Modelización de los Procesos de Cristalización en Poliolefinas

“Por lo tanto, la cristalización de polímeros se supone, y en las teorías se describe a menudo, como un proceso de múltiples pasos con muchos aspectos físico-químicos y estructurales influyendo en él. Debido a la propia estructura de la cadena, es fácil entender que un proceso que es termodinámicamente forzado a aumentar su ordenamiento local, se vea obstaculizado geométricamente y, por tanto, no puede conducirse a un estado de equilibrio final. Como resultado, se forman habitualmente estructuras de no equilibrio con diferentes características dependiendo de la temperatura, presión, cizallamiento y otros parámetros físico-químicos del sistema”. Estas palabras, pronunciadas recientemente por el profesor Bernhard Wunderlich, uno de los mas relevantes fisico-quimicos que han abordado en las ultimas décadas el estudio del estado físico de las macromoléculas, adelantan lo que de alguna manera se explicita en esta memoria y constituyen el “leitmotiv” de este trabajo de tesis. El mecanismo de la cristalización de polímeros esta aun bajo debate en la comunidad de la física de polímeros y la mayoría de los abordajes experimentales se explican a través de la teoría LH. Esta teoría clásica debida a Lauritzen y Hoffman (LH), y que es una generalización de la teoría de cristalización de una molécula pequeña desde la fase de vapor, describe satisfactoriamente muchas observaciones experimentales aunque esta lejos de explicar el complejo fenómeno de la cristalización de polímeros. De hecho, la formulación original de esta teoría en el National Bureau of Standards, a comienzos de la década de los 70, sufrió varias reformulaciones importantes a lo largo de la década de los 80, buscando su adaptación a los hallazgos experimentales. Así nació el régimen III de cristalización que posibilita la creacion de nichos moleculares en la superficie y que dio pie al paradigma ofrecido por Sadler y col., para justificar los experimentos que se obtenian por “scattering” de neutrones y otras técnicas como la técnica de “droplets” o enfriamiento rapido. Por encima de todo, el gran éxito de la teoría radica en que explica la dependencia inversa entre el tamaño del plegado molecular y el subenfriamiento, definido este ultimo como el intervalo de temperatura que media entre la temperatura de equilibrio y la temperatura de cristalización. El problema concreto que aborda esta tesis es el estudio de los procesos de ordenamiento de poliolefinas con distinto grado de ramificacion mediante simulaciones numéricas. Los copolimeros estudiados en esta tesis se consideran materiales modelo de gran homogeneidad molecular desde el punto de vista de la distribución de tamaños y de ramificaciones en la cadena polimérica. Se eligieron estas poliolefinas debido al gran interes experimental en conocer el cambio en las propiedades fisicas de los materiales dependiendo del tipo y cantidad de comonomero utilizado. Además, son modelos sobre los que existen una ingente cantidad de información experimental, que es algo que preocupa siempre al crear una realidad virtual como es la simulación. La experiencia en el grupo Biophym es que los resultados de simulación deben de tener siempre un correlato mas o menos próximo experimental y ese argumento se maneja a lo largo de esta memoria. Empíricamente, se conoce muy bien que las propiedades físicas de las poliolefinas, en suma dependen del tipo y de la cantidad de ramificaciones que presenta el material polimérico. Sin embargo, tal como se ha explicado no existen modelos teóricos adecuados que expliquen los mecanismos subyacentes de los efectos de las ramas. La memoria de este trabajo es amplia por la complejidad del tema. Se inicia con una extensa introducción sobre los conceptos básicos de una macromolecula que son relevantes para entender el contenido del resto de la memoria. Se definen los conceptos de macromolecula flexible, distribuciones y momentos, y su comportamiento en disolución y fundido con los correspondientes parametros caracteristicos. Se pone especial énfasis en el concepto de “entanglement” o enmaranamiento por considerarse clave a la hora de tratar macromoléculas con una longitud superior a la longitud critica de enmaranamiento. Finaliza esta introducción con una reseña sobre el estado del arte en la simulación de los procesos de cristalización. En un segundo capitulo del trabajo se expone detalladamente la metodología usada en cada grupo de casos. En el primer capitulo de resultados, se discuten los estudios de simulación en disolución diluida para sistemas