Use of alternative fuels obtained from renewable sources in brayton cycles

Analysis and simulation of the behaviour of gas turbines for power generation using different nonconventional fuels obtained from different renewable sources are presented. Three biomass-tobiofuel processes are considered: anaerobic digestion of biomass (biogas), biomass gasification (synthesis gas) and alcoholic fermentation of biomass and dehydration (bioethanol), each of them with two different biomass substrates (energy crops and municipal solid waste) as input. The gas turbine behaviour in a Brayton cycle is simulated both in an isolated operation and in combined cycle. The differences in gas turbine performance when fired with the considered biofuels compared to natural gas are studied from different points of view related with the current complex energetic context: energetic and exergetic efficiency of the simple/combined cycle and CO2 emissions. Two different tools have been used for the simulations, each one with a different approach: while PATITUG (own software) analyses the behaviour of a generic gas turbine allowing a total variability of parameters, GT-PRO (commercial software) is more rigid, albeit more precise in the prediction of real gas turbine behaviour. Different potentially interesting configurations and its thermodynamic parameters have been simulated in order to obtain the optimal range for all of them and its variation for each fuel.

Analysis of the Behaviour of Biofuel-Fired Gas Turbine Power Plants

The utilisation of biofuels in gas turbines is a promising alternative to fossil fuels for power generation. It would lead to significant reduction of CO2 emissions using an existing combustion technology, although significant changes seem to be needed and further technological development is necessary. The goal of this work is to perform energy and exergy analyses of the behaviour of gas turbines fired with biogas, ethanol and synthesis gas (bio-syngas), compared with natural gas. The global energy transformation process (i.e. from biomass to electricity) has also been studied. Furthermore, the potential reduction of CO2 emissions attained by the use of biofuels has been determined, considering the restrictions regarding biomass availability. Two different simulation tools have been used to accomplish the aims of this work. The results suggest a high interest and the technical viability of the use of Biomass Integrated Gasification Combined Cycle (BIGCC) systems for large scale power generation.

Realidad estratégica de la sostenibilidad de los recursos naturales: La explotación del hierro

