DYNAMICS AND CONTROL OF REACTIVE DISTILLATION PROCESS FOR MONOMER SYNTHESIS OF POLYCARBONATE PLANTS

Polycarbonate (PC) is an important engineering thermoplastic that is currently produced in large industrial scale using bisphenol A and monomers such as phosgene. Since phosgene is highly toxic, a non-phosgene approach using diphenyl carbonate (DPC) as an alternative monomer, as developed by Asahi Corporation of Japan, is a significantly more environmentally friendly alternative. Other advantages include the use of CO2 instead of CO as raw material and the elimination of major waste water production. However, for the production of DPC to be economically viable, reactive-distillation units are needed to obtain the necessary yields by shifting the reaction-equilibrium to the desired products and separating the products at the point where the equilibrium reaction occurs. In the field of chemical reaction engineering, there are many reactions that are suffering from the low equilibrium constant. The main goal of this research is to determine the optimal process needed to shift the reactions by using appropriate control strategies of the reactive distillation system. An extensive dynamic mathematical model has been developed to help us investigate different control and processing strategies of the reactive distillation units to increase the production of DPC. The high-fidelity dynamic models include extensive thermodynamic and reaction-kinetics models while incorporating the necessary mass and energy balance of the various stages of the reactive distillation units. The study presented in this document shows the possibility of producing DPC via one reactive distillation instead of the conventional two-column, with a production rate of 16.75 tons/h corresponding to start reactants materials of 74.69 tons/h of Phenol and 35.75 tons/h of Dimethyl Carbonate. This represents a threefold increase over the projected production rate given in the literature based on a two-column configuration. In addition, the purity of the DPC produced could reach levels as high as 99.5% with the effective use of controls. These studies are based on simulation done using high-fidelity dynamic models.

3D-Druck von Kunststoff-Medizinprodukten

Das Additive Manufacturing gewinnt im Bereich der Medizintechnik zur Herstellung von Prototypen bis hin zu Endprodukten zunehmend an Bedeutung. Ein großes Hemmnis stellen allerdings die relativ hohen Fertigungskosten dar. Hier bietet der verstärkte Einsatz der 3D-Drucktechnologie (3D Printing) ein erhebliches Potential zur Reduktion der Kosten. Aus dieser Motivation heraus wurde ein 3D-Druckverfahren zur Herstellung biokompatibler, sterilisierbarer Kunststoffmodelle entwickelt. Beim 3D-Druck-Verfahren handelt es sich um einen pulverbasierten Prozess zur schichtweisen Herstellung von Modellen direkt aus Computerdaten. Dabei werden dünne Schichten eines Pulvers auf eine Grundplatte aufgebracht, die dann durch gezielte Binderzugabe entsprechend des aktuellen Bauteilquerschnitts verfestigt werden. Ausgangsmaterial für diesen Prozess ist ein Granulatgemisch auf Basis von PMMA (Polymethylmethacrylat). Als Binderflüssigkeit wird ein Lösungsmittel eingesetzt. Die 3D gedruckten Modelle werden nach einer entsprechenden Trocknungszeit im Pulverbett entpackt und warmgelagert, um das Abdampfen des Lösungsmittels zu beschleunigen. Der Nachweis der Biokompatibilität der hergestellten Modelle erfolgte durch einen Test nach DIN EN ISO 10993-5. In Kooperation mit Anwendern wurden verschiedene Anwendungsbeispiele wie Bohrschablonen, Otoplastiken, Gebissmodelle und Modelle für die präoperative Planung realisiert und charakterisiert.

Experimentelle Analyse von Last- und Treibketten zur Optimierung der Lebensdauer

Zusammen mit einem namhaften Kettenhersteller hat das Institut für Fördertechnik und Logistik (IFT) im Rahmen eines AIF-geförderten Forschungsprojektes einen Kettenverschleißprüfstand für Last- und Treibketten entwickelt und gebaut, um neuentwickelte Ketten in kurzen Testphasen unter normierter Umgebung auf ihre Lebensdauer bzw. Verschleißfestigkeit zu prüfen. Durch steigende Rohstoffkosten und den immer größer werdenden Konkurrenzdruck im Bereich der Ketten entsteht ein hoher Bedarf an der Entwicklung neuer leistungsfähigerer Produkte. Die Neuheit dieser Projektidee liegt in dem erstmaligen Einsatz alternativer Werkstoffe und Konstruktionen in Kombination mit neuen verschleißarmen Beschichtungsverfahren für Kettenbauteile um Schmierstoffe langfristig einzulagern und bedarfsgerecht abzugeben