lineales y ramificados de cadena única. Este caso mas simple depende claramente del potencial de torsión elegido tal como se discute a lo largo del texto. La formación de los núcleos “babys” propuestos por Muthukumar parece que son consecuencia del potencial de torsión, ya que este facilita los estados de torsión mas estables. Así que se propone el análisis de otros potenciales que son igualmente utilizados y los resultados obtenidos sobre la cristalización, discutidos en consecuencia. Seguidamente, en un segundo capitulo de resultados se estudian moleculas de alcanos de cadena larga lineales y ramificados en un fundido por simulaciones atomisticas como un modelo de polietileno. Los resultados atomisticos pese a ser de gran detalle no logran captar en su totalidad los efectos experimentales que se observan en los fundidos subenfriados en su etapa previa al estado ordenado. Por esta razon se discuten en los capítulos 3 y 4 de resultados sistemas de cadenas cortas y largas utilizando dos modelos de grano grueso (CG-PVA y CG-PE). El modelo CG-PE se desarrollo durante la tesis. El uso de modelos de grano grueso garantiza una mayor eficiencia computacional con respecto a los modelos atomísticos y son suficientes para mostrar los fenómenos a la escala relevante para la cristalización. En todos estos estudios mencionados se sigue la evolución de los procesos de ordenamiento y de fusión en simulaciones de relajación isoterma y no isoterma. Como resultado de los modelos de simulación, se han evaluado distintas propiedades fisicas como la longitud de segmento ordenado, la cristalinidad, temperaturas de fusion/cristalizacion, etc., lo que permite una comparación con los resultados experimentales. Se demuestra claramente que los sistemas ramificados retrasan y dificultan el orden de la cadena polimérica y por tanto, las regiones cristalinas ordenadas decrecen al crecer las ramas. Como una conclusión general parece mostrarse una tendencia a la formación de estructuras localmente ordenadas que crecen como bloques para completar el espacio de cristalización que puede alcanzarse a una temperatura y a una escala de tiempo determinada. Finalmente hay que señalar que los efectos observados, estan en concordancia con otros resultados tanto teoricos/simulacion como experimentales discutidos a lo largo de esta memoria. Su resumen se muestra en un capitulo de conclusiones y líneas futuras de investigación que se abren como consecuencia de esta memoria. Hay que mencionar que el ritmo de investigación se ha acentuado notablemente en el ultimo ano de trabajo, en parte debido a las ventajas notables obtenidas por el uso de la metodología de grano grueso que pese a ser muy importante para esta memoria no repercute fácilmente en trabajos publicables. Todo ello justifica que gran parte de los resultados esten en fase de publicación. Abstract “Polymer crystallization is therefore assumed, and in theories often described, to be a multi step process with many influencing aspects. Because of the chain structure, it is easy to understand that a process which is thermodynamically forced to increase local ordering but is geometrically hindered cannot proceed into a final equilibrium state. As a result, nonequilibrium structures with different characteristics are usually formed, which depend on temperature, pressure, shearing and other parameters”. These words, recently written by Professor Bernhard Wunderlich, one of the most prominent researchers in polymer physics, put somehow in value the "leitmotiv "of this thesis. The crystallization mechanism of polymers is still under debate in the physics community and most of the experimental findings are still explained by invoking the LH theory. This classical theory, which was initially formulated by Lauritzen and Hoffman (LH), is indeed a generalization of the crystallization theory for small molecules from the vapor phase. Even though it describes satisfactorily many experimental observations, it is far from explaining the complex phenomenon of polymer crystallization. This theory was firstly devised in the early 70s at the National Bureau of Standards. It was successively reformulated along the 80s to fit the experimental findings. Thus, the crystallization regime III was introduced into the theory in order to explain the results found in neutron scattering, droplet or quenching experiments. This concept defines the roughness of the crystallization surface leading to the paradigm proposed by Sadler et al. The great success of this theory is the ability to explain the inverse dependence of the molecular folding size