Es en el campo de los recursos naturales y su aplicación a la industria, el entorno donde se desarrolla esta Tesis. El objetivo de la misma es demostrar cómo la minería del hierro puede resultar una actividad sostenible, logrando continuar de esta manera la estrecha relación de siempre entre las necesidades del hombre y la pervivencia de los recursos naturales. Es en la minería del hierro donde hace mayor énfasis este trabajo, dando lugar a un nuevo Indicador Sostenible que intenta evaluar las explotaciones de mineral de hierro desde una visión sostenible, empleando el consumo energético y las emisiones de CO2 como principales herramientas. Como se observa en el día a día, el tema de la sostenibilidad es de plena actualidad, lográndose en este trabajo implicar, tanto a la eficiencia energética, como al control de emisiones de gases efecto invernadero; ambas herramientas cobran más importancia cada día que pasa. La Tesis se desarrolla en 5 capítulos, aparte de su bibliografía correspondiente. En el primer capítulo se introduce el sentido de la sostenibilidad, desde sus inicios conceptuales, hasta sus actuales clasificaciones y definiciones empleadas; todo ello desde el punto de vista de los recursos naturales, y más habitualmente desde la minería. Resulta llamativo el contraste de opiniones, en lo que se ha dado a llamar la paradoja de la minería sostenible, quedando tras su lectura, la posición de la minería en una situación, si no ventajosa, si de equilibrio en importancia entre las necesidades a cubrir y el agotamiento de recursos. El segundo capítulo nos muestra el entorno donde se va a conducir la Tesis. El marco que engloba este trabajo se extiende desde la extracción del mineral de hierro (minería), su tratamiento y concentración (mineralurgia), su venta a los hornos altos (mercados) hasta su posterior fabricación en acero terminado (siderurgia). En este capítulo se presentan los principales actores que entrarán en el sector de la minería del hierro (productores y fabricantes) incluyendo una serie de datos estadísticos de gran interés para el desarrollo de la Tesis. El tercer capítulo se refiere al proceso completo que precisa la actividad sobre la que se va a evaluar la sostenibilidad. Es donde se definen, paso a paso, y obteniendo todos los datos de consumos energéticos y emisiones de CO2, las diferentes etapas por las que pasa el mineral de hierro, hasta encontrarse laminado en la acería. Es aquí donde se analizan los diversos tipos de yacimientos de hierro dispersos por el mundo y el mineral extraído, de manera que las propiedades aprendidas se puedan emplear más adelante en un indicador, y que así diferencie la sostenibilidad en función de los orígenes motivo de las necesidades energéticas para su transformación. El capítulo 4 consta de dos bloques: el uso de las herramientas de medida de la sostenibilidad, a día de hoy en el mundo industrial, y de una manera pormenorizada, el consumo energético y sus emisiones medioambientales como herramienta de gestión ambiental para la minería del hierro. Esta herramienta resultará básica para el cálculo del indicador buscado para la medida de la sostenibilidad. El capítulo 5 constituye el núcleo de la tesis, y supone el desarrollo del indicador, la metodología de uso y las conclusiones obtenidas. A través de varios ejemplos se logra entender la aplicación del indicador, dando lugar a una clasificación sostenible sencilla y práctica, situando en orden las diferentes explotaciones en función de un nivel de sostenibilidad determinado. Este último capítulo da origen al Indicador Sostenible Energético buscado, mostrándose en todo su esplendor y descubriendo cómo la relación ponderada entre el consumo energético y sus emisiones de CO2 permite, a través de una valoración, mostrar todos los parámetros de relevancia para el mineral de hierro y su posterior transformación en acero. Esa cifra obtenida por el indicador, clasificará la explotación teniendo en cuenta, el tipo de yacimiento, características del mineral (especie mineralógica, tipo de mineral, ley del mineral en hierro, tipo de ganga, características físicas como dureza o tamaño de grano, susceptibilidad magnética, etc.), situación geográfica, infraestructuras, etc. Sin profundizar en la siderurgia, por lo menos sí incluir los principales parámetros (relacionados siempre desde el mineral) que pudieran tener influencia en la disminución de energía requerida (y sus emisiones de CO2 relacionadas): la reducibilidad, el contenido en hierro, y mencionar la influencia del SiO2. Se completa la Tesis con las referencias bibliográficas y documentales, así como con una bibliografía general. ABSTRACT This Thesis is set in a context of natural resources and applied science. The aim of this document is to prove that iron mining is a sustainable activity, so the ancient relationship between men and natural resources will continue. Iron mining is the main subject of this work, so a new sustainable indicator is created in order to evaluate the iron mining from a sustainable point of view. The main tools applied are energy consumption and CO2 emissions. In this research document two relevant issues are involved: energy efficiency and GHGs control; both tools gain significance by the day. This thesis develops along 5 chapters and its bibliography. The first chapter refers to the concept of sustainability, from the beginning to the current definitions and classifications; all this information is focused from the natural resources point of view, especially mining. The contrast of opinion is remarkable, which has been called the “paradox of sustainable mining”; however this chapter concludes that taking into account the less bright side of the mining its activity maintains an important balance between necessities to cover, available resources and environment. The second chapter sets out where this Thesis has been conducted. The frame of this work lies between iron mining, ore processing, the market and the latter steel fabrication (steelmaking). This chapter shows the iron mining key stakeholders, supported with statistical data. The third chapter refers to the whole process definition. From the iron mineral to the rolled steel, all data related with energy consumption and CO2 emissions are considered step by step. Different iron deposits widespread all over the world are analyzed now, as well as the exploited iron mineral in order to apply the lessons learned to create a new sustainability tool. Then, our sustainability studies will consider the influence of this in the energy necessities when iron is transformed. Chapter four is divided in the currently applied sustainability measurement tools, and focusing on energy consumption and CO2 emissions linked to the iron mining process. This tool is essential to calculate the required indicator that reflects the sustainability. Chapter five is the Thesis’ core: it is where the new sustainable indicator is developed, the methodology stated and the final conclusions obtained. Through several examples the indicator application is explained, and a practical and simple sustainable classification will show the ranking of every exploitation. This last chapter develops the sustainable tool and discovers how the weighted relation between energy consumption and CO2 emissions allows understanding all the relevant parameters in the iron mineral transformation. The number calculated will be used to classify the mineral exploitation, taking into account the deposit typology, mineral characteristics (mineralogy, type of mineral, iron percentage, physical properties as hardness or grain size, magnetic susceptibility, etc.), geographic situation, infrastructures, etc. Although steelmaking is not studied in depth, main parameters (from the mineral side) which can operate in the energy decrease (and CO2 emissions in parallel) are referred to: reducibility, iron content and SiO2 influence. The bibliography used is included at the end of this paper.

