Thermodynamics of zinc insertion in CuGaS2:Ti, used as a modulator agent in an intermediate-band photovoltaic material

An intermediate-bandphotovoltaicmaterial, which has an isolated metallic band located between the top of the valence band and bottom of the conduction band of some semiconductors, has been proposed as third generation solar cell to be used in photovoltaic applications. Density functional theory calculations of Zn in CuGaS2:Ti have previously shown that, the intermediate-band position can be modulated in proportion of Zn insertion in such a way that increasing Zn concentration can lead to aband-gap reduction, and an adjustment of the intermediate-band position. This could be interesting in the formation of an intermediate-bandmaterial, that has the maximum efficiency theoretically predicted for the intermediate-band solar cell. In this work, the energetics of several reaction schemes that could lead to the decomposition of the modulated intermediate-bandphotovoltaicmaterial, CuGaS2:Ti:Zn, is studied in order to assess the thermodynamic stability of this material. Calculations of the total free energy and disorder entropy have been taken into account, to get the reaction energy and free energy of the compound decomposition, which is found to be thermodynamically favorable

Refined second law of thermodynamics for fast random processes

We establish a refined version of the Second Law of Thermodynamics for Langevin stochastic processes describing mesoscopic systems driven by conservative or non-conservative forces and interacting with thermal noise. The refinement is based on the Monge-Kantorovich optimal mass transport and becomes relevant for processes far from quasi-stationary regime. General discussion is illustrated by numerical analysis of the optimal memory erasure protocol for a model for micron-size particle manipulated by optical tweezers.

Macroscopic motion and gravitation in thermodynamics

A series of examples rarely presented to students is discussed to illustrate a property of thermodynamic equilibrium: small parts of a fully isolated system move as if points of a rigid body, so as to minimize the macroscopic (kinetic) energy EM. Most examples lie in the fields of astronomy and astrophysics, EM then including the gravitational energy. The paradoxical behaviour of gravitation, in particular in the extreme case of black holes,is discussed.

A characterization of conserved quantities in non-equilibrium thermodynamics

The well-known Noether theorem in Lagrangian and Hamiltonian mechanics associates symmetries in the evolution equations of a mechanical system with conserved quantities. In this work, we extend this classical idea to problems of non-equilibrium thermodynamics formulated within the GENERIC (General Equations for Non-Equilibrium Reversible-Irreversible Coupling) framework. The geometric meaning of symmetry is reviewed in this formal setting and then utilized to identify possible conserved quantities and the conditions that guarantee their strict conservation. Examples are provided that demonstrate the validity of the proposed definition in the context of finite and infinite dimensional thermoelastic problems.

Equation of state for hot dense matter using a relativistic screened hydrogenic model

The study of matter under conditions of high density, pressure, and temperature is a valuable subject for inertial confinement fusion (ICF), astrophysical phenomena, high-power laser interaction with matter, etc. In all these cases, matter is heated and compressed by strong shocks to high pressures and temperatures, becomes partially or completely ionized via thermal or pressure ionization, and is in the form of dense plasma. The thermodynamics and the hydrodynamics of hot dense plasmas cannot be predicted without the knowledge of the equation of state (EOS) that describes how a material reacts to pressure and how much energy is involved. Therefore, the equation of state often takes the form of pressure and energy as functions of density and temperature. Furthermore, EOS data must be obtained in a timely manner in order to be useful as input in hydrodynamic codes. By this reason, the use of fast, robust and reasonably accurate atomic models, is necessary for computing the EOS of a material.

