Progress on optimization of the solar cell fabrication process by impurity-to-efficiency predictive simulator

To optimize the last high temperature step of a standard solar cell fabrication process (the contact cofiring step), the aluminium gettering is incorporated in the Impurity-to-Efficiency simulation tool, so that it models the phosphorus and aluminium co-gettering effect on iron impurities. The impact of iron on the cell efficiency will depend on the balance between precipitate dissolution and gettering. Gettering efficiency is similar in a wide range of peak temperatures (600-850 ºC), so that this peak temperature can be optimized favoring other parameters (e.g. ohmic contact). An industrial co-firing step can enhance the co-gettering effect by adding a temperature plateau after the peak of temperature. For highly contaminated materials, a short plateau (menor que 2 min) at low temperature (600 ºC) is shown to reduce the dissolved iron.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

The Influence of Communication Range on Connectivity for Resilient Wireless Sensor Networks Using a Probabilistic Approach.

Wireless sensor networks (WSNs) consist of thousands of nodes that need to communicate with each other. However, it is possible that some nodes are isolated from other nodes due to limited communication range. This paper focuses on the influence of communication range on the probability that all nodes are connected under two conditions, respectively: (1) all nodes have the same communication range, and (2) communication range of each node is a random variable. In the former case, this work proves that, for 0menor queepsmenor quee^(-1) , if the probability of the network being connected is 0.36eps , by means of increasing communication range by constant C(eps) , the probability of network being connected is at least 1-eps. Explicit function C(eps) is given. It turns out that, once the network is connected, it also makes the WSNs resilient against nodes failure. In the latter case, this paper proposes that the network connection probability is modeled as Cox process. The change of network connection probability with respect to distribution parameters and resilience performance is presented. Finally, a method to decide the distribution parameters of node communication range in order to satisfy a given network connection probability is developed.

Criteria for mathematical model selection for satellite vibro-acoustic analysis depending on frequency range

Satellites and space equipment are exposed to diffuse acoustic fields during the launch process. The use of adequate techniques to model the response to the acoustic loads is a fundamental task during the design and verification phases. Considering the modal density of each element is necessary to identify the correct methodology. In this report selection criteria are presented in order to choose the correct modelling technique depending on the frequency ranges. A model satellite’s response to acoustic loads is presented, determining the modal densities of each component in different frequency ranges. The paper proposes to select the mathematical method in each modal density range and the differences in the response estimation due to the different used techniques. In addition, the methodologies to analyse the intermediate range of the system are discussed. The results are compared with experimental testing data obtained in an experimental modal test.

Ratio-based temperature-sensing technique hardened against nanometer process variations

This letter presents a temperature-sensing technique on the basis of the temperature dependency of MOSFET leakage currents. To mitigate the effects of process variation, the ratio of two different leakage current measurements is calculated. Simulations show that this ratio is robust to process spread. The resulting sensor is quite small-0.0016 mm2 including an analog-to-digital conversion-and very energy efficient, consuming less than 640 pJ/conversion. After a two-point calibration, the accuracy in a range of 40°C-110°C is less than 1.5°C , which makes the technique suitable for thermal management applications.

V-substituted In2S3: an intermediate band material with photocatalytic activity in the whole visible light range

We proposed in our previous work V-substituted In2S3 as an intermediate band (IB) material able to enhance the efficiency of photovoltaic cells by combining two photons to achieve a higher energy electron excitation, much like natural photosynthesis. Here this hyper-doped material is tested in a photocatalytic reaction using wavelength-controlled light. The results evidence its ability to use photons with wavelengths of up to 750 nm, i.e. with energy significantly lower than the bandgap (=2.0 eV) of non-substituted In2S3, driving with them the photocatalytic reaction at rates comparable to those of non-substituted In2S3 in its photoactivity range (λ ≤ 650 nm). Photoluminescence spectra evidence that the same bandgap excitation as in V-free In2S3 occurs in V-substituted In2S3 upon illumination with photons in the same sub-bandgap energy range which is effective in photocatalysis, and its linear dependence on light intensity proves that this is not due to a nonlinear optical property. This evidences for the first time that a two-photon process can be active in photocatalysis in a single-phase material. Quantum calculations using GW-type many-body perturbation theory suggest that the new band introduced in the In2S3 gap by V insertion is located closer to the conduction band than to the valence band, so that hot carriers produced by the two-photon process would be of electron type; they also show that the absorption coefficients of both transitions involving the IB are of significant and similar magnitude. The results imply that V-substituted In2S3, besides being photocatalytically active in the whole visible light range (a property which could be used for the production of solar fuels), could make possible photovoltaic cells of improved efficiency.