Estudio técnico y económico para la sustitución del gasóleo por biomasa térmica en edificios urbanos

La finalidad del proyecto consiste en realizar la sustitución de calderas de gasóleo por calderas de biomasa para suministrar calefacción a edificios urbanos. En primer lugar, se ha hecho un estudio de la demanda calorífica de los edificios, y posteriormente se ha estudiado el ciclo completo de la biomasa, incluyendo el suministro y tipo de biomasa, dimensiones de los equipos y espacios necesarios para la instalación. Después de estudiar la viabilidad técnica y económica, podemos concluir que utilizar biomasa en edificios con calderas centralizadas nos aporta un gran ahorro en comparación con el gasóleo, además de evitar emisiones de CO2 y utilizar un combustible renovable y de producción nacional. ABSTRACT The purpose of the project consists of performing the substitution of diesel boilers by biomass boilers to provide the heating to urban buildings. In first place, it has been made a study of the calorific demand of the buildings. In addition, it has been studied the completed cycle of the biomass even including the supply and the type of biomass, the dimensions of the machines and the necessary spaces to carry out the installation. After studying the technical and economical viability, we can conclude that using biomass in buildings with central boilers provides us an important saving in comparison with diesel as well as to avoid CO2 emissions and using a renewable combustible of national production.

Energy- and environmentally efficient road management: The case of the Spanish motorway network

Transport is responsible for 41% of CO2 emissions in Spain, and around 65% of that figure is due to road traffic. Tolled motorways are currently managed according to economic criteria: minimizing operational costs and maximizing revenues from tolls. Within this framework, this paper develops a new methodology for managing motorways based on a target of maximum energy efficiency. It includes technological and demand-driven policies, which are applied to two case studies. Various conclusions emerge from this study. One is, that the use of intelligent payment systems is recommended; and another, is that the most sustainable policy would involve defining the most efficient strategy for each motorway section, including the maximum use of its capacity, the toll level which attracts the most vehicles, and the optimum speed limit for each type of vehicle.

Use of alternative fuels obtained from renowable sources in Brayton cycles

Analysis and simulation of the behaviour of gas turbines for power generation using different nonconventional fuels obtained from different renewable sources are presented. Three biomass-tobiofuel processes are considered: anaerobic digestion of biomass (biogas), biomass gasification (synthesis gas) and alcoholic fermentation of biomass and dehydration (bioethanol), each of them with two different biomass substrates (energy crops and municipal solid waste) as input. The gas turbine behaviour in a Brayton cycle is simulated both in an isolated operation and in combined cycle. The differences in gas turbine performance when fired with the considered biofuels compared to natural gas are studied from different points of view related with the current complex energetic context: energetic and exergetic efficiency of the simple/combined cycle and CO2 emissions. Two different tools have been used for the simulations, each one with a different approach: while PATITUG (own software) analyses the behaviour of a generic gas turbine allowing a total variability of parameters, GT-PRO (commercial software) is more rigid, albeit more precise in the prediction of real gas turbine behaviour. Different potentially interesting configurations and its thermodynamic parameters have been simulated in order to obtain the optimal range for all of them and its variation for each fuel.

Development of mathematical models to elaborate strategies, select alternatives and development of plans for adaptation of communities to climate change in different geographical areas including costs to implement it.

There is evidence that the climate changes and that now, the change is influenced and accelerated by the CO2 augmentation in atmosphere due to combustion by humans. Such ?Climate change? is on the policy agenda at the global level, with the aim of understanding and reducing its causes and to mitigate its consequences. In most countries and international organisms UNO (e.g. Rio de Janeiro 1992), OECD, EC, etc . . . the efforts and debates have been directed to know the possible causes, to predict the future evolution of some variable conditioners, and trying to make studies to fight against the effects or to delay the negative evolution of such. The Protocol of Kyoto 1997 set international efforts about CO2 emissions, but it was partial and not followed e.g. by USA and China . . . , and in Durban 2011 the ineffectiveness of humanity on such global real challenges was set as evident. Among all that, the elaboration of a global model was not boarded that can help to choose the best alternative between the feasible ones, to elaborate the strategies and to evaluate the costs, and the authors propose to enter in that frame for study. As in all natural, technological and social changes, the best-prepared countries will have the best bear and the more rapid recover. In all the geographic areas the alternative will not be the same one, but the model must help us to make the appropriated decision. It is essential to know those areas that are more sensitive to the negative effects of climate change, the parameters to take into account for its evaluation, and comprehensive plans to deal with it. The objective of this paper is to elaborate a mathematical model support of decisions, which will allow to develop and to evaluate alternatives of adaptation to the climatic change of different communities in Europe and Latin-America, mainly in especially vulnerable areas to the climatic change, considering in them all the intervening factors. The models will consider criteria of physical type (meteorological, edaphic, water resources), of use of the ground (agriculturist, forest, mining, industrial, urban, tourist, cattle dealer), economic (income, costs, benefits, infrastructures), social (population), politician (implementation, legislation), educative (Educational programs, diffusion) and environmental, at the present moment and the future. The intention is to obtain tools for aiding to get a realistic position for these challenges, which are an important part of the future problems of humanity in next decades.

