comprendieron que debían independizar del contexto italiano, desarrollando su propio método a partir de 1985 con la Analoge Architektur. El valor de la preexistencia de acuerdo a este método incipiente se hallaba en su papel articulador de la continuidad cultural de una comunidad, que Miroslav Sik definió a partir de su concepto de Altneue (literalmente, lo Nuevo-Viejo). La fusión entre lo nuevo y lo viejo era la base de la espontaneidad con la que habían crecido los asentamientos históricamente. Sik consideraba que la continuidad dependía de la comprensión de los patrones preexistentes, con el objeto de mantener su vigencia mediante la incorporación de estrategias contemporáneas, que renovarían su significado sin perder su esencia. La Casa Gugalun en Versam de Zumthor de 1994 supone una aproximación a escala doméstica a este planteamiento. La arquitectura suizo alemana reciente a menudo busca en sus referentes plásticos una manera de explorar ámbitos poco accesibles para la disciplina arquitectónica. El pensamiento arquitectónico basado en la imagen poética se implementa a partir de la tectónica de la construcción, que es el medio para comunicar una idea vertebradora del proyecto de principio a fin. La construcción como medio introduce el concepto clave de la apariencia de la arquitectura, estrechamente relacionado con la filosofía idealista de Friedrich Schiller. La apariencia debe expresar el sentido conceptual de la obra, que los arquitectos suizo alemanes denominan idea, por lo que la construcción no tiene un valor por sí misma, sino en cuanto a la apariencia. La Capilla de Oberrealta de Christian Kerez de 1993 puede ser considerada una obra escultórica en el paisaje, más próxima a las artes plásticas que a la arquitectura. La tensión que surge entre la figura ideal y la pieza sometida a una sutil deformación confiere un carácter dinámico a la composición, que intensifica el efecto perceptivo, de acuerdo a la teoría del pensamiento visual de Rudolph Arnheim. La deformación al servicio de la psicología de la percepción es un fenómeno que caracteriza la arquitectura suizo alemana reciente. El concepto de Forme Forte (forma fuerte) fue introducido por Martin Steinmann para caracterizar el objeto arquitectónico denominado internacionalmente Swiss Box. Este concepto se caracteriza por una predilección por lo monolítico, lo unitario y lo arquetípico. La condición más sustancial de una Forme Forte es, sin embargo, la de configurar un elemento estructurador del entorno. Tanto la base morfológica de una Forme Forte, como su capacidad para estructurar el lugar, se corresponden con los conceptos de arquetipo y monumento de la teoría de Rossi. La tesis explora el sentido de la deformación en la producción suizo alemana reciente, a partir de la Escuela de Paspels de Valerio Olgiati de 1998 y la Torre Roccolo de Villa Garbald de Miller&Maranta de 1998. La teoría tectónica de Gottfried Semper y la razón de la forma de Adolf Loos constituyen el sustrato teórico, que relaciona la actividad existencial de habitar con la materialidad de la arquitectura suizo alemana reciente. La teoría tectónica de Semper fundamenta las revisiones posteriores de los sistemas constructivos tradicionales suizo alemanes. Esta influencia sirvió como base a la vanguardia suiza de la Neues Bauen, que desarrolló un racionalismo funcionalista durante las décadas de 1920 y 1930, que constituye una gramática de base no simbólica. Esta gramática constituye el fundamento de la transición del orden clásico a la materialidad como instrumento compositivo durante la segunda mitad del siglo XX, consolidando el concepto de la base material de la forma. La revisión de la tradición regionalista y racionalista llevada a cabo por la generación de arquitectos suizo alemanes de la década de 1950 y 1960, constituyó una investigación lingüística sustancial. Rudolph Olgiati es la figura determinante de este periodo. La revisión de esta investigación se codificó en clave estructuralista durante los años 70 en la ETHZ, influenciada por la presencia de Roland Barthes como profesor invitado. Esta revisión constituyó la base de la articulación tectónica propiamente suizo alemana todavía vigente, como ilustra expresamente la obra de Burkhalter&Sumi en esta tesis. La obra de Gion Caminada en Vrin entre 1995 y 2002 aporta una intensa investigación sobre el Strickbau, que implementa una y otra vez variaciones sobre un sistema tradicional, ilustrando las infinitas posibilidades que ofrece un lenguaje, paradójicamente limitado por los medios disponibles en un entorno alpino aislado. Para terminar Jürg Conzett es el ingeniero con el que han desarrollado sus proyectos la mayoría de los arquitectos en el entorno de los Grisones, formado durante 8 años con Zumthor y colaborador habitual de Caminada entre otros. Conzett es el referente que relaciona la ingeniería con la arquitectura en el ámbito de esta tesis, imprescindible en el contexto de esta investigación. ABSTRACT The Alpine setting of Grisons has been a laboratory for architectural experimentation with an approach forged in the 1970s from various sources in the Swiss Federal Institute of Technology in Zurich (ETHZ). This method has produced a uniquely German-Swiss theoretical discourse over the past three