Production of Ethanol from Hardwood

Diminishing crude oil and natural gas supplies, along with concern about greenhouse gas are major driving forces in the search for efficient renewable energy sources. The conversion of lignocellulosic biomass to energy and useful chemicals is a component of the solution. Ethanol is most commonly produced by enzymatic hydrolysis of complex carbohydrates to simple sugars followed by fermentation using yeast. C6Hl0O5 + H2O −Enxymes→ C6H12O6 −Yeast→ 2CH3CH2OH + 2C02 In the U.S. corn is the primary starting raw material for commercial ethanol production. However, there is insufficient corn available to meet the future demand for ethanol as a gasoline additive. Consequently a variety of processes are being developed for producing ethanol from biomass; among which is the NREL process for the production of ethanol from white hardwood. The objective of the thesis reported here was to perform a technical economic analysis of the hardwood to ethanol process. In this analysis a Greenfield plant was compared to co-locating the ethanol plant adjacent to a Kraft pulp mill. The advantage of the latter case is that facilities can be shared jointly for ethanol production and for the production of pulp. Preliminary process designs were performed for three cases; a base case size of 2205 dry tons/day of hardwood (52 million gallons of ethanol per year) as well as the two cases of half and double this size. The thermal efficiency of the NREL process was estimated to be approximately 36%; that is about 36% of the thermal energy in the wood is retained in the product ethanol and by-product electrical energy. The discounted cash flow rate of return on investment and the net present value methods of evaluating process alternatives were used to evaluate the economic feasibility of the NREL process. The minimum acceptable discounted cash flow rate of return after taxes was assumed to be 10%. In all of the process alternatives investigated, the dominant cost factors are the capital recovery charges and the cost of wood. The Greenfield NREL process is not economically viable with the cost of producing ethanol varying from $2.58 to $2.08/gallon for the half capacity and double capacity cases respectively. The co-location cases appear more promising due to reductions in capital costs. The most profitable co-location case resulted in a discounted cash flow rate of return improving from 8.5% for the half capacity case to 20.3% for the double capacity case. Due to economy of scale, the investments become more and more profitable as the size of the plant increases. This concept is limited by the amount of wood that can be delivered to the plant on a sustainable basis as well as the demand for ethanol within a reasonable distance of the plant.

Caracterización de germoplasma de topinambur (Helianthus tuberosus L.) por aptitud agronómica e industrial

El topinambur pertenece a la familia de las Asteráceas, es una especie originaria de América del Norte, de la que fundamentalmente se aprovechan sus tubérculos; tiene gran potencial como alimento, materia prima para productos industriales y producción de biocombustibles. En Argentina no hay cultivares de topinambur registrados. Sin embargo hay documentación y testimonios del ingreso de distintas variedades al país a principios del siglo XX. El objetivo de esta tesis fue caracterizar el germoplasma de topinambur que se cultiva, a pequeña escala, en distintas regiones de la Argentina. Se formó una colección de trabajo con introducciones provenientes de 5 provincias del país (Río Negro, Chubut, Buenos Aires, Mendoza y Córdoba), y se condujeron ensayos experimentales en dos ambientes de la provincia de Mendoza. Se evaluaron caracteres morfológicos (altura de plantas, dimensiones y ángulo de inserción de hojas, tamaño de tubérculos), fenológicos (emergencia, inicio, fin y duración de floración, senescencia del cultivo) y rendimiento. Se detectaron diferencias morfológicas que permitieron agrupar a las introducciones en dos grupos, correspondiendo uno a introducciones de tubérculos rojos y el otro a introducciones de tubérculos blancos. Se valoró la aptitud hortícola de las introducciones mediante evaluación sensorial; se realizó una prueba de preferencia y percepción de distintos aspectos de la hortaliza (color, olor, sabor y textura), consumida cruda. El nivel de aceptación general de la hortaliza fue bueno. Se evaluó el potencial industrial (obtención de inulina y producción de etanol). Se determinó por HPLC el contenido de inulina de cada introducción, que varió de 18.07 a 22.95 % y se estimó el potencial para producir etanol a partir de los hidratos de carbono fermentables de los tubérculos, que llegó a 4.934 litros por ha, aunque sin diferencias entre introducciones.