Management of Urban Mobility to Control Climate Change in Cities

The need of decarbonization of urban mobility is one of the main priorities for all countries to achieve greenhouse gas (GHG) emissions reduction targets. In general, the transport modes which have experienced the most growth in recent years tend to be the most polluting. Most efforts have been focused on the vehicle efficiency improvements and vehicle fleet renewal; nevertheless more emphasis should be placed on strategies related to the management of urban mobility and modal share. Research of individual travel which analyzes CO2 emissions and car and public transport share in daily mobility will enable better assessments of the potential of urban mobility measures introduced to limit GHG emissions produced by transport in cities. This paper explores the sustainability impacts of daily mobility in Spain using data from two National Travel Surveys (NTSs) (2000 and 2006) and includes a method by which to estimate the CO2 emissions associated with each journey and each surveyed individual. The results demonstrate that in the 2000 to 2006 period, there has been an increase in daily mobility which has led to a 17% increase in CO2 emissions. When separated by transport mode, cars prove to be the main contributor to that increase, followed by public transport. More focus should be directed toward modal shift strategies which not only take the number of journeys into account but also consider distance. The contributions of this paper have potential applications in the assessment of current and future urban transport policies.

Decarbonization of toll plazas: impact assessment of toll collection system management

Transport climate change impacts have become a worldwide concern. The use of Intelligent Transport Systems (ITS) could contribute to a more effective use of resources in toll road networks. Management of toll plazas is central to the reduction of greenhouse gas (GHG) emissions, as it is there that bottlenecks and congestion occur. This study focuses on management strategies aimed at reducing climate change impacts of toll plazas by managing toll collection systems. These strategies are based on the use of different collection system technologies – Electronic Toll Collection (ETC) and Open Road Tolling (ORT) – and on queue management. The carbon footprint of various toll plazas is determined by a proposed integrated methodology which estimates the carbon dioxide (CO2) emissions of the different operational stages at toll plazas (deceleration, service time, acceleration, and queuing) for the different toll collection systems. To validate the methodology, two main-line toll plazas of a Spanish toll highway were evaluated. The findings reveal that the application of new technologies to toll collection systems is an effective management strategy from an environmental point of view. The case studies revealed that ORT systems lead to savings of up to 70% of CO2 emissions at toll plazas, while ETC systems save 20% comparing to the manual ones. Furthermore, queue management can offer a 16% emissions savings when queue time is reduced by 116 seconds. The integrated methodology provides an efficient environmental management tool for toll plazas. The use of new technologies is the future of the decarbonization of toll plazas.

Energy consumption and intensity of toll highway transport in Spain

We estimate the energy consumption of toll highway transport on a number of Spanish roads. Regression parameters are balanced according to coefficients from an empirical analysis based on survey data by vehicle type. The mean energy consumption and subsequent CO2 emissions on the toll highway sections are estimated as 1895 MJ/h/lane-km and 0.15 tCO2 eq./h/lane-km, values that increase to 2644 and 0.22 when energy and carbon emissions of transport infrastructure are considered based on the life cycle energy consumption for toll highway construction and use. If the energy intensity of infrastructure construction is allocated to the users according to traffic, it is much higher for motorcycles than for cars, and is significantly lower for articulated trucks than for vans.

Management of urban mobility to control climate change in cities in Spain

The need to decarbonize urban mobility is one of the main motivations for all countries to achieve reduction targets for greenhouse gas (GHG) emissions. In general, the transport modes that have experienced the most growth in recent years tend to be the most polluting. Most efforts have focused on improvements in vehicle efficiency and on the renewal of vehicle fleets; more emphasis should be placed on strategies related to the management of urban mobility and modal share. Research of individual travel that analyzes carbon dioxide (CO2) emissions and car and public transport share in daily mobility will enable better assessments of the potential of urban mobility measures introduced to limit GHG emissions produced by transport in cities. The climate change impacts of daily mobility in Spain are explored with data from two national travel surveys in 2000 and 2006, and a method for estimating the CO2 emissions associated with each journey and each surveyed individual is provided. The results demonstrate that from 2000 to 2006, daily mobility has increased and has led to a 17% increase in CO2 emissions. When these results are separated by transport mode, cars prove to be the main contributor to that increase, followed by public transport. More focus should be directed toward modal shift strategies, which take into account not only the number of journeys but also the distance traveled. These contributions have potential applications in the assessment of current and future urban transport policies related to low-carbon urban transportation.