El microclima urbano en los espacios abiertos : estudio de casos en Madrid

El microclima urbano juega un rol importante en el consumo energético de los edificios y en las sensaciones de confort en los espacios exteriores. La urgente necesidad de aumentar la eficiencia energética, reducir las emisiones de los contaminantes y paliar la evidente falta de sostenibilidad que afecta a las ciudades, ha puesto la atención en el urbanismo bioclimático como referente para una propuesta de cambio en la forma de diseñar y vivir la ciudad. Hasta ahora las investigaciones en temas de microclima y eficiencia energética se han concentrado principalmente en como orientar el diseño de nuevos desarrollo. Sin embargo los principales problemas de la insostenibilidad de las actuales conurbaciones son el resultado del modelo de crecimiento especulativo y altamente agotador de recursos que han caracterizado el boom inmobiliario de las últimas décadas. Vemos entonces, tanto en España como en el resto de los Países Europeos, la necesidad de reorientar el sector de la construcción hacía la rehabilitación del espacio construido, como una alternativa capaz de dar una solución más sostenible para el mercado inmobiliario. En este propósito de mejorar la calidad de las ciudades actuales, el espacio público juega un papel fundamental, sobre todo como lugar para el encuentro y la socialización entre los ciudadanos. La sensación térmica condiciona la percepción de un ambiente, así que el microclima puede ser determinante para el éxito o el fracaso de un espacio urbano. Se plantea entonces cómo principal objetivo de la investigación, la definición de estrategias para el diseño bioclimático de los entornos urbanos construidos, fundamentados en las componentes morfotipológica, climática y de los requerimientos de confort para los ciudadanos. Como ulterior elemento de novedad se decide estudiar la rehabilitación de los barrios de construcción de mediado del siglo XX, que en muchos casos constituyen bolsas de degrado en la extendida periferia de las ciudades modernas. La metodología empleada para la investigación se basa en la evaluación de las condiciones climáticas y de confort térmico de diferentes escenarios de proyecto, aplicados a tres casos de estudio situados en un barrio periurbano de la ciudad de Madrid. Para la determinación de los parámetros climáticos se han empleado valores obtenidos con un proceso de simulación computarizada, basados en los principios de fluidodinámica, termodinámica y del intercambio radioactivo en el espacio construido. A través de uso de programas de simulación podemos hacer una previsión de las condiciones microclimáticas de las situaciones actuales y de los efectos de la aplicación de medidas. La gran ventaja en el uso de sistemas de cálculo es que se pueden evaluar diferentes escenarios de proyecto y elegir entre ellos el que asegura mejores prestaciones ambientales. Los resultados obtenidos en los diferentes escenarios han sido comparados con los valores de confort del estado actual, utilizando como indicador de la sensación térmica el índice UTCI. El análisis comparativo ha permitido la realización de una tabla de resumen donde se muestra la evaluación de las diferentes soluciones de rehabilitación. Se ha podido así demostrar que no existe una solución constructiva eficaz para todas las aplicaciones, sino que cada situación debe ser estudiada individualmente, aplicando caso por caso las medidas más oportunas. Si bien los sistemas de simulación computarizada pueden suponer un importante apoyo para la fase de diseño, es responsabilidad del proyectista emplear las herramientas más adecuadas en cada fase y elegir las soluciones más oportunas para cumplir con los objetivos del proyecto. The urban microclimate plays an important role on buildings energy consumption and comfort sensation in exterior spaces. Nowadays, cities need to increase energy efficiency, reduce the pollutants emissions and mitigate the evident lack of sustainability. In reason of this, attention has focused on the bioclimatic urbanism as a reference of change proposal of the way to design and live the city. Hitherto, the researches on microclimate and energy efficiency have mainly concentrated on guiding the design of new constructions. However the main problems of unsustainability of existing conurbations are the result of the growth model highly speculative and responsible of resources depletion that have characterized the real estate boom of recent decades. In Spain and other European countries, become define the need to redirect the construction sector towards urban refurbishment. This alternative is a more sustainable development model and is able to provide a solution for the real estate sector. In order to improve the quality of today's cities, the public space plays a key role, especially in order to provide to citizens places for meeting and socializing. The thermal sensation affects the environment perception, so microclimate conditions can be decisive for the success or failure of urban space. For this reasons, the main objective of this work is focused on the definition of bioclimatic strategies for existing urban spaces, based on the morpho-typological components, climate and comfort requirements for citizens. As novelty element, the regeneration of neighborhoods built in middle of the twentieth century has been studied, because are the major extended in periphery of modern cities and, in many cases, they represent deprived areas. The research methodology is based on the evaluation of climatic conditions and thermal comfort of different project scenarios, applied to three case studies located in a suburban neighborhood of Madrid. The climatic parameters have been obtained by computer simulation process, based on fluid dynamics, thermodynamics and radioactive exchange in urban environment using numerical approach. The great advantage in the use of computing systems is the capacity for evaluate different project scenarios. The results in the different scenarios were compared with the comfort value obtained in the current state, using the UTCI index as indicator of thermal sensation. Finally, an abacus of the thermal comfort improvement obtained by different countermeasures has been performed. One of the major achievement of doctoral work is the demonstration of there are not any design solution suitable for different cases. Each situation should be analyzed and specific design measures should be proposed. Computer simulation systems can be a significant support and help the designer in the decision making phase. However, the election of the most suitable tools and the appropriate solutions for each case is designer responsibility.