decades. Tradition continues to be a cultural value for Grisons, a region committed to continue linking its architecture with the region’s history and landscape. The specificity of the German-Swiss environment is obvious, but beyond its characteristic features, there is a common denominator that gives these settings a silent unity: it is an idea of building. The phenomenon of Grisons is geographic in its specific location, but it shares the theoretical basis of the rest of the new German-Swiss architecture. This thesis transversely delves into the conditions that have shaped this common path up to the present, just as German-Swiss architecture is going through a time of generational change. In this thesis, Märkli Peter's work constitutes a paradigm of the German-Swiss will to uphold the cultural and architectural continuity of the region, exemplifying an attitude of shared resistance to the globalized world. The thesis is structured around eight recent projects carried out by German-Swiss architects in the Alpine region of Grisons. These projects represent the trajectory of twentieth century German-Swiss architectural history, as well as the architectural phenomenon that has taken place in the environs of Grisons over the past three decades. Through these projects the thesis analyzes the most relevant theoretical, artistic and philosophical references that are synthesized in the works, as well as their architectural references and the transcendental dimension of the materials in which Swiss culture is rooted: wood, stone and concrete. The artistic avant-garde, together with Modernism and the humanistic and regional movements that occurred during the last century, set the stage for present-day German-Swiss architectural sensitivity, which emerges from a complex web of relationships established between the Swiss and international panorama. This same theoretical background and experience underlies all of the German-Swiss territory in general, so associating it through this thesis to a particular context allows the description of a specific embodiment of this debate, within the unique environment of Grisons. The methodological approach to analyzing the projects was phenomenological: direct experience is the main substrate underpinning the focus of the thesis. Field work was not limited to visiting the projects featured in the thesis, but rather encompassed the most important works of recent German-Swiss construction in the Grisons in order to gain some degree of perceptual sensitivity to the uniqueness of its territorial identity. The present paper puts special emphasis on the works of Peter Märkli and Peter Zumthor, who share the formal classicist perspective of the German-Swiss context but stand on opposite sides of the philosophical spectrum with regard to the notion of materiality and the nature of space, which they conceive as systematic or fluid, respectively. The two projects that establish the boundaries of the time period 1992–2004 explored by this research represent two key milestones. The Museum La Congiunta in Giornico, by Peter Märkli, was built in 1992 and quickly established itself as an architectural icon of German-Swiss reductionism. This paradigm of conceptual and constructive synthesis began to take shape in the 1930s under the banner of Konkrete Kunst (Concrete Art), led by Max Bill. The only genuinely Swiss artistic movement of the twentieth century, Konkrete Kunst was characterized by the artistic values of precision, rigor, rationalism and abstraction, sentiments that were very close to the German-Swiss tradition. Secondly, the project for the rehabilitation of Villa Garbald and the construction of the Roccolo Tower in Castasegna, conducted by Miller&Maranta in 2004, represented the consummation of the Analoge Architektur, which was the first truly Swiss architectural movement, spearheaded in the 1980s by Miroslav Sik. The Deutscher Tendenza is a little-known period of recent German-Swiss history, represented by the important figure of Peter Zumthor. The projects that Zumthor led between 1979 and 1985 are part of a period when Italian Neo-Rationalism exercised a profound influence on the architect, as illustrated by the Churwalden School, circa 1983. Recent German-Swiss architecture systematically explored the compositional systems of the artistic avant-garde and Modernism, beyond its specific formal aspects. The second phase of Zumthor's work, between 1985 and 1996, is characterized by the transfiguration of the free plane, neoplastic compositional system developed by De Stijl, a plane that thickened until it became the box articulating fluidity from the spatial sequence. Zumthor's formalism in this phase prioritizes the compositional scheme, consisting of a regular perimeter in which the boxes that -like Mondrian’s colored surfaces- arrange the space around it. Zumthor’s Masans Residence, circa 1993, is a canonical project of this compositional system, which culminates in the radial pattern of the Therme Vals, circa 1996. The poetic image became the appropriate language of thought for German-Swiss architecture, which invited a nonverbal reflection inspired by a few fundamental archetypes. The architects of Ticino sought, through the Italian Tendenza of the 1970s, an alternative