Carbon dioxide adsorption in chemically activated carbon from sewage sludge

In this work, sewage sludge was used as precursor in the production of activated carbon by means of chemical activation with KOH and NaOH. The sludge-based activated carbons were investigated for their gaseous adsorption characteristics using CO2 as adsorbate. Although both chemicals were effective in the development of the adsorption capacity, the best results were obtained with solid NaOH (SBAT16). Adsorption results were modeled according to the Langmuir and Freundlich models, with resulting CO2 adsorption capacities about 56 mg/g. The SBAT16 was characterized for its surface and pore characteristics using continuous volumetric nitrogen gas adsorption and mercury porosimetry. The results informed about the mesoporous character of the SBAT16 (average pore diameter of 56.5 Å). The Brunauer-Emmett-Teller (BET) surface area of the SBAT16 was low (179 m2/g) in comparison with a commercial activated carbon (Airpel 10; 1020 m2/g) and was mainly composed of mesopores and macropores. On the other hand, the SBAT16 adsorption capacity was higher than that of Airpel 10, which can be explained by the formation of basic surface sites in the SBAT16 where CO2 experienced chemisorption. According to these results, it can be concluded that the use of sewage-sludge-based activated carbons is a promising option for the capture of CO2. Implications: Adsorption methods are one of the current ways to reduce CO2 emissions. Taking this into account, sewage-sludge-based activated carbons were produced to study their CO2 adsorption capacity. Specifically, chemical activation with KOH and NaOH of previously pyrolyzed sewage sludge was carried out. The results obtained show that even with a low BET surface area, the adsorption capacity of these materials was comparable to that of a commercial activated carbon. As a consequence, the use of sewage-sludge-based activated carbons is a promising option for the capture of CO2 and an interesting application for this waste.

Estudio microestructural y de los procesos de hidratación de cementos con adiciones