Arquitectura industrial tabacalera en la España peninsular: secaderos y fábricas

La Arquitectura industrial del tabaco en España está representada por dos tipos de construcciones, que corresponden a las dos fases en las que se divide el proceso de producción del tabaco: los secaderos (arquitectura bioclimática donde se realiza el secado), y las fábricas (centros donde se elabora el tabaco procedente de los secaderos). Las fábricas se repartieron por todo el territorio español, ocupando preferiblemente los lugares costeros, aunque existen casos en los que su localización obedecía a razones políticas. Estos edificios, en su mayoría, incluidos en los centros históricos de las ciudades, han cambiando de uso, y las antiguas fábricas de tabaco se han transformado en su mayoría, en centros de cultura, o centros sociales y representativos. La tesis surge del análisis de las características constructivas de la arquitectura industrial del tabaco: de los secaderos y de las fábricas, por tratarse de una tipología con suficiente entidad y un ejemplo de arquitectura bioclimática de producción en el caso de los secaderos, y por conseguir haberse adaptado a otros usos en el caso de las fábricas. La arquitectura de producción emplea un lenguaje acorde con los avances de la industrialización, anticipando materiales y estructuras, y condensando en una tipología específica las complejas relaciones establecidas entre producto, hombres y espacio. Estos edificios tuvieron una extensa implantación en el territorio, y se caracterizan por una serie de valores tecnológicos, arquitectónicos, sociológicos y paisajísticos, que hacen de ellos un documento de primera magnitud para conocer: la evolución e implantación de las técnicas constructivas (materiales y estructuras), los procesos de innovación tipológica y la estructura económica y procedimientos técnicos utilizados. El territorio en el que se insertan constituye su contexto territorial, por lo que no sería adecuado considerar estos edificios como elementos aislados, sin analizar la relación con el entorno en el que se generaron. Por este motivo, se analizan las condiciones higrotérmicas ambientales de los secaderos para compararlas con las de confort humano y establecer relaciones y parámetros compatibles. Los ejemplos analizados de secaderos son todos de fábrica. El uso del ladrillo como módulo principal para la elaboración de un edificio, supone la consideración de un “grado cero” de todo el aparato constructivo y compositivo de la arquitectura. Dejar el ladrillo visto, supone hacer explícitos todos los procesos acumulativos. Este elemento mínimo, permite unas posibilidades enormemente abiertas, pero no absolutamente aleatorias, que definen su propia lógica combinatoria. La exigencia de sinceridad, característica de la arquitectura industrial, en la exposición de los materiales, exhibiéndolos en su propia naturaleza y en el modo real de ser utilizados, se hace patente en este tipo de construcción. Se realiza un estudio de permeabilidad en las fachadas de los secaderos, para determinar el grado de ventilación y su relación con la orientación, el patrón de celosía empleado y el volumen total. Este sistema de acondicionamiento climático específico, puede servir de recurso a otras construcciones, por lo que se podría trasladar el sistema constructivo y formal de los secaderos a otros usos, desde una doble vertiente: Arquitectura para la adaptación climática al entorno. Arquitectura como generadora de condiciones climáticas específicas, en el interior. La utilidad de los secaderos es fundamentalmente: proporcionar sombra, ventilación y un espacio cubierto, pero permeable en sus fachadas. La arquitectura industrial debe ser reconocida dentro del conjunto patrimonial, debido a sus características propias que permiten su diferenciación del resto de la arquitectura. Conocer la estructura productiva permite analizar correctamente estas construcciones, ya que el programa inicial es básico para entender la organización del espacio interior. Las fábricas no se situaron cerca de las zonas de producción del tabaco, excepto en dos casos: Cádiz y Palazuelo, en los que existen secaderos y campos de cultivo de hoja de tabaco en las áreas cercanas. La principal causa de esta separación es que el proceso de obtención de tabaco es un proceso dividido en dos fases principales: proceso primario y proceso secundario. En el proceso primario la hoja de tabaco se seca en los secaderos, en los que es determinante el clima, pero únicamente en el caso del secado del tabaco al aire. En el proceso secundario sin embargo, el tabaco llega previamente tratado a las fábricas, por lo que no influye el clima en esta parte del proceso. Esta razón determina que en las áreas climáticas donde se centra el estudio, haya zonas en las que existen fábrica y secaderos y otras en las que únicamente existe fábrica, o sólo secaderos. La localización de las fábricas atendía a razones de muy diferente índole, las más importantes fueron: geográficas, estratégicas, y políticas. En la mayoría de las fábricas la elección de la ciudad de emplazamiento estaba ligada a la recepción de la materia prima, que principalmente se hacía por vía marítima, o acuática (el caso de Sevilla), y por vía terrestre, utilizando como medio de transporte el ferrocarril. Sólo dos casos, de las antiguas fábricas, corresponden a razones políticas, son las dos únicas que no están en la costa: Madrid y Logroño. La de Madrid se construyó por centralidad política, y porque geográficamente ocupaba el punto central de todas las comunicaciones terrestres por carretera y ferrocarril. Muchas de las fábricas se situaron cercanas a las estaciones de ferrocarril. La de Logroño atendió, sin embargo, a razones políticas. Para finalizar, se realiza un estudio comparativo de las fábricas de Sevilla, Madrid y San Sebastián. Las razones que justifican esta elección son: - La de Sevilla fue históricamente la primera fábrica y la más importante. - La de Madrid fue la más importante a nivel administrativo, la sede de Tabacalera se instaló en la capital, y después de la de Sevilla, fue la que sirvió de modelo al resto de las fábricas. - La de San Sebastián era la más grande del Norte. Los análisis que se han realizado son de: volumen y superficies de patios, superficies de cubierta, permeabilidad o huecos en fachadas, orientación y soleamiento de patios, distribución espacial interior y organización, y evolución de usos. Podemos observar que en la mayoría de estas fábricas ha habido una transformación en el uso, pasando de ser edificios industriales a edificios culturales. Estas construcciones se pueden considerar como infraestructuras adaptables, por ser útiles, sostenibles y funcionales. ABSTRACT The Spanish industrial architecture of tobacco is represented by two construction types that correspond to the two phases of tobacco production: the drying sheds (bioclimatic constructions where the drying process takes place) and factories (centres where tobacco is processed after the drying process). The factories were distributed throughout the Spanish territory, preferably occupying coastal locations, although some of them were located elsewhere following political reasons. Most of the buildings inside city centres have suffered changes in their use, becoming cultural, social or representative centres. This thesis attempts the analysis of the constructive systems employed in tobacco industrial architecture, from drying sheds to factories. The drying sheds are an example of bioclimatic industrial architecture. The factories are a typology that have successfully adapted to new uses. Industrial architecture uses a language that follows the advances in industrialization, anticipating new materials and structures, and merging the complex relationships established among products, human beings, space and locations. These buildings were promoted extensively in the country. They are characterized by technological architectural sociological and landscaping innovations. They are considered as important examples of the evolution and the implementation of construction techniques (building materials and structures). They are also considered as examples of innovation in the building typology, in their economic structure and in the technologies that they have applied. The settings in which the drying sheds are placed have an important influence in them. They cannot be considered as isolated elements. Instead, there is a close relationship between drying sheds and the surroundings in which they are located. Drying sheds’ hygrotermal and environmental conditions are analyzed in this thesis to compare them with the values of human comfort and find suitable relationships and parameters. All the drying sheds that have been analyzed are constructed with brick. This implies a consideration of “zero degree” for both the construction and the composition of the architectural process. The detailing - entails making all the accumulative processes explicit as the brick walls are left exposed. This minimal component allows a wide range of options that are never random but based on the logic of the way in which it is combined. The “sincerity” in the exposition of material, displaying them in their very nature and showing how they are really used, is a basic characteristic of industrial architecture, and it is even more expressive in these types of buildings. The walls of the drying sheds undergo a permeability assessment in order to determine the degree of ventilation and orientation, the lattice pattern used and the overall volume. This specific conditioning system can serve as a resource for other buildings, and consequently, it could be transferred to other uses within a two-pronged approach: -Climatically adapted architecture that takes into account the surroundings. -Architecture as a generator of specific climatic conditions indoors. Drying sheds’ main purposes / aims deal with how to provide shade, ventilation and a covered space as well as permeability. The industrial architecture must be recognized as historical valuable buildings due to its intrinsic and distinctive characteristics. Knowing the productive structure, allow us to make a proper analysis of these buildings, since the basic aim, is to understand the spatial organization indoors. Factories did not come close to the tobacco production, with the exception of Cádiz and Palazuelo, where there are sheds and tobacco croplands nearby. The main reason for this separation is that the process of obtaining tobacco has two processes: the primary process and the secondary process. In the primary process tobacco leaves are left to dry. In the secondary process, previously manufactured tobacco allocated in the factories where the weather conditions are not important. This fact determines that in the climate areas where this study tales place there are some cases in which we can find both factories and drying sheds, and others where there are either factories or drying sheds only. The location of these factories met various demands, being the most outstanding the ones related to geographic, strategic and political reasons. In most factories the choice of its location was often linked to the incoming of raw goods, mainly delivered through waterways –it is the case of Seville,) and by land, using railways. The location of the factories was linked to political reasons in only two cases Madrid and Logroño, which are the only ones that are not placed near the coast. The one in Madrid was built due to its political centrality and because geographically speaking, it was the reference landmark of means of land and rail transports. Many factories, in fact, were settled nearby rail stations. For the factory in Logroño, only political reasons were taken into consideration. I should like to close by undertaking a comparative study of factories in Seville, Madrid and San Sebastian. There are a number of reasons to substantiate this choice: -The factory in Seville was historically speaking the first that was built and the most important one. -The factory in Madrid was the most important one administratively. This factory was the headquarters as well as being, after Seville, the one which provided a model for other factories. -The factory in San Sebastian is the biggest in the North of Spain. The analysis carried out are related to the volume of the buildings and the surface areas of the courtyards, the surface of the roofs, the permeability of the walls and the openings of the façade, the orientation and the sun exposure, the indoor spatial distribution and organization and evolution of the uses (formerly and currently) I observe that in most of these factories there has been a change in the use of the buildings, from industrial cultural purposes. These buildings can be considered as adaptable infrastructures based on a combination of architectural practicability, sustainability and functionality.