A fatigue damage model for seismic response of RC structures

Numerous damage models have been developed in order to analyze seismic behavior. Among the different possibilities existing in the literature, it is very clear that models developed along the lines of continuum damage mechanics are more consistent with the definition of damage as a phenomenon with mechanical consequences because they include explicitly the coupling between damage and mechanical behavior. On the other hand, for seismic processes, phenomena such as low cycle fatigue may have a pronounced effect on the overall behavior of the frames and, therefore, its consideration turns out to be very important. However, most of existing models evaluate the damage only as a function of the maximum amplitude of cyclic deformation without considering the number of cycles. In this paper, a generalization of the simplified model proposed by Cipollina et al. [Cipollina A, López-Hinojosa A, Flórez-López J. Comput Struct 1995;54:1113–26] is made in order to include the low cycle fatigue. Such a model employs in its formulation irreversible thermodynamics and internal state variable theory.

A damage model for seismic retrofitting of structures

Numerous damage models have been developed in order to analyse the seismic behavior. Among the different possibilities existing in the literature, it is very clear that models developed along the lines of Continuum Damage Mechanics are more consistent with the definition of damage like a phenomenon with mechanical consequences as they include explicitly the coupling between damage and mechanical behavior. On the other hand, for seismic processes, phenomena such as low cycle fatigue may have a pronounced effect on the overall behavior of the frames and, therefore, its consideration turns out to be very important. However, many of existing models evaluate the damage only as a function of the maximum amplitude of cyclic deformation without considering the number of cycles. In this paper, a generalization of the simplified model proposed by Flórez is made in order to include the low cycle fatigue. Such model employs in its formulation irreversible thermodynamics and internal state variable theory.

A simplified model for evaluation of fatigue damage in frames

Many studies have been developed to analyze the structural seismic behavior through the damage index concept. The evaluation of this index has been employed to quantify the safety of new and existing structures and, also, to establish a framework for seismic retrofitting decision making of structures. Most proposed models are based in a posterthquake evaluation in such a way they uncouple the structural response from the damage evaluation. In this paper, a generalization of the model by Flórez-López (1995) is proposed. The formulation employs irreversible thermodynamics and internal state variable theory applied to the study of beams and frames and it allows and explicit coupling between the degradation and the structural mechanical behavior. A damage index es defined in order to model elastoplasticity coupled with damage and fatigue damage.

A derivation of thermodynamic principles

A detailed macroscopic description as in continuum mechanics, and just the concept of microstate,have been used to derive thermodynamics from mechanics. In opposition to statistical physics, the derivation lays emphasis on a definite prescription for macrostates (and non-equilibrium entropy), and uses basic features of the macrostate concept: complementary descriptions, involving either conservative and additive quantities or densities;scale-free character; reference to finite velocities and regions distant in space, thus introducing time indirectly. On the other hand, the derivation keeps the particle substratum (limit of number of particles N taken at fixed densities), and makes no ergodic-type considerations.

Decomposition driven interface evolution for layers of binary mixtures: I. Model dirivation and base states

A dynamical model is proposed to describe the coupled decomposition and profile evolution of a free surfacefilm of a binary mixture. An example is a thin film of a polymer blend on a solid substrate undergoing simultaneous phase separation and dewetting. The model is based on model-H describing the coupled transport of the mass of one component (convective Cahn-Hilliard equation) and momentum (Navier-Stokes-Korteweg equations) supplemented by appropriate boundary conditions at the solid substrate and the free surface. General transport equations are derived using phenomenological nonequilibrium thermodynamics for a general nonisothermal setting taking into account Soret and Dufour effects and interfacial viscosity for the internal diffuse interface between the two components. Focusing on an isothermal setting the resulting model is compared to literature results and its base states corresponding to homogeneous or vertically stratified flat layers are analyzed.