En los últimos años, las sociedades industrializadas han tomado una mayor conciencia sobre el problema que suponen las emisiones indiscriminadas de gases de efecto invernadero a la atmósfera. El hormigón, cuyo principal componente es el cemento, es probablemente el material más utilizado en construcción. En la actualidad, las emisiones globales de CO2 debidas a la combustión del CaCO3 del cemento Pórtland representan entre el 5% y el 10% respecto del total. Estos valores son de gran interés si se considera que el compromiso aceptado al firmar el Protocolo de Kioto es de una reducción del 5% antes del año 2020, sobre el total de gases producidos. El principal objetivo del presente trabajo es el estudio microestructural y de los procesos de hidratación de los cementos con adiciones. Para ello se propone contribuir a la investigación sobre nuevos productos cementicios basados en micropartículas esféricas vítreas que pueden adicionarse al cemento antes del proceso de amasado. Los resultados obtenidos se han contrastado con las adiciones convencionales de más uso en la actualidad. El nuevo material basa su composición en la química del aluminio y el silicio. Al disminuir la cantidad de CaCO3, se contribuye al desarrollo sostenible y a la reducción de emisiones de CO2. La patente creada por el Grupo Cementos Pórtland Valderrivas (GCPV), describe el proceso de producción de las cemesferas (WO 2009/007470, 2010). Los productos que forman la materia prima para la elaboración de las cemesferas son arcillas, calizas, margas o productos o subproductos industriales, que tras su molienda, son fundidos mediante un fluido gaseoso a elevada temperatura (entre 1250ºC y 1600ºC). Este proceso permite obtener un producto final en forma esférica maciza o microesfera, que tras estabilizarse mediante un enfriamiento rápido, consigue una alta vitrificación idónea para su reactividad química, con una mínima superficie específica en relación a su masa. El producto final obtenido presenta prácticamente la finura requerida y no precisa ser molido, lo que reduce las emisiones de CO2 por el ahorro de combustible durante el proceso de molienda. El proceso descrito permite obtener un amplio abanico de materiales cementantes que, no solo pueden dar respuesta a los problemas generados por las emisiones de CO2, sino también a la disponibilidad de materiales en países donde hasta el momento no se puede fabricar cemento debido a la falta de calizas. Complementariamente se ha optimizado el método de cálculo del grado de hidratación a partir de los resultados del ensayo de ATD-TG en base a los modelos de cálculo de Bhatty y Pane. El método propuesto permite interpretar el comportamiento futuro del material a partir de la interpolación numérica de la cantidad de agua químicamente enlazada. La evolución del grado de hidratación tiene una relación directa con el desarrollo de la resistencia mecánica del material. Con el fin de caracterizar los materiales de base cemento, se ha llevado a cabo una amplia campaña experimental en pasta de cemento, mortero y hormigón. La investigación abarca tres niveles: caracterización microestructural, macroestructural y caracterización del comportamiento a largo plazo, fundamentalmente durabilidad. En total se han evaluado ocho adiciones diferentes: cuatro adiciones convencionales y cuatro tipos de cemesferas con diferente composición química. Los ensayos a escala microscópica comprenden la caracterización química, granulométrica y de la superficie específica BET de los materiales anhidros, análisis térmico diferencial y termogravimétrico en pasta de cemento y mortero, resonancia magnética de silicio en pasta de cemento, difracción de rayos X de los materiales anhidros y de las probetas de pasta, microscopía electrónica de barrido con analizador de energía dispersiva por rayos X en pasta y mortero, y porosimetría por intrusión de mercurio en mortero. La caracterización macroscópica del material comprende ensayos de determinación del agua de consistencia normal y de los tiempos de inicio y fin de fraguado en pasta de cemento, ensayos de resistencia mecánica a flexión y compresión en probetas prismáticas de mortero, y ensayos de resistencia a compresión en probetas de hormigón. Para caracterizar la durabilidad se han desarrollado ensayos de determinación del coeficiente de migración de cloruros y ensayos de resistividad eléctrica en probetas de mortero. Todos los ensayos enumerados permiten clarificar el comportamiento de las cemesferas y compararlo con las distintas adiciones de uso convencional. Los resultados reflejan un buen comportamiento resistente y durable de los materiales con adición de cemesferas. La caracterización microscópica refleja su relación con las propiedades mesoscópicas y permite comprender mejor la evolución en los procesos de hidratación de las cemesferas. In recent years industrialised societies have become increasingly aware of the problem posed by indiscriminate emission of greenhouse gases into the atmosphere. Concrete, with a main component being cement, is arguably the most widely used construction material. At present, global emissions of CO2 due to the combustion of CaCO3 from Portland cement represent between 5% and 10% of the total. If the requirement of the Kyoto Protocol of a reduction of 5% of the total gas produced before 2020 is considered, then such values are of significant interest. The main objective of this work is the assessment of the microstructure and the hydration processes of cements with additions. Such an examination proposes research into new cementitious products based on vitreous spherical microparticles that may be added to the cement before the mixing process. The results are compared with the most commonly used conventional additions. The new material bases its composition on the chemistry of aluminium and silicates. By decreasing the amount of CaCO3, it is possible both to contribute to sustainable development and reduce CO2 emissions. The patent created by Grupo Cementos Portland Valderrivas (GCPV) describes the production process of microspheres (WO 2009/007470, 2010). The products that form the raw material for manufacture are clays, lime-stone, marl and industrial products or by-products that melt after being ground and fed into a gaseous fluid at high temperatures (1250°C and 1600°C). This process allows the obtaining of a product with a solid-spherical or micro-spherical shape and which, after being stabilised in a solid state by rapid cooling, obtains a high vitrification suitable for chemical reactivity, having a minimal surface in relation to its mass. Given that the final product has the fineness required, it prevents grinding that reduces CO2 emissions by saving fuel during this process. The process, which allows a wide range of cementitious materials to be obtained, not only addresses the problems caused by CO2 emissions but also enhances the availability of materials in countries that until the time of writing have not produced cement due to a lack of limestone. In addition, the calculation of the degree of hydration from the test results of DTA-TG is optimised and based on Bhatty and Pane calculation models. The proposed method allows prediction of the performance of the material from numerical interpolation of the amount of chemically bound water. The degree of hydration has a direct relationship with the development of material mechanical strength. In order to characterise the cement-based materials, an extensive experimental campaign in cement paste, concrete and mortar is conducted. The research comprises three levels: micro-structural characterisation, macro-structural and long-term behaviour (mainly durability). In total, eight additions are assessed: four conventional additions and four types of microspheres with different chemical compositions. The micro-scale tests include characterisation of chemical composition, particle size distribution and the BET specific surface area of anhydrous material, differential thermal and thermogravimetric analysis in cement paste and mortar, silicon-29 nuclear magnetic resonance in cement paste, X-ray diffraction of the anhydrous materials and paste specimens, scanning of electron microscopy with energy dispersive X-ray analyser in cement paste and mortar, and mercury intrusion porosimetry in mortar. The macroscopic material characterisation entails determination of water demand for normal consistency, and initial and final setting times of cement paste, flexural and compressive mechanical strength tests in prismatic mortar specimens, and compressive strength tests in concrete specimens. Tests for determining the chloride migration coefficient are performed to characterise durability, together with electrical resistivity tests in mortar specimens. All the tests listed allow clarification of the behaviour of the microspheres and comparison with the various additions of conventional use. The results show good resistance and durable behaviour of materials with a microsphere addition. Microscopic characterisation reflects their relationship with mesoscopic properties and provides insights into the hydration processes of the microspheres.