Contribución al estudio de las metodologías de cálculo realista con incertidumbre (BEPU), dentro del análisis determinista de seguridad de plantas nucleares

El análisis determinista de seguridad (DSA) es el procedimiento que sirve para diseñar sistemas, estructuras y componentes relacionados con la seguridad en las plantas nucleares. El DSA se basa en simulaciones computacionales de una serie de hipotéticos accidentes representativos de la instalación, llamados escenarios base de diseño (DBS). Los organismos reguladores señalan una serie de magnitudes de seguridad que deben calcularse en las simulaciones, y establecen unos criterios reguladores de aceptación (CRA), que son restricciones que deben cumplir los valores de esas magnitudes. Las metodologías para realizar los DSA pueden ser de 2 tipos: conservadoras o realistas. Las metodologías conservadoras utilizan modelos predictivos e hipótesis marcadamente pesimistas, y, por ello, relativamente simples. No necesitan incluir un análisis de incertidumbre de sus resultados. Las metodologías realistas se basan en hipótesis y modelos predictivos realistas, generalmente mecanicistas, y se suplementan con un análisis de incertidumbre de sus principales resultados. Se les denomina también metodologías BEPU (“Best Estimate Plus Uncertainty”). En ellas, la incertidumbre se representa, básicamente, de manera probabilista. Para metodologías conservadores, los CRA son, simplemente, restricciones sobre valores calculados de las magnitudes de seguridad, que deben quedar confinados en una “región de aceptación” de su recorrido. Para metodologías BEPU, el CRA no puede ser tan sencillo, porque las magnitudes de seguridad son ahora variables inciertas. En la tesis se desarrolla la manera de introducción de la incertidumbre en los CRA. Básicamente, se mantiene el confinamiento a la misma región de aceptación, establecida por el regulador. Pero no se exige el cumplimiento estricto sino un alto nivel de certidumbre. En el formalismo adoptado, se entiende por ello un “alto nivel de probabilidad”, y ésta corresponde a la incertidumbre de cálculo de las magnitudes de seguridad. Tal incertidumbre puede considerarse como originada en los inputs al modelo de cálculo, y propagada a través de dicho modelo. Los inputs inciertos incluyen las condiciones iniciales y de frontera al cálculo, y los parámetros empíricos de modelo, que se utilizan para incorporar la incertidumbre debida a la imperfección del modelo. Se exige, por tanto, el cumplimiento del CRA con una probabilidad no menor a un valor P0 cercano a 1 y definido por el regulador (nivel de probabilidad o cobertura). Sin embargo, la de cálculo de la magnitud no es la única incertidumbre existente. Aunque un modelo (sus ecuaciones básicas) se conozca a la perfección, la aplicación input-output que produce se conoce de manera imperfecta (salvo que el modelo sea muy simple). La incertidumbre debida la ignorancia sobre la acción del modelo se denomina epistémica; también se puede decir que es incertidumbre respecto a la propagación. La consecuencia es que la probabilidad de cumplimiento del CRA no se puede conocer a la perfección; es una magnitud incierta. Y así se justifica otro término usado aquí para esta incertidumbre epistémica: metaincertidumbre. Los CRA deben incorporar los dos tipos de incertidumbre: la de cálculo de la magnitud de seguridad (aquí llamada aleatoria) y la de cálculo de la probabilidad (llamada epistémica o metaincertidumbre). Ambas incertidumbres pueden introducirse de dos maneras: separadas o combinadas. En ambos casos, el CRA se convierte en un criterio probabilista. Si se separan incertidumbres, se utiliza una probabilidad de segundo orden; si se combinan, se utiliza una probabilidad única. Si se emplea la probabilidad de segundo orden, es necesario que el regulador imponga un segundo nivel de cumplimiento, referido a la incertidumbre epistémica. Se denomina nivel regulador de confianza, y debe ser un número cercano a 1. Al par formado por los dos niveles reguladores (de probabilidad y de confianza) se le llama nivel regulador de tolerancia. En la Tesis se razona que la mejor manera de construir el CRA BEPU es separando las incertidumbres, por dos motivos. Primero, los expertos defienden el tratamiento por separado de incertidumbre aleatoria y epistémica. Segundo, el CRA separado es (salvo en casos excepcionales) más conservador que el CRA combinado. El CRA BEPU no es otra cosa que una hipótesis sobre una distribución de probabilidad, y su comprobación se realiza de forma estadística. En la tesis, los métodos estadísticos para comprobar el CRA BEPU en 3 categorías, según estén basados en construcción de regiones de tolerancia, en estimaciones de cuantiles o en estimaciones de probabilidades (ya sea de cumplimiento, ya sea de excedencia de límites reguladores). Según denominación propuesta recientemente, las dos primeras categorías corresponden a los métodos Q, y la tercera, a los métodos P. El propósito de la clasificación no es hacer un inventario de los distintos métodos en cada categoría, que son muy numerosos y variados, sino de relacionar las distintas categorías y citar los métodos más utilizados y los mejor considerados desde el punto de vista regulador. Se hace mención especial del método más utilizado hasta el momento: el método no paramétrico de Wilks, junto con su extensión, hecha por Wald, al caso multidimensional. Se decribe su método P homólogo, el intervalo de Clopper-Pearson, típicamente ignorado en el ámbito BEPU. En este contexto, se menciona el problema del coste computacional del análisis de incertidumbre. Los métodos de Wilks, Wald y Clopper-Pearson requieren que la muestra aleatortia utilizada tenga un tamaño mínimo, tanto mayor cuanto mayor el nivel de tolerancia exigido. El tamaño de muestra es un indicador del coste computacional, porque cada elemento muestral es un valor de la magnitud de seguridad, que requiere un cálculo con modelos predictivos. Se hace especial énfasis en el coste computacional cuando la magnitud de seguridad es multidimensional; es decir, cuando el CRA es un criterio múltiple. Se demuestra que, cuando las distintas componentes de la magnitud se obtienen de un mismo cálculo, el carácter multidimensional no introduce ningún coste computacional adicional. Se prueba así la falsedad de una creencia habitual en el ámbito BEPU: que el problema multidimensional sólo es atacable desde la extensión de Wald, que tiene un coste de computación creciente con la dimensión del problema. En el caso (que se da a veces) en que cada componente de la magnitud se calcula independientemente de los demás, la influencia de la dimensión en el coste no se puede evitar. Las primeras metodologías BEPU hacían la propagación de incertidumbres a través de un modelo sustitutivo (metamodelo o emulador) del modelo predictivo o código. El objetivo del metamodelo no es su capacidad predictiva, muy inferior a la del modelo original, sino reemplazar a éste