Hydrothermal waves and corotating rolls in laterally heated convection in simple liquids.

The stability of a liquid layer with an undeformable interface open to the atmo- sphere, subjected to a horizontal temperature gradient, is theoretically analysed. Buoyancy and surface tension forces give rise to a basic flow for any temperature dif- ference applied on the system. Depending on the liquid depth, this basic flow is desta- bilised either by an oscillatory instability, giving rise to the so-called hydrothermal waves, or by a stationary instability leading to corotating rolls. Oscillatory perturba- tions are driven by the basic flow and therefore one must distinguish between convec- tive and absolute thresholds. The instability mechanisms as well as the di¿erent re- gimes observed in experiments are discussed. The calculations are performed for a fluid used in recent experiments, namely silicone oil of 0.65 cSt ðPr 1?4 10Þ. In partic- ular, it is shown that two branches of absolute instability exist, which may be related to the two types of hydrothermal waves observed experimentally

Estudio teórico de propiedades termodinámicas y optoelectronicas de nuevos materiales fotovoltaicos de banda intermedia = Theoretical study of thermodynamic and optoelectronic properties of new intermediate band photovoltaic materials

Los materiales de banda intermedia han atraido la atención de la comunidad científica en el campo de la energía solar fotovoltaica en los últimos años. Sin embargo, con el objetivo de entender los fundamentos de las células solares de banda intermedia, se debe llevar a cabo un estudio profundo de la características de los materiales. Esto se puede hacer mediante un modelo teórico usando Primeros Principios. A partir de este enfoque se pueden obtener resultados tales como la estructura electrónica y propiedades ópticas, entre otras, de los semiconductores fuertemente dopados y sus precursores. Con el fin de desentrañar las estructuras de estos sistemas electrónicos, esta tesis presenta un estudio termodinámico y optoelectrónico de varios materiales fotovoltaicos. Específicamente se caracterizaron los materiales avanzados de banda intermedia y sus precursores. El estudio se hizo en términos de caracterización teórica de la estructura electrónica, la energética del sistema, entre otros. Además la estabilidad se obtuvo usando configuraciones adaptadas a la simetría del sistema y basado en la combinatoria. Las configuraciones de los sitios ocupados por defectos permiten obtener información sobre un espacio de configuraciones donde las posiciones de los dopantes sustituidos se basan en la simetría del sólido cristalino. El resultado puede ser tratado usando elementos de termodinámica estadística y da información de la estabilidad de todo el espacio simétrico. Además se estudiaron otras características importantes de los semiconductores de base. En concreto, el análisis de las interacciones de van der Waals fueron incluidas en el semiconductor en capas SnS2, y el grado de inversión en el caso de las espinelas [M]In2S4. En este trabajo además realizamos una descripción teórica exhaustiva del sistema CdTe:Bi. Este material de banda-intermedia muestra características que son distintas a las de los otros materiales estudiados. También se analizó el Zn como agente modulador de la posición de las sub-bandas prohibidas en el material de banda-intermedia CuGaS2:Ti. Analizándose además la viabilidad termodinámica de la formación de este compuesto. Finalmente, también se describió el GaN:Cr como material de banda intermedia, en la estructura zinc-blenda y en wurtztite, usando configuraciones de sitios ocupados de acuerdo a la simetría del sistema cristalino del semiconductor de base. Todos los resultados, siempre que fue posible, fueron comparados con los resultados experimentales. ABSTRACT The intermediate-band materials have attracted the attention of the scientific community in the field of the photovoltaics in recent years. Nevertheless, in order to understand the intermediate-band solar cell fundamentals, a profound study of the characteristics of the materials is required. This can be done using theoretical modelling from first-principles. The electronic structure and optical properties of heavily doped semiconductors and their precursor semiconductors are, among others, results that can be obtained from this approach. In order to unravel the structures of these crystalline systems, this thesis presents a thermodynamic and optoelectronic study of several photovoltaic materials. Specifically advanced intermediate-band materials and their precursor semiconductors were characterized. The study was made in terms of theoretical characterization of the electronic structure, energetics among others. The stability was obtained using site-occupancy-disorder configurations adapted to the symmetry of the system and based on combinatorics. The site-occupancy-disorder method allows the formation of a configurational space of substitutional dopant positions based on the symmetry of the crystalline solid. The result, that can be treated using statistical thermodynamics, gives information of the stability of the whole space of symmetry of the crystalline lattice. Furthermore, certain other important characteristics of host semiconductors were studied. Specifically, the van der Waal interactions were included in the SnS2 layered semiconductor, and the inversion degree in cases of [M]In2S4 spinels. In this work we also carried out an exhaustive theoretical description of the CdTe:Bi system. This intermediate-band material shows characteristics that are distinct from those of the other studied intermediate-band materials. In addition, Zn was analysed as a modulator of the positions of the sub-band gaps in the CuGaS2:Ti intermediate-band material. The thermodynamic feasibility of the formation of this compound was also carried out. Finally GaN:Cr intermediate-band material was also described both in the zinc-blende and the wurtztite type structures, using the symmetry-adapted-space of configurations. All results, whenever possible, were compared with experimental results.