to the unsustainable territorial model that was destroying their cultural landscape. Some of these architects began to teach during that decade at ETHZ, and naturally they transmitted their unease to their students. These architects also introduced Aldo Rossi, one of the leading representatives of the Tendenza, to the school. Rossi’s analogue method, based on the analytical psychology of Carl Jung, was a major influence on the ETHZ during the 1970s. Rossi’s theoretical grounding was very much in tune with Swiss intellectualism, and it did not take long for architects from ETHZ to realize that they should break away from the Italian context, developing their own method from 1985 on with the Analoge Architektur. The value of the pre-existing conformity of this emerging method, stemmed from its role in facilitating the cultural continuity of a community, which Miroslav Sik defined in his concept of Altneue (literally, Old-new). This fusion of old and new was the basis for the spontaneity with which settlements had historically grown. Sik considered that continuity depended on understanding the existing patterns and sustaining their relevance through the incorporation of contemporary strategies, which would renew their meaning without losing their essence. Zumthor’s Gugalun House in Versam, circa 1994, is a domestic-scale approach to this philosophy. Modern German-Swiss architecture often looks to its references in visual art for a way to explore areas that are normally inaccessible to the architectural discipline. Architectural thinking based on the poetic image is achieved through a building’s tectonics, which communicate the core idea of a project from start to finish. The understanding of construction as a medium introduces the key concept of the appearance in architecture, closely related to the idealistic philosophy of Friedrich Schiller. The appearance should express the conceptual meaning of the work, which German-Swiss architects call the idea, so that the building does not have value in and of itself, but only in terms of its appearance. The Oberrealta Chapel by Christian Kerez, circa 1993, can be considered a sculpture in the landscape, closer to the visual arts than to architecture. The tension that arises between the ideal figure and the piece subjected to a subtle deformation confers a dynamic character onto the composition, intensifying the perceptual effect, according to Rudolf Arnheim’s theory of visual thought. The deformation in the service of the psychology of perception is a phenomenon that characterizes recent German-Swiss architecture. Martin Steinmann introduced the Forme Forte (Strong Form) concept to describe the architectural object known internationally as the Swiss Box. This concept is characterized by a predilection for all things monolithic, unitary and archetypal. The most substantial condition of a Forme Forte, however, is the configuration of a structuring element in the environment. Both the morphological basis of a Forme Forte and its ability to frame the place, correspond to the concepts of archetype and monument put forward by Rossi’s theory. The present thesis explores the sense of deformation in recent German-Swiss production, based on the School of Paspels by Valerio Olgiati, circa 1998 and the Roccolo Tower in Villa Garbald, by Miller&Maranta, circa 1998. Gottfried Semper’s tectonic theory and Adolf Loos’s reason for form constitute the theoretical foundation that links the existential activity of dwelling to the materiality of recent German-Swiss architecture. Semper’s tectonic theory laid the foundation for subsequent revisions of the German-Swiss traditional building systems. This influence was the basis for the Swiss avant-garde of Neues Bauen, which developed a functional rationalism during the 1920s and 30s that served as a non-symbolic grammatical foundation for the transition from classical order to materiality as a compositional tool. During the second half of the twentieth century, this architectural grammar helped consolidate the concept of the material base of the form. The revision of the regionalist and rationalist tradition, carried out by the generation of German-Swiss architects of the 1950s and 60s, constituted a substantial linguistic investigation. Rudolph Olgiati is the key figure of this period. The research was codified in terms of structuralism in the 1970s in ETHZ and influenced by the presence of Roland Barthes as a visiting professor. This revision was the basis of the uniquely German-Swiss tectonic design still in use today, as specifically illustrated by the work of Burkhalter & Sumi in this thesis. Gion Caminada's work in Vrin between 1995 and 2002 offers an extensive study on the Strickbau, which implements variations on a traditional system again and again, illustrating the endless possibilities of a language that paradoxically seems limited by the available resources in a remote Alpine setting. Finally, Jürg Conzett is the engineer with whom most architects in the Grisons region have developed their projects. Trained under Zumthor for 8 years, and a regular collaborator of Caminada, among others, Conzett is the reference point linking engineering with architecture in this thesis, essential in the context of this research.