exclusivamente en la propagación de incertidumbres. Para ello, el metamodelo se debe construir con los parámetros de input que más contribuyan a la incertidumbre del resultado, y eso requiere un análisis de importancia o de sensibilidad previo. Por su simplicidad, el modelo sustitutivo apenas supone coste computacional, y puede estudiarse exhaustivamente, por ejemplo mediante muestras aleatorias. En consecuencia, la incertidumbre epistémica o metaincertidumbre desaparece, y el criterio BEPU para metamodelos se convierte en una probabilidad simple. En un resumen rápido, el regulador aceptará con más facilidad los métodos estadísticos que menos hipótesis necesiten; los exactos más que los aproximados; los no paramétricos más que los paramétricos, y los frecuentistas más que los bayesianos. El criterio BEPU se basa en una probabilidad de segundo orden. La probabilidad de que las magnitudes de seguridad estén en la región de aceptación no sólo puede asimilarse a una probabilidad de éxito o un grado de cumplimiento del CRA. También tiene una interpretación métrica: representa una distancia (dentro del recorrido de las magnitudes) desde la magnitud calculada hasta los límites reguladores de aceptación. Esta interpretación da pie a una definición que propone esta tesis: la de margen de seguridad probabilista. Dada una magnitud de seguridad escalar con un límite superior de aceptación, se define el margen de seguridad (MS) entre dos valores A y B de la misma como la probabilidad de que A sea menor que B, obtenida a partir de las incertidumbres de A y B. La definición probabilista de MS tiene varias ventajas: es adimensional, puede combinarse de acuerdo con las leyes de la probabilidad y es fácilmente generalizable a varias dimensiones. Además, no cumple la propiedad simétrica. El término margen de seguridad puede aplicarse a distintas situaciones: distancia de una magnitud calculada a un límite regulador (margen de licencia); distancia del valor real de la magnitud a su valor calculado (margen analítico); distancia desde un límite regulador hasta el valor umbral de daño a una barrera (margen de barrera). Esta idea de representar distancias (en el recorrido de magnitudes de seguridad) mediante probabilidades puede aplicarse al estudio del conservadurismo. El margen analítico puede interpretarse como el grado de conservadurismo (GC) de la metodología de cálculo. Utilizando la probabilidad, se puede cuantificar el conservadurismo de límites de tolerancia de una magnitud, y se pueden establecer indicadores de conservadurismo que sirvan para comparar diferentes métodos de construcción de límites y regiones de tolerancia. Un tópico que nunca se abordado de manera rigurosa es el de la validación de metodologías BEPU. Como cualquier otro instrumento de cálculo, una metodología, antes de poder aplicarse a análisis de licencia, tiene que validarse, mediante la comparación entre sus predicciones y valores reales de las magnitudes de seguridad. Tal comparación sólo puede hacerse en escenarios de accidente para los que existan valores medidos de las magnitudes de seguridad, y eso ocurre, básicamente en instalaciones experimentales. El objetivo último del establecimiento de los CRA consiste en verificar que se cumplen para los valores reales de las magnitudes de seguridad, y no sólo para sus valores calculados. En la tesis se demuestra que una condición suficiente para este objetivo último es la conjunción del cumplimiento de 2 criterios: el CRA BEPU de licencia y un criterio análogo, pero aplicado a validación. Y el criterio de validación debe demostrarse en escenarios experimentales y extrapolarse a plantas nucleares. El criterio de licencia exige un valor mínimo (P0) del margen probabilista de licencia; el criterio de validación exige un valor mínimo del margen analítico (el GC). Esos niveles mínimos son básicamente complementarios; cuanto mayor uno, menor el otro. La práctica reguladora actual impone un valor alto al margen de licencia, y eso supone que el GC exigido es pequeño. Adoptar valores menores para P0 supone menor exigencia sobre el cumplimiento del CRA, y, en cambio, más exigencia sobre el GC de la metodología. Y es importante destacar que cuanto mayor sea el valor mínimo del margen (de licencia o analítico) mayor es el coste computacional para demostrarlo. Así que los esfuerzos computacionales también son complementarios: si uno de los niveles es alto (lo que aumenta la exigencia en el cumplimiento del criterio) aumenta el coste computacional. Si se adopta un valor medio de P0, el GC exigido también es medio, con lo que la metodología no tiene que ser muy conservadora, y el coste computacional total (licencia más validación) puede optimizarse. ABSTRACT Deterministic Safety Analysis (DSA) is the procedure used in the design of safety-related systems, structures and components of nuclear power plants (NPPs). DSA is based on computational simulations of a set of hypothetical accidents of the plant, named Design Basis Scenarios (DBS). Nuclear regulatory authorities require the calculation of a set of safety magnitudes, and define the regulatory acceptance criteria (RAC) that must be fulfilled by them. Methodologies for performing DSA van be categorized as conservative or realistic. Conservative methodologies make use of pessimistic model and assumptions, and are relatively simple. They do not need an uncertainty analysis of their results. Realistic methodologies are based on realistic (usually mechanistic) predictive models and assumptions, and need to be supplemented with uncertainty analyses of their results. They are also termed BEPU (“Best Estimate Plus Uncertainty”) methodologies, and are typically based on a probabilistic representation of the uncertainty. For conservative methodologies, the RAC are simply the restriction of calculated values of safety magnitudes to “acceptance regions” defined on their range. For BEPU methodologies, the RAC cannot be so simple, because the safety magnitudes are now uncertain. In the present Thesis, the inclusion of uncertainty in RAC is studied. Basically, the restriction to the acceptance region must be fulfilled “with a high certainty level”. Specifically, a high probability of fulfillment is required. The calculation uncertainty of the magnitudes is considered as propagated from inputs through the predictive model. Uncertain inputs include model empirical parameters, which store the uncertainty due to the model imperfection. The fulfillment of the RAC is required with a probability not less than a value P0 close to 1 and defined by the regulator (probability or coverage level). Calculation uncertainty is not the only one involved. Even if a model (i.e. the basic equations) is perfectly known, the input-output mapping produced by the model is imperfectly known (unless the model is very simple). This ignorance is called epistemic uncertainty, and it is associated to the process of propagation). In fact, it is propagated to the probability