on the supercooling, the latter defined as the temperature interval between the equilibrium temperature and the crystallization temperature. The main scope of this thesis is the study of ordering processes in polyolefins with different degree of branching by using computer simulations. The copolymers studied along this work are considered materials of high molecular homogeneity, from the point of view of both size and branching distributions of the polymer chain. These polyolefins were selected due to the great interest to understand their structure– property relationships. It is important to note that there is a vast amount of experimental data concerning these materials, which is essential to create a virtual reality as is the simulation. The Biophym research group has a wide experience in the correlation between simulation data and experimental results, being this idea highly alive along this work. Empirically, it is well-known that the physical properties of the polyolefins depend on the type and amount of branches presented in the polymeric material. However, there are not suitable models to explain the underlying mechanisms associated to branching. This report is extensive due to the complexity of the topic under study. It begins with a general introduction to the basics concepts of macromolecular physics. This chapter is relevant to understand the content of the present document. Some concepts are defined along this section, among others the flexibility of macromolecules, size distributions and moments, and the behavior in solution and melt along with their corresponding characteristic parameters. Special emphasis is placed on the concept of "entanglement" which is a key item when dealing with macromolecules having a molecular size greater than the critical entanglement length. The introduction finishes with a review of the state of art on the simulation of crystallization processes. The second chapter of the thesis describes, in detail, the computational methodology used in each study. In the first results section, we discuss the simulation studies in dilute solution for linear and short chain branched single chain models. The simplest case is clearly dependent on the selected torsion potential as it is discussed throughout the text. For example, the formation of baby nuclei proposed by Mutukhumar seems to result from the effects of the torsion potential. Thus, we propose the analysis of other torsion potentials that are also used by other research groups. The results obtained on crystallization processes are accordingly discussed. Then, in a second results section, we study linear and branched long-chain alkane molecules in a melt by atomistic simulations as a polyethylene-like model. In spite of the great detail given by atomistic simulations, they are not able to fully capture the experimental facts observed in supercooled melts, in particular the pre-ordered states. For this reason, we discuss short and long chains systems using two coarse-grained models (CG-PVA and CG-PE) in section 3 and 4 of chapter 2. The CG-PE model was developed during the thesis. The use of coarse-grained models ensures greater computational efficiency with respect to atomistic models and is enough to show the relevant scale phenomena for crystallization. In all the analysis we follow the evolution of the ordering and melting processes by both isothermal and non isothermal simulations. During this thesis we have obtained different physical properties such as stem length, crystallinity, melting/crystallization temperatures, and so on. We show that branches in the chains cause a delay in the crystallization and hinder the ordering of the polymer chain. Therefore, crystalline regions decrease in size as branching increases. As a general conclusion, it seems that there is a tendency in the macromolecular systems to form ordered structures, which can grown locally as blocks, occupying the crystallization space at a given temperature and time scale. Finally it should be noted that the observed effects are consistent with both, other theoretical/simulation and experimental results. The summary is provided in the conclusions chapter along with future research lines that open as result of this report. It should be mentioned that the research work has speeded up markedly in the last year, in part because of the remarkable benefits obtained by the use of coarse-grained methodology that despite being very important for this thesis work, is not easily publishable by itself. All this justify that most of the results are still in the publication phase.