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Este trabajo presenta un método discreto para el cálculo de estabilidad hidrodinámica y análisis de sensibilidad a perturbaciones externas para ecuaciones diferenciales y en particular para las ecuaciones de Navier-Stokes compressible. Se utiliza una aproximación con variable compleja para obtener una precisión analítica en la evaluación de la matriz Jacobiana. Además, mapas de sensibilidad para la sensibilidad a las modificaciones del flujo de base y a una fuerza constante permiten identificar las regiones del campo fluido donde una modificacin (ej. fuerza puntual) tiene un efecto estabilizador del flujo. Se presentan cuatro casos de prueba: (1) un caso analítico para comprobar la derivación discreta, (2) una cavidad cerrada a bajo Reynolds para mostrar la mayor precisión en el cálculo de los valores propios con la aproximación de paso complejo, (3) flujo 2D en un cilindro circular para validar la metodología, y (4) flujo en un cavidad abierta, presentado para validar el método en casos de inestabilidades convectivamente inestables. Los tres últimos casos mencionados (2-4) se resolvieron con las ecuaciones de Navier-Stokes compresibles, utilizando un método Discontinuous Galerkin Spectral Element Method. Se obtuvo una buena concordancia para el caso de validación (3), cuando se comparó el nuevo método con resultados de la literatura. Además, este trabajo muestra que para el cálculo de los modos propios directos y adjuntos, así como para los mapas de sensibilidad, el uso de variables complejas es de suprema importancia para obtener una predicción precisa. El método descrito es aplicado al análisis para la estabilización de la estela generada por un disco actuador, que representa un modelo sencillo para hélices, rotores de helicópteros o turbinas eólicas. Se explora la primera bifurcación del flujo para un disco actuador, y se sugiere que está asociada a una inestabilidad de tipo Kelvin-Helmholtz, cuya estabilidad se controla con en el número de Reynolds y en la resistencia del disco actuador (o fuerza resistente). En primer lugar, se verifica que la disminución de la resistencia del disco tiene un efecto estabilizador parecido a una disminución del Reynolds. En segundo lugar, el análisis hidrodinmico discreto identifica dos regiones para la colocación de una fuerza puntual que controle las inestabilidades, una cerca del disco y otra en una zona aguas abajo. En tercer lugar, se muestra que la inclusión de un forzamiento localizado cerca del actuador produce una estabilización más eficiente que al forzar aguas abajo. El análisis de los campos de flujo controlados confirma que modificando el gradiente de velocidad cerca del actuador es más eficiente para estabilizar la estela. Estos resultados podrían proporcionar nuevas directrices para la estabilización de la estela de turbinas de viento o de marea cuando estén instaladas en un parque eólico y minimizar las interacciones no estacionarias entre turbinas. ABSTRACT A discrete framework for computing the global stability and sensitivity analysis to external perturbations for any set of partial differential equations is presented. In particular, a complex-step approximation is used to achieve near analytical accuracy for the evaluation of the Jacobian matrix. Sensitivity maps for the sensitivity to base flow modifications and to a steady force are computed to identify regions of the flow field where an input could have a stabilising effect. Four test cases are presented: (1) an analytical test case to prove the theory of the discrete framework, (2) a lid-driven cavity at low Reynolds case to show the improved accuracy in the calculation of the eigenvalues when using the complex-step approximation, (3) the 2D flow past a circular cylinder at just below the critical Reynolds number is used to validate the methodology, and finally, (4) the flow past an open cavity is presented to give an example of the discrete method applied to a convectively unstable case. The latter three (2–4) of the aforementioned cases were solved with the 2D compressible Navier–Stokes equations using a Discontinuous Galerkin Spectral Element Method. Good agreement was obtained for the validation test case, (3), with appropriate results in the literature. Furthermore, it is shown that for the calculation of the direct and adjoint eigenmodes and their sensitivity maps to external perturbations, the use of complex variables is paramount for obtaining an accurate prediction. An analysis for stabilising the wake past an actuator disc, which represents a simple model for propellers, helicopter rotors or wind turbines is also presented. We explore the first flow bifurcation for an actuator disc and it suggests that it is associated to a Kelvin- Helmholtz type instability whose stability relies on the Reynolds number and the flow resistance applied through the disc (or actuator forcing). First, we report that decreasing the disc resistance has a similar stabilising effect to an decrease in the Reynolds number. Second, a discrete sensitivity analysis identifies two regions for suitable placement of flow control forcing, one close to the disc and one far downstream where the instability originates. Third, we show that adding a localised forcing close to the actuator provides more stabilisation that forcing far downstream. The analysis of the controlled flow fields, confirms that modifying the velocity gradient close to the actuator is more efficient to stabilise the wake than controlling the sheared flow far downstream. An interesting application of these results is to provide guidelines for stabilising the wake of wind or tidal turbines when placed in an energy farm to minimise unsteady interactions.