of fulfilling the RAC. Another term used on the Thesis for this epistemic uncertainty is metauncertainty. The RAC must include the two types of uncertainty: one for the calculation of the magnitude (aleatory uncertainty); the other one, for the calculation of the probability (epistemic uncertainty). The two uncertainties can be taken into account in a separate fashion, or can be combined. In any case the RAC becomes a probabilistic criterion. If uncertainties are separated, a second-order probability is used; of both are combined, a single probability is used. On the first case, the regulator must define a level of fulfillment for the epistemic uncertainty, termed regulatory confidence level, as a value close to 1. The pair of regulatory levels (probability and confidence) is termed the regulatory tolerance level. The Thesis concludes that the adequate way of setting the BEPU RAC is by separating the uncertainties. There are two reasons to do so: experts recommend the separation of aleatory and epistemic uncertainty; and the separated RAC is in general more conservative than the joint RAC. The BEPU RAC is a hypothesis on a probability distribution, and must be statistically tested. The Thesis classifies the statistical methods to verify the RAC fulfillment in 3 categories: methods based on tolerance regions, in quantile estimators and on probability (of success or failure) estimators. The former two have been termed Q-methods, whereas those in the third category are termed P-methods. The purpose of our categorization is not to make an exhaustive survey of the very numerous existing methods. Rather, the goal is to relate the three categories and examine the most used methods from a regulatory standpoint. Special mention deserves the most used method, due to Wilks, and its extension to multidimensional variables (due to Wald). The counterpart P-method of Wilks’ is Clopper-Pearson interval, typically ignored in the BEPU realm. The problem of the computational cost of an uncertainty analysis is tackled. Wilks’, Wald’s and Clopper-Pearson methods require a minimum sample size, which is a growing function of the tolerance level. The sample size is an indicator of the computational cost, because each element of the sample must be calculated with the predictive models (codes). When the RAC is a multiple criteria, the safety magnitude becomes multidimensional. When all its components are output of the same calculation, the multidimensional character does not introduce additional computational cost. In this way, an extended idea in the BEPU realm, stating that the multi-D problem can only be tackled with the Wald extension, is proven to be false. When the components of the magnitude are independently calculated, the influence of the problem dimension on the cost cannot be avoided. The former BEPU methodologies performed the uncertainty propagation through a surrogate model of the code, also termed emulator or metamodel. The goal of a metamodel is not the predictive capability, clearly worse to the original code, but the capacity to propagate uncertainties with a lower computational cost. The emulator must contain the input parameters contributing the most to the output uncertainty, and this requires a previous importance analysis. The surrogate model is practically inexpensive to run, so that it can be exhaustively analyzed through Monte Carlo. Therefore, the epistemic uncertainty due to sampling will be reduced to almost zero, and the BEPU RAC for metamodels includes a simple probability. The regulatory authority will tend to accept the use of statistical methods which need a minimum of assumptions: exact, nonparametric and frequentist methods rather than approximate, parametric and bayesian methods, respectively. The BEPU RAC is based on a second-order probability. The probability of the safety magnitudes being inside the acceptance region is a success probability and can be interpreted as a fulfillment degree if the RAC. Furthermore, it has a metric interpretation, as a distance (in the range of magnitudes) from calculated values of the magnitudes to acceptance regulatory limits. A probabilistic definition of safety margin (SM) is proposed in the thesis. The same from a value A to other value B of a safety magnitude is defined as the probability that A is less severe than B, obtained from the uncertainties if A and B. The probabilistic definition of SM has several advantages: it is nondimensional, ranges in the interval (0,1) and can be easily generalized to multiple dimensions. Furthermore, probabilistic SM are combined according to the probability laws. And a basic property: probabilistic SM are not symmetric. There are several types of SM: distance from a calculated value to a regulatory limit (licensing margin); or from the real value to the calculated value of a magnitude (analytical margin); or from the regulatory limit to the damage threshold (barrier margin). These representations of distances (in the magnitudes’ range) as probabilities can be applied to the quantification of conservativeness. Analytical margins can be interpreted as the degree of conservativeness (DG) of the computational methodology. Conservativeness indicators are established in the Thesis, useful in the comparison of different methods of constructing tolerance limits and regions. There is a topic which has not been rigorously tackled to the date: the validation of BEPU methodologies. Before being applied in licensing, methodologies must be validated, on the basis of comparisons of their predictions ad real values of the safety magnitudes. Real data are obtained, basically, in experimental facilities. The ultimate goal of establishing RAC is to verify that real values (aside from calculated values) fulfill them. In the Thesis it is proved that a sufficient condition for this goal is the conjunction of 2 criteria: the BEPU RAC and an analogous criterion for validation. And this las criterion must be proved in experimental scenarios and extrapolated to NPPs. The licensing RAC requires a minimum value (P0) of the probabilistic licensing margin; the validation criterion requires a minimum value of the analytical margin (i.e., of the DG). These minimum values are basically complementary; the higher one of them, the lower the other one. The regulatory practice sets a high value on the licensing margin, so that the required DG is low. The possible adoption of lower values for P0 would imply weaker exigence on the RCA fulfillment and, on the other hand, higher exigence on the conservativeness of the methodology. It is important to highlight that a higher minimum value of the licensing or analytical margin requires a higher computational cost. Therefore, the computational efforts are also complementary. If medium levels are adopted, the required DG is also medium, and the methodology does not need to be very conservative. The total computational effort (licensing plus validation) could be optimized.