Multiscale-fiber-reinforced thermoplastic composites incorporating carbon nanotubes: A review

This article reviews recent literature on hierarchical thermoplastic-based composites that simultaneously incorporate carbon nanotubes (CNTs) and conventional microscale fibers, and discusses the structure?property relationships of the resulting hybrids. The mixing of multiple and multiscale constituents enables the preparation of materials with new or improved properties due to synergistic effects. By exploiting the outstanding mechanical, thermal and electrical properties of CNTs, a new generation of multifunctional high-performance composites suitable for a wide variety of applications can be developed.

Structure function and Multifractal spectrum applied to Digital Elevation Model

A Digital Elevation Model (DEM) provides the information basis used for many geographic applications such as topographic and geomorphologic studies, landscape through GIS (Geographic Information Systems) among others. The DEM capacity to represent Earth?s surface depends on the surface roughness and the resolution used. Each DEM pixel depends on the scale used characterized by two variables: resolution and extension of the area studied. DEMs can vary in resolution and accuracy by the production method, although there are statistical characteristics that keep constant or very similar in a wide range of scales. Based on this property, several techniques have been applied to characterize DEM through multiscale analysis directly related to fractal geometry: multifractal spectrum and the structure function. The comparison of the results by both methods is discussed. The study area is represented by a 1024 x 1024 data matrix obtained from a DEM with a resolution of 10 x 10 m each point, which correspond with a region known as ?Monte de El Pardo? a property of Spanish National Heritage (Patrimonio Nacional Español) of 15820 Ha located to a short distance from the center of Madrid. Manzanares River goes through this area from North to South. In the southern area a reservoir is found with a capacity of 43 hm3, with an altitude of 603.3 m till 632 m when it is at the highest capacity. In the middle of the reservoir the minimum altitude of this area is achieved.

On the structure of the floating zone in melting

Floating zone melting is used in crystal growth and purification of high melting materials. The use of a reduced gravity environment will remove the constraint imposed on the length of the zone by the hydrostatic pressure. The equilibrium of the fioatmg zone may involve, (1)Hydrostatic forces, when the zone rotates as a whole. (2)Convective driving forces, when the zone is stationary but fluid property gradients appear.(3) Hydrodynamic forces, when some parts of the zone are set into motion with respect to others. The last effects are considered in this paper. The flow pattern of a floating zone held between two discs in relative motion is complicated, and thence the solution of the problem is difficult even assuming a constant property-newtonian liquid Nevertheless, when a small parameter appears m the problem, the complete flow field can be split into zones where simple solutions are found. To illustrate this approach, the spin up from rest of an initially cylindrical floating zone is considered with detail. Here the small parameter is the time elapsed from the impulsive starting of motion. Since the problem which has been considered, as well as some others which can be tackled by use of similar methods, concern the viscous layer close to either plate, they can be simulated experimentally in the ground laboratory with short floating zones. Procedures to produce these zones are indicated.

Influence of crowds in the dynamic characteristics of a structure

The interest for modelling of human actions acting on structures has been recurrent since the first accidents on suspension bridges in the nineteenth century like Broughton (1831) in the U.K. or Angers (1850) in France. Stadiums, gymnasiums are other type of structure where the human induced vibration is very important. In these structures appear particular phenomenon like the interaction person-structure (lock-in), the person-person synchronization, and the influence of the mass and damping of the people in the structure behaviour. This work focuses on the latter topic. The dynamic characteristic of a structure can be changed due to the presence of people on it. In order to evaluate these property modifications several testing have been carried out on a structure designed to be a gymnasium. For the test an electro-dynamic shaker was installed in a fixed point of the gym slab and different groups of people were located around the shaker. In each test the number of people was changed and also their posture (standing and sitting). Test data were analyzed and processed to verify modifications in the structure behaviour.