Continuum models of the mechanical behavior of rolled and die-cast magnesium alloys

En los últimos años ha habido una fuerte tendencia a disminuir las emisiones de CO2 y su negativo impacto medioambiental. En la industria del transporte, reducir el peso de los vehículos aparece como la mejor opción para alcanzar este objetivo. Las aleaciones de Mg constituyen un material con gran potencial para el ahorro de peso. Durante la última década se han realizado muchos esfuerzos encaminados a entender los mecanismos de deformación que gobiernan la plasticidad de estos materiales y así, las aleaciones de Mg de colada inyectadas a alta presión y forjadas son todavía objeto de intensas campañas de investigación. Es ahora necesario desarrollar modelos que contemplen la complejidad inherente de los procesos de deformación de éstos. Esta tesis doctoral constituye un intento de entender mejor la relación entre la microestructura y el comportamiento mecánico de aleaciones de Mg, y dará como resultado modelos de policristales capaces de predecir propiedades macro- y microscópicas. La deformación plástica de las aleaciones de Mg está gobernada por una combinación de mecanismos de deformación característicos de la estructura cristalina hexagonal, que incluye el deslizamiento cristalográfico en planos basales, prismáticos y piramidales, así como el maclado. Las aleaciones de Mg de forja presentan texturas fuertes y por tanto los mecanismos de deformación activos dependen de la orientación de la carga aplicada. En este trabajo se ha desarrollado un modelo de plasticidad cristalina por elementos finitos con el objetivo de entender el comportamiento macro- y micromecánico de la aleación de Mg laminada AZ31 (Mg-3wt.%Al-1wt.%Zn). Este modelo, que incorpora el maclado y tiene en cuenta el endurecimiento por deformación debido a las interacciones dislocación-dislocación, dislocación-macla y macla-macla, predice exitosamente las actividades de los distintos mecanismos de deformación y la evolución de la textura con la deformación. Además, se ha llevado a cabo un estudio que combina difracción de electrones retrodispersados en tres dimensiones y modelización para investigar el efecto de los límites de grano en la propagación del maclado en el mismo material. Ambos, experimentos y simulaciones, confirman que el ángulo de desorientación tiene una influencia decisiva en la propagación del maclado. Se ha observado que los efectos no-Schmid, esto es, eventos de deformación plástica que no cumplen la ley de Schmid con respecto a la carga aplicada, no tienen lugar en la vecindad de los límites de baja desorientación y se hacen más frecuentes a medida que la desorientación aumenta. Esta investigación también prueba que la morfología de las maclas está altamente influenciada por su factor de Schmid. Es conocido que los procesos de colada suelen dar lugar a la formación de microestructuras con una microporosidad elevada, lo cuál afecta negativamente a sus propiedades mecánicas. La aplicación de presión hidrostática después de la colada puede reducir la porosidad y mejorar las propiedades aunque es poco conocido su efecto en el tamaño y morfología de los poros. En este trabajo se ha utilizado un enfoque mixto experimentalcomputacional, basado en tomografía de rayos X, análisis de imagen y análisis por elementos finitos, para la determinación de la distribución tridimensional (3D) de la porosidad y de la evolución de ésta con la presión hidrostática en la aleación de Mg AZ91 (Mg- 9wt.%Al-1wt.%Zn) colada por inyección a alta presión. La distribución real de los poros en 3D obtenida por tomografía se utilizó como input para las simulaciones por elementos finitos. Los resultados revelan que la aplicación de presión tiene una influencia significativa tanto en el cambio de volumen como en el cambio de forma de los poros que han sido cuantificados con precisión. Se ha observado que la reducción del tamaño de éstos está íntimamente ligada con su volumen inicial. En conclusión, el modelo de plasticidad cristalina propuesto en este trabajo describe con éxito los mecanismos intrínsecos de la deformación de las aleaciones de Mg a escalas meso- y microscópica. Más especificamente, es capaz de capturar las activadades del deslizamiento cristalográfico y maclado, sus interacciones, así como los efectos en la porosidad derivados de los procesos de colada. ---ABSTRACT--- The last few years have seen a growing effort to reduce CO2 emissions and their negative environmental impact. In the transport industry more specifically, vehicle weight reduction appears as the most straightforward option to achieve this objective. To this end, Mg alloys constitute a significant weight saving material alternative. Many efforts have been devoted over the last decade to understand the main mechanisms governing the plasticity of these materials and, despite