On sonic anemometer measurement theory

In this paper a model for the measuring process of sonic anemometers (ultrasound pulse based) is presented. The differential equations that describe the travel of ultrasound pulses are solved in the general case of non-steady, non-uniform atmospheric flow field. The concepts of instantaneous line-average and travelling pulse-referenced average are established and employed to explain and calculate the differences between the measured turbulent speed (travelling pulse-referenced average) and the line-averaged one. The limit k1l=1 established by Kaimal in 1968, as the maximum value which permits the neglect of the influence of the sonic measuring process on the measurement of turbulent components is reviewed here. Three particular measurement cases are analysed: A non-steady, uniform flow speed field, a steady, non-uniform flow speed field and finally an atmospheric flow speed field. In the first case, for a harmonic time-dependent flow field, Mach number, M (flow speed to sound speed ratio) and time delay between pulses have revealed themselves to be important parameters in the behaviour of sonic anemometers, within the range of operation. The second case demonstrates how the spatial non-uniformity of the flow speed field leads to an influence of the finite transit time of the pulses (M≠0) even in the absence of non-steady behaviour of the wind speed. In the last case, a model of the influence of the sonic anemometer processes on the measurement of wind speed spectral characteristics is presented. The new solution is compared to the line-averaging models existing in the literature. Mach number and time delay significantly distort the measurement in the normal operational range. Classical line averaging solutions are recovered when Mach number and time delay between pulses go to zero in the new proposed model. The results obtained from the mathematical model have been applied to the calculation of errors in different configurations of practical interest, such as an anemometer located on a meteorological mast and the transfer function of a sensor in an atmospheric wind. The expressions obtained can be also applied to determine the quality requirements of the flow in a wind tunnel used for ultrasonic anemometer calibrations.

La memoria en el proceso creativo de Juan Muñoz = Memory in the creative process of Juan Muñoz