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The aim of this report is to discuss the method of determination of lattice-fluid binary interaction parameters by comparing well characterized immiscible blends and block copolymers of poly(methyl methacrylate) (PMMA) and poly(ϵ−caprolactone) (PCL). Experimental pressure-volume-temperature (PVT) data in the liquid state were correlated with the Sanchez—Lacombe (SL) equation of state with the scaling parameters for mixtures and copolymers obtained through combination rules of the characteristic parameters for the pure homopolymers. The lattice-fluid binary parameters for energy and volume were higher than those of block copolymers implying that the copolymers were more compatible due to the chemical links between the blocks. Therefore, a common parameter cannot account for both homopolymer blend and block copolymer phase behaviors based on current theory. As we were able to adjust all data of the mixtures with a single set of lattice-binary parameters and all data of the block copolymers with another single set we can conclude that both parameters did not depend on the composition for this system. This characteristic, plus the fact that the additivity law of specific volumes can be suitably applied for this system, allowed us to model the behavior of the immiscible blend with the SL equation of state. In addition, a discussion on the relationship between lattice-fluid binary parameters and the Flory–Huggins interaction parameter obtained from Leibler's theory is presented.
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The general purpose of the EQUIFASE Conference is to promote the Scientific and Technologic exchange between people from both the academic and the industrial environment in the field of Phase Equilibria and Thermodynamic Properties for the Design of Chemical Processes. Topics: Measurement of Thermodynamic Properties. Phase Equilibria and Chemical Equilibria. Theory and Modelling. Alternative Solvents. Supercritical Fluids. Ionic Liquids. Energy. Gas and oil. Petrochemicals. Environment and sustainability. Biomolecules and Biotechnology. Product and Process Design. Databases and Software. Education.
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To solve problems in polymer fluid dynamics, one needs the equation of continuity, motion, and energy. The last two equations contain the stress tensor and the heat-flux vector for the material. There are two ways to formulate the stress tensor: (1) one can write a continuum expression for the stress tensor in terms of kinematic tensors, or (2) one can select a molecular model that represents the polymer molecule, and then develop an expression for the stress tensor from kinetic theory. The advantage of the kinetic theory approach is that one gets information about the relation between the molecular structure of the polymers and the rheological properties. In this review, we restrict the discussion primarily to the simplest stress tensor expressions or “constitutive equations” containing from two to four adjustable parameters, although we do indicate how these formulations may be extended to give more complicated expressions. We also explore how these simplest expressions are recovered as special cases of a more general framework, the Oldroyd 8-constant model. The virtue of studying the simplest models is that we can discover some general notions as to which types of empiricisms or which types of molecular models seem to be worth investigating further. We also explore equivalences between continuum and molecular approaches. We restrict the discussion to several types of simple flows, such as shearing flows and extensional flows. These are the flows that are of greatest importance in industrial operations. Furthermore, if these simple flows cannot be well described by continuum or molecular models, then it is not necessary to lavish time and energy to apply them to more complex flow problems.