Residuos orgánicos como fuentes de fósforo

En este trabajo, se han llevado a cabo distintos experimentos en laboratorio, con el objetivo de estudiar el efecto de la aplicación de residuos orgánicos como fuentes de P en las pérdidas de este elemento, que se producen en suelo, tanto por escorrentía superficial como por lixiviación. El interés por evaluar las pérdidas de P se debe a la necesidad de conocer mejor los factores que influyen en los procesos de pérdidas de este elemento y así, poder reducir los problemas de eutrofización de aguas, tanto superficiales como subterráneas, provocadas por un exceso de este nutriente, junto con otros como el nitrógeno. Los trabajos experimentales que se han llevado a cabo se detallan a continuación: Se ha realizado el estudio de las formas de P contenidas en una serie de 14 residuos orgánicos, de distinto origen y tratamiento (compost, lodos, purines y digestato), comparando la información aportada por tres protocolos de fraccionamientos de P diferentes, seleccionados entre los principales métodos utilizados: protocolo de fraccionamiento de Ruttemberg (1992), protocolo de Normas, medidas y ensayos (Ruban et al., 2001a) y protocolo de Huang et al. (2008). Todos los métodos de fraccionamiento empleados aportaron información útil para conocer las formas de P de los residuos, a pesar de que alguno de ellos fue descrito para sedimentos o suelos. Sin embargo, resulta difícil comparar los resultados entre unos y otros, ya que cada uno emplea extractantes y tiempos de ensayos diferentes. Las cantidades de P total determinadas por cada método mantienen una relación lineal, aunque el método SMT, por ser más directo, obtiene las cantidades más elevadas para todos los residuos. Los métodos secuenciales (métodos de Huang y Ruttemberg), a pesar de ser más largos y tediosos, aportan información más detallada de la disponibilidad de las formas de P, y con ello, permiten obtener una mejor estimación de las pérdidas potenciales de este elemento tras su aplicación en suelo. Se han encontrado relaciones positivas entre las fracciones determinadas por estos dos métodos. Así mismo, se encuentra una correlación entre las formas solubles de P y la concentración de los iones [Ca + Fe + Al] de los residuos, útiles como indicadores de la disponibilidad de este elemento. Sin embargo, el protocolo SMT, no obtiene información de la solubilidad o disponibilidad de las formas de P contenidas, ni las formas determinadas mantienen relaciones directas con las de los otros métodos, con excepción del P total. Para el estudio del comportamiento de los residuos aplicados en suelos, se pusieron a punto sistemas de lluvia simulada, con el objetivo de caracterizar las pérdidas de P en la escorrentía superficial generada. Por otra parte, se emplearon columnas de suelos enmendados con residuos orgánicos, para el estudio de las pérdidas de P por lixiviación. Los ensayos de simulación de lluvia se llevaron a cabo de acuerdo al “National Phosphorus Research proyect“ (2001), que consigue simular eventos sucesivos de lluvia en unas condiciones semejantes a la realidad, empleando cajas llenas de suelo del horizonte superficial, con residuos aplicados tanto superficialmente como mediante mezcla con el propio suelo. Los ensayos se realizaron con seis residuos de diferente naturaleza y sometidos a distintos tratamientos. Se encontraron diferencias significativas en las pérdidas de las formas de P analizadas, tanto disueltas como particuladas, en las aguas de escorrentía generadas. En general, las pérdidas en el primer evento de lluvia tras la aplicación de los residuos fueron mayores a las generadas en el segundo evento, predominando las formas de P particuladas respecto a las disueltas en ambos. Se encontró una relación positiva entre las pérdidas de P en las aguas de escorrentía generadas en cada ensayo, con los contenidos de P soluble en agua y fácilmente disponible de los residuos empleados, determinados por los protocolos de fraccionamientos secuenciales. Además, se emplearon los modelos matemáticos desarrollados por Vadas et al. (2005, 2007), de evaluación de las pérdidas de P por escorrentía para fertilizantes y estiércoles. La predicción de estos modelos no se cumple en el caso de todos los residuos. Las distintas propiedades físicas de los residuos pueden afectar a las diferencias entre las pérdidas experimentales y las esperadas. Los ensayos de simulación del proceso de lixiviación se llevaron a cabo en columnas de percolación, con suelos enmendados con residuos orgánicos, de acuerdo a la norma “CEN/TS 14405–2004: Caracterización de los residuos – Test de comportamiento de lixiviación – Test de flujo ascendente”. Las pérdidas de P por procesos de lixiviación de agua, han sido despreciadas durante mucho tiempo respecto a las pérdidas por escorrentía. Sin embargo, se ha demostrado que deben tenerse en consideración, principalmente en algunos tipos de suelos o zonas cercanas a acuíferos. Se utilizaron tres suelos de distinta procedencia para los ensayos, de manera que se pudo estudiar la influencia del tipo de suelo en las pérdidas de P para cada tipo de residuo (purín, compost, digestato y lodo de EDAR). Los índices de adsorción de P determinados para cada suelo permiten evaluar aquellos que presentarán más riesgo de producir pérdidas de este elemento al aplicarse fuentes externas de P, encontrando una relación positiva entre ambos. Las pérdidas de P en los lixiviados varían en función tanto del residuo como del suelo empleado. Para el compost, el purín y el lodo, se encontró una relación entre las pérdidas generadas en el agua lixiviada de las columnas y las formas de P soluble contenidas en los residuos. Sin embargo, en el caso del digestato, no existía esta correlación. Las pérdidas para este residuo fueron en todos los casos menores a las estimadas, considerando las formas de P contenido. El estudio de la mojabilidad, propiedad física del residuo que evalúa la capacidad de interacción residuo-agua, permitió explicar el comportamiento anómalo de este residuo, con una mayor resistencia a que el agua entrara en su estructura y por tanto, una mayor dificultad de solubilizar el