Esta tesis integra un estudio reflexivo sobre la relación de dependencia entre la creación y la memoria a través del análisis de la última obra del escultor Juan Muñoz: Double Bind (Tate Modern, Londres, 2001). Desde esta posición es obligado replantear el análisis de la obra, lo que hace necesario su estudio cubriendo el mayor espectro posible de información accesible más allá de la obra en sí, para aproximarse a la convergencia entre memoria y creación. La perspectiva de análisis propuesta abre camino a nuevas consideraciones so¬bre la relevancia del conocimiento en el desarrollo del proceso creativo. Este análisis no debe tan sólo suponer una aportación al conocimiento del trabajo de Juan Muñoz. Debe también desprenderse de él la innegable participación y necesaria lectura del pasado en el presente. La amnesia de los tiempos pasados impide completar el atlas de imágenes en las que se apoya la creación impidiendo el conocimiento del origen de las fuentes de inspi¬ración y las bases de la creación de una determinada obra. Este hecho limita y distorsiona sus posibles interpretaciones. Pretendo un acercamiento al entendimiento de la forma de mirar y de crear a través del tiempo que es memoria. La memoria tiene un cometido de crucial importancia para la actividad mental y juega un papel fundamental en la conducta y en la creación. La obra es el resultado de la búsqueda de una idea que exprese algo que el creador no puede ex¬presar de otra manera. Es la necesidad de expresar las ideas mediante un lenguaje que se desarrolla en el tiempo y en el espacio, reflejo del ser que responde al pensamiento. Es una forma de experiencia donde subyacen las sendas del pasado y donde se plantea el futuro. Sólo el creador accede a la obra desde dentro, el observador llega a ella desde el exterior y mediante su propia subjetividad. Las obras son formas de experiencia de sus autores, comunicar el mensaje de dicha experiencia supone por tanto interpretar. Persiguiendo la necesidad de saber y entender, pretender explicar el sentido de una cosa implica una apreciación intencionada asociada al entendimiento del intérprete. Las obras son produc¬tos que portan un mensaje y que contienen en su estructura las trazas del tiempo vivido por su creador. Si se quiere adquirir un acercamiento que represente la posición de un autor, será necesario no solo mirar a través de ella, si no introducirse en el contexto de su historia. Mirar hacia atrás, hacia la profundidad del presente para tener conciencia del pensamiento presente y futuro. Recorrer de este modo la instalación Double Bind de Juan Muñoz proporciona una síntesis de sus preocupaciones e intereses a la vez que aporta un conocimiento no necesariamente inmediato, pero relevante y trascendente de la obra, su creador y la historia. ABSTRACT This thesis comprises a reflective study of the dependence relationship between creation and memory through the analysis of the latest work by the sculptor Juan Muñoz: Double Bind (Tate Modern, London, 2001). From this position, it is mandatory to rethink the analysis of the work, making it necessary to cover the widest possible range of information available beyond the work itself, in order to obtain a closer view of the convergence between memory and creation. The proposed analytical approach opens up new considerations on the relevance of knowledge during the development of the creative process. This analysis should not only make a contribution to the knowledge of the work of Juan Muñoz. It should also infer the undeniable involvement and the necessary reading of the past in the present. Amnesia regarding past makes it impossible to complete the atlas of images on which the creation is based, blocking knowledge of the origin of the sources of inspiration and the basis for the creation of a specific work. This fact limits and distorts its possible interpretations. My intention is an approach to how to understand memory as the way of looking and creating over time. Memory has a crucial role to mental activity and plays a key role in behaviour and creation. The work is the result of finding an idea that expresses something that the creator can not express otherwise. It is the need to express ideas by means of a language that develops throughout time and space, a reflection of the being that responds to the thought. It is a way of experience underlying the paths of the past and where the future is set out. Only the creator can access the work from the inside. The observer sees it from the outside and in accordance with his/her own subjectivity. The works form a part of the experience of their authors, thus implying the interpretation of the message of their experience being passed on. The pursuit of knowledge and understanding, and trying to explain the meaning of something implies a deliberate appreciation associated with the understanding of the interpreter. The works are products bearing a message and containing in their structure traces of the time lived by their creator. If one wants to come close to what the author’s posture represents, it will not only be necessary to penetrate it, but also to introduce oneself into the context of its history. Take a look back, towards the depth of the present in order to become aware of present and future thinking. To go across the installation of Double Bind by Juan Muñoz in this way offers a synthesis of his concerns and interests while also providing a not necessarily immediate knowledge, but one which is relevant and important to the work, its creator and history.

Energy efficiency evaluation of zero energy houses

Given the global energy and environmental situation, the European Union has been issuing directives with increasingly demanding requirements in term of the energy efficiency in buildings. The international competition of sustainable houses, Solar Decathlon Europe (SDE), is aligned with these European objectives. SDE houses are low energy solar buildings that must reach the near to zero energy houses’ goal. In the 2012 edition, in order to emphasize its significance, the Energy Efficiency Contest was added. SDE houses’ interior comfort, functioning and energy performance is monitored. The monitoring data can give an idea about the efficiency of the houses. However, a jury comprised by international experts is responsible for carrying out the houses energy efficiency evaluation. Passive strategies and houses services are analyzed. Additionally, the jury's assessment has been compared with the behavior of the houses during the monitoring period. Comparative studies make emphasis on the energy aspects, houses functioning and their interior comfort. Conclusions include thoughts related with the evaluation process, the results of the comparative studies and suggestions for the next competitions.

Proceso metodológico para optimizar la toma de decisiones en el proyecto de envolventes arquitectónicas multicapa = Methodological process for the optimization of the decision making in multilayer building envelope projects

La presente tesis doctoral se enmarca dentro del concepto de la sistematización del conocimiento en arquitectura, más concretamente en el campo de las construcciones arquitectónicas y la toma de decisiones en la fase de proyecto de envolventes arquitectónicas multicapa. Por tanto, el objetivo principal es el establecimiento de las bases para una toma de decisiones informadas durante el proyecto de una envolvente multicapa con el fin de colaborar en su optimización. Del mismo modo que la historia de la arquitectura está relacionada con la historia de la innovación en construcción, la construcción está sujeta a cambios como respuesta a los fracasos anteriores. En base a esto, se identifica la toma de decisiones en la fase de proyecto como el estadio inicial para establecer un punto estratégico de reflexión y de control sobre los procesos constructivos. La presente investigación, conceptualmente, define los parámetros intervinientes en el proyecto de envolventes arquitectónicas multicapa a partir de una clasificación y sistematización de todos los componentes (elementos, unidades y sistemas constructivos) utilizados en las fachadas multicapa. Dicha sistematización se materializa en una hoja matriz de datos en la que, dentro de una organización a modo de árbol, se puede acceder a la consulta de cada componente y de su caracterización. Dicha matriz permite la incorporación futura de cualquier componente o sistema nuevo que aparezca en el mercado, relacionándolo con aquellos con los que comparta ubicación, tipo de material, etc. Con base en esa matriz de datos, se diseña la sistematización de la toma de decisiones en la fase de proyecto de una envolvente arquitectónica, en concreto, en el caso de una fachada. Operativamente, el resultado se presenta como una herramienta que permite al arquitecto o proyectista reflexionar y seleccionar el sistema constructivo más adecuado, al enfrentarse con las distintas decisiones o elecciones posibles. La herramienta se basa en las elecciones iniciales tomadas por el proyectista y se estructura, a continuación y sucesivamente, en distintas aproximaciones, criterios, subcriterios y posibilidades que responden a los distintos avances en la definición del sistema constructivo. Se proponen una serie de fichas operativas de comprobación que informan sobre el estadio de decisión y de definición de proyecto alcanzados en cada caso. Asimismo, el sistema permite la conexión con otros sistemas de revisión de proyectos para fomentar la reflexión sobre la normalización de los riesgos asociados tanto al proprio sistema como a su proceso constructivo y comportamiento futuros. La herramienta proporciona un sistema de ayuda para ser utilizado en el proceso de toma de decisiones en la fase de diseño de una fachada multicapa, minimizando la arbitrariedad y ofreciendo una cualificación previa a la cuantificación que supondrá la elaboración del detalle constructivo y de su medición en las sucesivas fases del proyecto. Al mismo tiempo, la sistematización de dicha toma de decisiones en la fase del proyecto puede constituirse como un sistema de comprobación en las diferentes fases del proceso de decisión proyectual y de definición de la envolvente de un edificio. ABSTRACT The central issue of this doctoral Thesis is founded on the framework of the concept of the systematization of knowledge in architecture, in particular, in respect of the field of building construction and the decision making in the design stage of multilayer building envelope projects. Therefore, the main objective is to establish the bases for knowledgeable decision making during a multilayer building envelope design process, in order to collaborate with its optimization. Just as the history of architecture is connected to the history of innovation in construction, construction itself is subject to changes as a response to previous failures. On this basis, the decisions made during the project design phase are identified as the initial state to establish an strategic point for reflection and control, referred to the constructive processes. Conceptually, this research defines the parameters involving the multilayer building envelope projects, on the basis of a classification and systematization for all the components (elements, constructive units and constructive systems) used in multilayer façades. The mentioned systematization is materialized into a data matrix sheet in which, following a tree‐like organization, the access to every single component and its characterization is possible. The above data matrix allows the future inclusion of any new component or system that may appear in the construction market. That new component or system can be put into a relationship with another, which it shares location, type of material,… with. Based on the data matrix, the systematization of the decision making process for a building envelope design stage is designed, more particularly in the case of a façade. Putting this into practice, it is represented as a tool which allows the architect or the designer, to reflect and to select the appropriate building system when facing the different elections or the different options. The tool is based on the initial elections taken by the designer. Then and successively, it is shaped on the form of different operative steps, criteria, sub‐criteria and possibilities which respond to a different progress in the definition of the building construction system. In order to inform about the stage of the decision and the definition reached by the project in every particular case, a range of operative sheets are proposed. Additionally, the system allows the connection with other reviewing methods for building projects. The aim of this last possibility is to encourage the reflection on standardization of the associated risks to the building system itself and its future performance. The tool provides a helping system to be used during the decision making process for a multilayer façade design. It minimizes the arbitrariness and offers a qualification previous to the quantification that will be done with the development of the construction details and their bill of quantities, that in subsequent project stages will be executed. At the same time, the systematization of the mentioned decision making during the design phase, can be found as a checking system in the different stages of the decision making design process and in the different stages of the building envelope definition.