being already widely used, high pressure die-casting and wrought Mg alloys are still the subject of intense research campaigns. Developing models that can contemplate the complexity inherent to the deformation of Mg alloys is now timely. This PhD thesis constitutes an attempt to better understand the relationship between the microstructure and the mechanical behavior of Mg alloys, as it will result in the design of polycrystalline models that successfully predict macro- and microscopic properties. Plastic deformation of Mg alloys is driven by a combination of deformation mechanisms specific to their hexagonal crystal structure, namely, basal, prismatic and pyramidal dislocation slip as well as twinning. Wrought Mg alloys present strong textures and thus specific deformation mechanisms are preferentially activated depending on the orientation of the applied load. In this work a crystal plasticity finite element model has been developed in order to understand the macro- and micromechanical behavior of a rolled Mg AZ31 alloy (Mg-3wt.%Al-1wt.%Zn). The model includes twinning and accounts for slip-slip, slip-twin and twin-twin hardening interactions. Upon calibration and validation against experiments, the model successfully predicts the activity of the various deformation mechanisms and the evolution of the texture at different deformation stages. Furthermore, a combined three-dimensional electron backscatter diffraction and modeling approach has been adopted to investigate the effect of grain boundaries on twin propagation in the same material. Both experiments and simulations confirm that the misorientation angle has a critical influence on twin propagation. Non-Schmid effects, i.e. plastic deformation events that do not comply with the Schmid law with respect to the applied stress, are absent in the vicinity of low misorientation boundaries and become more abundant as misorientation angle increases. This research also proves that twin morphology is highly influenced by the Schmid factor. Finally, casting processes usually lead to the formation of significant amounts of gas and shrinkage microporosity, which adversely affect the mechanical properties. The application of hydrostatic pressure after casting can reduce the porosity and improve the properties but little is known about the effects on the casting’s pores size and morphology. In this work, an experimental-computational approach based on X-ray computed tomography, image analysis and finite element analysis is utilized for the determination of the 3D porosity distribution and its evolution with hydrostatic pressure in a high pressure diecast Mg AZ91 alloy (Mg-9wt.%Al-1wt.%Zn). The real 3D pore distribution obtained by tomography is used as input for the finite element simulations using an isotropic hardening law. The model is calibrated and validated against experimental stress-strain curves. The results reveal that the pressure treatment has a significant influence both on the volume and shape changes of individuals pores, which have been precisely quantified, and which are found to be related to the initial pore volume. In conclusion, the crystal plasticity model proposed in this work successfully describes the intrinsic deformation mechanisms of Mg alloys both at the mesoscale and the microscale. More specifically, it can capture slip and twin activities, their interactions, as well as the potential porosity effects arising from casting processes.

Using floating car data to analyse the effects of ITS measures and eco-driving

The road transportation sector is responsible for around 25% of total man-made CO2 emissions worldwide. Considerable efforts are therefore underway to reduce these emissions using several approaches, including improved vehicle technologies, traffic management and changing driving behaviour. Detailed traffic and emissions models are used extensively to assess the potential effects of these measures. However, if the input and calibration data are not sufficiently detailed there is an inherent risk that the results may be inaccurate. This article presents the use of Floating Car Data to derive useful speed and acceleration values in the process of traffic model calibration as a means of ensuring more accurate results when simulating the effects of particular measures. The data acquired includes instantaneous GPS coordinates to track and select the itineraries, and speed and engine performance extracted directly from the on-board diagnostics system. Once the data is processed, the variations in several calibration parameters can be analyzed by comparing the base case model with the measure application scenarios. Depending on the measure, the results show changes of up to 6.4% in maximum speed values, and reductions of nearly 15% in acceleration and braking levels, especially when eco-driving is applied.