A puzzling solar cell structure: an exercise to get insight on intermediate band solar cells

We introduce one trivial but puzzling solar cell structure. It consists of a high bandgap pn junction (top cell) grown on a substrate of lower bandgap. Let us assume, for example, that the bandgap of the top cell is 1.85 eV (Al 0.3Ga 0.7As) and the bandgap of the substrate is 1.42 eV (GaAs). Is the open-circuit of the top cell limited to 1.42 V or to 1.85 V? If the answer is ldquo1.85 Vrdquo we could then make the mind experiment in which we illuminate the cell with 1.5 eV photons (notice these photons would only be absorbed in the substrate). If we admit that these photons can generate photocurrent, then because we have also admitted that the voltage is limited to 1.85 V, it might be possible that the electron-hole pairs generated by these photons were extracted at 1.6 V for example. However, if we do so, the principles of thermodynamics could be violated because we would be extracting more energy from the photon than the energy it initially had. How can we then solve this puzzle?

Entornos termodinámicos. Una cartografía crítica en torno a la energía y la arquitectura

En los últimos años, y a la luz de los retos a los que se enfrenta la sociedad, algunas voces están urgiendo a dejar atrás los paradigmas modernos —eficiencia y rendimiento— que sustentan a las llamadas prácticas sostenibles, y están alentando a repensar, en el contexto de los cambios científicos y culturales, una agenda termodinámica y ecológica para la arquitectura. La cartografía que presenta esta tesis doctoral se debe de entender en este contexto. Alineándose con esta necesidad, se esfuerza por dar a este empeño la profundidad histórica de la que carece. De este modo, el esfuerzo por dotar a la arquitectura de una agenda de base científica, se refuerza con una discusión cultural sobre el progresivo empoderamiento de las ideas termodinámicas en la arquitectura. Esta cartografía explora la historia de las ideas termodinámicas en la arquitectura desde el principio del siglo XX hasta la actualidad. Estudia, con el paso de los sistemas en equilibrio a los alejados del equilibrio como trasfondo, como las ideas termodinámicas han ido infiltrándose gradualmente en la arquitectura. Este esfuerzo se ha planteado desde un doble objetivo. Primero, adquirir una distancia crítica respecto de las prácticas modernas, de modo que se refuerce y recalibre el armazón intelectual y las herramientas sobre las que se está apoyando esta proyecto termodinámico. Y segundo, desarrollar una aproximación proyectual sobre la que se pueda fundamentar una agenda termodinámica para la arquitectura, asunto que se aborda desde la firme creencia de que es posible una re-descripción crítica de la realidad. De acuerdo con intercambios de energía que se dan alrededor y a través de un edificio, esta cartografía se ha estructurado en tres entornos termodinámicos, que sintetizan mediante un corte transversal la variedad de intercambios de energía que se dan en la arquitectura: -Cualquier edificio, como constructo espacial y material inmerso en el medio, intercambia energía mediante un flujo bidireccional con su contexto, definiendo un primer entorno termodinámico al que se denomina atmósferas territoriales. -En el interior de los edificios, los flujos termodinámicos entre la arquitectura y su ambiente interior definen un segundo entorno termodinámico, atmósferas materiales, que explora las interacciones entre los sistemas materiales y la atmósfera interior. -El tercer entorno termodinámico, atmosferas fisiológicas, explora los intercambios de energía que se dan entre el cuerpo humano y el ambiente invisible que lo envuelve, desplazando el objeto de la arquitectura desde el marco físico hacia la interacción entre la atmósfera y los procesos somáticos y percepciones neurobiológicas de los usuarios. A través de estos tres entornos termodinámicos, esta cartografía mapea aquellos patrones climáticos que son relevantes para la arquitectura, definiendo tres situaciones espaciales y temporales sobre las que los arquitectos deben actuar. Estudiando las conexiones entre la atmósfera, la energía y la arquitectura, este mapa presenta un conjunto de ideas termodinámicas disponibles —desde los parámetros de confort definidos por la industria del aire acondicionado hasta las técnicas de acondicionamiento pasivo— que, para ser efectivas, necesitan ser evaluadas, sintetizadas y recombinadas a la luz de los retos de nuestro tiempo. El resultado es un manual que, mediando entre la arquitectura y la ciencia, y a través de este relato histórico, acorta la distancia entre la arquitectura y la termodinámica, preparando el terreno para la definición de una agenda termodinámica para el proyecto de arquitectura. A este respecto, este mapa se entiende como uno de los pasos necesarios para que la arquitectura recupere la capacidad de intervenir en la acuciante realidad a la que se enfrenta. ABSTRACT During the last five years, in the light of current challenges, several voices are urging to leave behind the modern energy paradigms —efficiency and performance— on which the so called sustainable practices are relying, and are posing the need to rethink, in the light of the scientific and cultural shifts, the thermodynamic and ecological models for architecture. The historical cartography this PhD dissertation presents aligns with this effort, providing the cultural background that this endeavor requires. The drive to ground architecture on a scientific basis needs to be complemented with a cultural discussion of the history of thermodynamic ideas in architecture. This cartography explores the history of thermodynamic ideas in architecture, from the turn of the 20th century until present day, focusing on the energy interactions between architecture and atmosphere. It surveys the evolution of thermodynamic ideas —the passage from equilibrium to far from equilibrium thermodynamics— and how these have gradually empowered within design and building practices. In doing so, it has posed a double-objective: first, to acquire a critical distance with modern practices which strengthens and recalibrates the intellectual framework and the tools in which contemporary architectural endeavors are unfolding; and second, to develop a projective approach for the development a thermodynamic agenda for architecture and atmosphere, with the firm belief that a critical re-imagination of reality is possible. According to the different systems which exchange energy across a building, the cartography has been structured in three particular thermodynamic environments, providing a synthetic cross-section of the range of thermodynamic exchanges which take place in architecture: -Buildings, as spatial and material constructs immersed in the environment, are subject to a contiuous bidirectional flow of energy with its context, defining a the first thermodynamic environment called territorial atmospheres. -Inside buildings, the thermodynamic flow between architecture and its indoor ambient defines a second thermodynamic environment, material atmospheres, which explores the energy interactions between the indoor atmosphere and its material systems. -The third thermodynamic environment, physiological atmospheres, explores the energy exchanges between the human body and the invisible environment which envelopes it, shifting design drivers from building to the interaction between the atmosphere and the somatic processes and neurobiological perceptions of users. Through these three thermodynamic environments, this cartography maps those climatic patterns which pertain to architecture, providing three situations on which designers need to take stock. Studying the connections between atmosphere, energy and architecture this map presents, not a historical paradigm shift from mechanical climate control to bioclimatic passive techniques, but a range of available thermodynamic ideas which need to be assessed, synthesized and recombined in the light of the emerging challenges of our time. The result is a manual which, mediating between architecture and science, and through this particular historical account, bridges the gap between architecture and thermodynamics, paving the way to a renewed approach to atmosphere, energy and architecture. In this regard this cartography is understood as one of the necessary steps to recuperate architecture’s lost capacity to intervene in the pressing reality of contemporary societies.