Mechanical behaviour and formation process of silkworm silk gut

High performance silk fibers were produced directly from the silk glands of silkworms ("Bombyx mori") following an alternative route to natural spinning. This route is based on a traditional procedure that consists of soaking the silk glands in a vinegar solution and stretching them by hand leading to the so called silkworm guts. Here we present, to the authors’ best knowledge, the first comprehensive study on the formation, properties and microstructure of silkworm gut fibers. Comparison of the tensile properties and microstructural organization of the silkworm guts with those of naturally spun fibers allows gain of a deeper insight into the mechanisms that lead to the formation of the fiber, as well as the relationship between the microstructure and properties of these materials. In this regard, it is proved that an acidic environment and subsequent application of tensile stress in the range of 1000 kPa are sufficient conditions for the formation of a silk fiber.

Two-dimensional IR correlation spectroscopy: Sequential events in the unfolding process of the λ Cro-V55C repressor protein

A question often posed in protein folding/unfolding studies is whether the process is fully cooperative or whether it contains sequential elements. To address this question, one needs tools capable of resolving different events. It seems that, at least in certain cases, two-dimensional (2D) IR correlation spectroscopy can provide answers to this question. To illustrate this point, we have turned to the Cro-V55C dimer of the λ Cro repressor, a protein known to undergo thermal unfolding in two discrete steps through a stable equilibrium intermediate. The secondary structure of this intermediate is compatible with that of a partially unfolded protein and involves a reorganization of the N terminus, whereas the antiparallel β-ribbon formed by the C-terminal part of each subunit remains largely intact. To establish whether the unfolding process involves sequential events, we have performed a 2D correlation analysis of IR spectra recorded over the temperature range of 20–95°C. The 2D IR correlation analysis indeed provides evidence for a sequential formation of the stable intermediate, which is created in three (closely related) steps. A first step entails the unfolding of the short N-terminal β-strand, followed by the unfolding of the α-helices in a second step, and the third step comprises the reorganization of the remaining β-sheet and of some unordered segments in the protein. The complete unfolding of the stable intermediate at higher temperatures also undergoes sequential events that ultimately end with the breaking of the H bonds between the two β-strands at the dimer interface.

Dynamics of fluorescence fluctuations in green fluorescent protein observed by fluorescence correlation spectroscopy

We have investigated the pH dependence of the dynamics of conformational fluctuations of green fluorescent protein mutants EGFP (F64L/S65T) and GFP-S65T in small ensembles of molecules in solution by using fluorescence correlation spectroscopy (FCS). FCS utilizes time-resolved measurements of fluctuations in the molecular fluorescence emission for determination of the intrinsic dynamics and thermodynamics of all processes that affect the fluorescence. Fluorescence excitation of a bulk solution of EGFP decreases to zero at low pH (pKa = 5.8) paralleled by a decrease of the absorption at 488 nm and an increase at 400 nm. Protonation of the hydroxyl group of Tyr-66, which is part of the chromophore, induces these changes. When FCS is used the fluctuations in the protonation state of the chromophore are time resolved. The autocorrelation function of fluorescence emission shows contributions from two chemical relaxation processes as well as diffusional concentration fluctuations. The time constant of the fast, pH-dependent chemical process decreases with pH from 300 μs at pH 7 to 45 μs at pH 5, while the time-average fraction of molecules in a nonfluorescent state increases to 80% in the same range. A second, pH-independent, process with a time constant of 340 μs and an associated fraction of 13% nonfluorescent molecules is observed between pH 8 and 11, possibly representing an internal proton transfer process and associated conformational rearrangements. The FCS data provide direct measures of the dynamics and the equilibrium properties of the protonation processes. Thus FCS is a convenient, intrinsically calibrated method for pH measurements in subfemtoliter volumes with nanomolar concentrations of EGFP.