P contenido en el propio residuo, que en el caso de otros residuos. En general, podemos considerar que el estudio de las formas de P más disponibles o solubles en agua, aporta información útil de las pérdidas potenciales de P. Sin embargo, es necesario estudiar las propiedades físicas de los residuos orgánicos aplicados y la capacidad de adsorción de P de los suelos, para estimar las pérdidas de P y con ello, colaborar a controlar los procesos de eutrofización en aguas. ABSTRACT This dissertation explores the effect of organic wastes application as sources of P in losses of this element that occur by both surface runoff and leaching in soil. To do so, diverse laboratory experiments are conducted and presented here. Evaluating P losses is necessary to better understand the factors that influence the processes behind the loss of this element. Reducing P losses reduces eutrophication problems of both surface water and groundwater caused by an excess of this nutrient, along with other as nitrogen. Details of the experiments are presented below: The first experiment studies the forms of P contained in a series of 14 organic wastes of different origin and treatment (compost, sludge, slurry and digestate), comparing the information provided by three methods of P fractionation. The methods selected were: Ruttemberg protocol (1992); Standards, Measurements and Testing protocol (Ruban et al., 2001a); and Huang protocol (Huang et al., 2008). All fractionation methods employed successfully contribute to our knowledge of P forms in wastes, even though one of them was originally described for sediments or soils information. However, it is difficult to compare results among each other, as each protocol employs different extractants and time in the trials. Total amounts of P obtained by each method show a linear relationship, although the SMT method, which is more direct, obtains the highest amounts for all residues. Sequential methods (Huang and Ruttemberg’s protocols), despite being longer and more tedious, provide more detailed information on the availability of the forms of P. Therefore, allow the estimation of the potential losses of P after application in soil. Furthermore, positive relationships have been found among fractions obtained by these methods. Positive relationship has been found also among soluble forms of P and the concentration of ions Fe + Ca + Al, which is useful as an indicator of the availability of this element. However, the SMT protocol does not collect information about solubility or availability of forms of P contained; neither do certain forms maintain direct relations with the forms from other methods, with the exception of total P methods. To study the behavior of wastes applied to soils two experiments were conducted. Simulated rain systems were prepared to characterize P losses in the surface runoff generated. In addition, columns of soils amended with organic waste were developed for the study of P leaching losses. Simulated rain systems were carried out according to the ’National Phosphorus Research Project’ (2001), which manages to simulate successive rainfall events in conditions resembling reality. The experiment uses boxes filled with soil from the surface horizon amended with residues, both superficially and by mixing with the soil. Tests were conducted with six residues of different type and subjected to diverse treatments. Findings show significant differences in losses of the P forms analyzed in the generated runoff water, in both solution and particulate forms. In general, losses in the first rainfall event after application of waste were higher than the losses generated in the second event, predominating particulate forms of P over dissolved forms in both events. In all trials, a positive relationship was found between various P forms determined by sequential fractionation protocols (water soluble P and readily available P forms) and P losses in runoff. Furthermore, results from Vadas´s mathematical models (Vadas et al., 2005; 2007) to assess P losses by runoff fertilizers and manures indicate that the prediction of this model is not fulfilled in the case of all residues. The diverse physical properties of wastes may affect the differences between experimental and expected losses. Finally, leaching simulation processes were carried out in percolation columns, filled with soils amended with organic wastes, following the ‘CEN/TS 14405-2004 standard: Characterization of waste - Leaching behavior test - Test Flow ascending ’. P losses by leaching have been neglected for a long time with respect to runoff losses. However, findings corroborate previous studies showing that these P losses have to be taken into account, especially in certain types of soils and in zones near aquifers. To study the influence of soil type on P losses, experiments were carried out with three different soils and for each type of waste (manure, compost, digestate and sludge WWTP). Each soil’s P adsorption rates allow assessing which soils imply a higher risk of P losses when external sources of P are applied. P losses in leachate vary according to the type of soil employed and according to the specific residue. In the case of compost, manure and sludge, there is a relationship between leaching losses and residues’ soluble forms of P. The exception being the digestate, where there was no such correlation. Digestate P losses by leaching were lower than expected in all cases considering the forms of P contained. Moreover, examining digestate wettability -- that is, the physical property of the residue that assesses the capacity of waste-water interaction -- allowed explaining the anomalous behavior of this residue. Digestate has a high resistance to water entering its structure and thus higher difficulty to solubilize the P contained. Overall, studying the more available or soluble P forms provides useful information about the potential loss of P. However, this dissertation shows that it is necessary to examine the physical properties of organic residues applied as well as the P adsorption capacity of soils to estimate P losses, and thus to control eutrophication in water.