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"To be presented to the Fluid Dynamics Panel of the Advisory Group for Aeronautical Research and Development of the North Atlantic Treaty Organization, 10 April through 17 April 1961."
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pt. 1. Their theory and application.
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Mode of access: Internet.
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Mode of access: Internet.
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Flows of complex fluids need to be understood at both macroscopic and molecular scales, because it is the macroscopic response that controls the fluid behavior, but the molecular scale that ultimately gives rise to rheological and solid-state properties. Here the flow field of an entangled polymer melt through an extended contraction, typical of many polymer processes, is imaged optically and by small-angle neutron scattering. The dual-probe technique samples both the macroscopic stress field in the flow and the microscopic configuration of the polymer molecules at selected points. The results are compared with a recent tube model molecular theory of entangled melt flow that is able to calculate both the stress and the single-chain structure factor from first principles. The combined action of the three fundamental entangled processes of reptation, contour length fluctuation, and convective constraint release is essential to account quantitatively for the rich rheological behavior. The multiscale approach unearths a new feature: Orientation at the length scale of the entire chain decays considerably more slowly than at the smaller entanglement length.
Resumo:
We present a new approach accounting for the nonadditivity of attractive parts of solid-fluid and fluidfluid potentials to improve the quality of the description of nitrogen and argon adsorption isotherms on graphitized carbon black in the framework of non-local density functional theory. We show that the strong solid-fluid interaction in the first monolayer decreases the fluid-fluid interaction, which prevents the twodimensional phase transition to occur. This results in smoother isotherm, which agrees much better with experimental data. In the region of multi-layer coverage the conventional non-local density functional theory and grand canonical Monte Carlo simulations are known to over-predict the amount adsorbed against experimental isotherms. Accounting for the non-additivity factor decreases the solid-fluid interaction with the increase of intermolecular interactions in the dense adsorbed fluid, preventing the over-prediction of loading in the region of multi-layer adsorption. Such an improvement of the non-local density functional theory allows us to describe experimental nitrogen and argon isotherms on carbon black quite accurately with mean error of 2.5 to 5.8% instead of 17 to 26% in the conventional technique. With this approach, the local isotherms of model pores can be derived, and consequently a more reliab * le pore size distribution can be obtained. We illustrate this by applying our theory against nitrogen and argon isotherms on a number of activated carbons. The fitting between our model and the data is much better than the conventional NLDFT, suggesting the more reliable PSD obtained with our approach.
Resumo:
In this paper, we applied a version of the nonlocal density functional theory (NLDFT) accounting radial and longitudinal density distributions to study the adsorption and desorption of argon in finite as well as infinite cylindrical nanopores at 87.3 K. Features that have not been observed before with one-dimensional NLDFT are observed in the analysis of an inhomogeneous fluid along the axis of a finite cylindrical pore using the two-dimensional version of the NLDFT. The phase transition in pore is not strictly vapor-liquid transition as assumed and observed in the conventional version, but rather it exhibits a much elaborated feature with phase transition being complicated by the formation of solid phase. Depending on the pore size, there are more than one phase transition in the adsorption-desorption isotherm. The solid formation in finite pore has been found to be initiated by the presence of the meniscus. Details of the analysis of the extended version of NLDFT will be discussed in the paper. (C) 2004 American Institute of Physics.
Resumo:
A new approach based on the nonlocal density functional theory to determine pore size distribution (PSD) of activated carbons and energetic heterogeneity of the pore wall is proposed. The energetic heterogeneity is modeled with an energy distribution function (EDF), describing the distribution of solid-fluid potential well depth (this distribution is a Dirac delta function for an energetic homogeneous surface). The approach allows simultaneous determining of the PSD (assuming slit shape) and EDF from nitrogen or argon isotherms at their respective boiling points by using a set of local isotherms calculated for a range of pore widths and solid-fluid potential well depths. It is found that the structure of the pore wall surface significantly differs from that of graphitized carbon black. This could be attributed to defects in the crystalline structure of the surface, active oxide centers, finite size of the pore walls (in either wall thickness or pore length), and so forth. Those factors depend on the precursor and the process of carbonization and activation and hence provide a fingerprint for each adsorbent. The approach allows very accurate correlation of the experimental adsorption isotherm and leads to PSDs that are simpler and more realistic than those obtained with the original nonlocal density functional theory.