Modifications in the Dynamic Properties of a Structure due to Human Actions

The interest for modelling of human actions acting on structures has been recurrent since the first accidents on suspension bridges in the nineteenth century such as Broughton (1831) in the U.K. or Angers (1850) in France. Stadiums, gymnasiums are other types of structure where human induced vibration is very important. In these structures a particular phenomenon appears such as the interaction personstructure (lock-in), the person-person synchronization, and the influence of the mass and damping of the people in the structural behaviour. This paper focuses on the latter topic. In order to evaluate these property modifications several tests have been carried out on a stand-alone building. For the test an electro-dynamic shaker was installed at a fixed point of the gym slab and different groups of people were located around the shaker. The dynamic characteristics of the structure without people inside have been calculated by two methods: using a three-dimensional finite element model of the building and by operational modal analysis. These calculated experimental and numerical values are the reference values used to evaluate the modifications in the dynamic properties of the structure.

Spatial divisions of society

The encounter of architecture and urbanism with parcelisation is marked with the sign of a historical debt. Parcelisation is a tremendously powerful design tool. Architecture and urban planning attest to its capacity to shape sociospatial relations across a range of scales and contexts. From Renaissance palazzi to modernist slabs, from nation-wide agrarian reforms and Haussmann’s Paris to Christopher Alexander’s new theory of urban design and Michael Webb’s Suitaloon — most of the historical revolutions and experimental projects that have shaken these fields have relied, consciously or not, on a critique and restructuration of inherited divisions of land and space. The layout of parcel patterns has a series of implications including forms of property, the divide between private and public realms, the distribution of spatial contents and uses through zoning, typological decisions and so forth. The behaviour of any urban structure depends on the tissue of plots that configures the urban fabric and many of the challenges urban design faces today —complexity, urban vitality, social equality, etc.— hinge upon the forms of land division and distribution we adopt.

Optoelectronic property analysis of MCrO4 (M=Ba, Sr) with a response to visible light irradiation

Ternary MCrO4 (M = Ba, Sr) semiconductors are materials with a variety of photocatalyst and optoelectronic applications. We present detailed microscopic analyses based on first principles of the structure, the electronic properties and the optical absorption in which the difference between symmetrically non-equivalent atoms has been considered. The high absorption coefficients of these materials are split into chemical species contributions in accordance with the symmetry. The high optical absorption in these materials is mainly because of the Cr–O inter-species transitions.