Tecnología cerámica : estudios experimentales sobre la cerámica del sitio arqueológico San Ignacio (Noroeste de Mendoza)

El propósito de este trabajo es explorar la disponibilidad de materias primas que pudieron ser utilizadas en el proceso de manufactura de la cerámica gris del sitio arqueológico San Ignacio, en el Valle de Potrerillos, ubicado al Norte de la provincia de Mendoza (640 dC). Se pretende, además, reproducir las técnicas de producción y cocción cerámica, a fin de obtener un producto de características análogas a las de la colección estudiada. La metodología utilizada presentó las siguientes etapas: recolección de materiales arcillosos; caracterización de las propiedades físicas en estado crudo; análisis químicos; desarrollo experimental de cocción y ensayos post-cocción de los mismos. Los productos obtenidos muestran una buena estructura y sinterización, aunque no se logró una atmósfera completamente reductora con este tipo de combustible.

Uso de aguas residuales urbanas en el riego de colza (Brassica napus L.) con destino a biocombustible

El aceite de colza es comestible pero también puede utilizarse en la producción de biodiesel. Cuando el destino es el energético, el cultivo puede regarse con aguas residuales urbanas o cloacales. La mayor proporción del uso de éstas en el mundo ocurre en regiones áridas donde otras fuentes de agua son escasas, situación que se plantea en los oasis irrigados de Mendoza. En este trabajo se comparó el rendimiento de un cultivar invernal de colza regado con agua cloacal (AC) y agua subterránea (AS), y su potencial para producir biodiesel. La experiencia se llevó a cabo en una planta de tratamiento de agua cloacal de Obras Sanitarias en el departamento Tunuyán (33° 32’ 89’’ S; 69° 00’ 80’’ O; 859 m snm). El rendimiento de semilla de AC fue significativamente mayor que el de AS (7690 y 3886 kg/ha, respectivamente). La cantidad de biodiesel factible de producir por cada hectárea de cultivo asciende a 2800 kg en el tratamiento AC y a 1400 kg en AS. El uso de aguas residuales urbanas genera un nicho interesante para la producción de biocombustibles, utilizando un recurso hídrico con limitaciones para producir alimentos.

Uso de agua en industrias de elaboración de conservas de tomate y de durazno de Mendoza, Argentina

El objetivo de este trabajo es conocer, a nivel de cuenca, el volumen de agua utilizado por las industrias de elaboración de conservas de tomate y de durazno de Mendoza. Para ello se estima la materia prima utilizada en la elaboración de estas conservas a partir de datos de superficie cultivada para tal destino y de rendimientos por superficie obtenidos en el Registro Permanente de Uso de la Tierra de Mendoza y el Instituto Nacional de Tecnología Agropecuaria. Se emplearon coeficientes de volumen de agua utilizada por unidad de materia prima procesada, que varían entre 5 y 25 L kg-1 de producto procesado, sin incluir el uso de agua para riego en fincas. Los resultados se analizaron para diferentes valores de coeficientes asociados a la eficiencia del uso del agua, en escenarios optimista y pesimista. Se concluye que las industrias elaboradoras de conservas de tomate y de durazno de Mendoza utilizan entre 0,66 y 6,15 hm3/año. El mayor consumo de agua de las conserveras de tomate ocurre en la cuenca Norte, alcanzando el 64,9% del total demandado por tales industrias. Para las conserveras de durazno, el mayor consumo se produce en la cuenca Sur con un 46% de total demandado.

Sedimentology on two core from the Bransfield Strait area

The raw material for these investigations are samples from marine (sub)surface sediments around the northern part of the Antarctic Peninsula. They had been sampled in the years 1981 to 1986 during several expeditions of the research vessels Meteor, Polarstern and Walther Herwig. 83 box core, gravity core and dredge samples from the area of the Bransfield Strait, the Powell Basin and the northern Weddell Sea have been examined for their grain-size distribution, their mineralogical and petrographical composition. Silt prevails and its clay proportions exceed 25% wt. in water depths greater than 2000 m. The granulometrical results reveal some typical sedimentation processes within the area of investigation. While turbiditic processes together with sediment input from melting icebergs control the sedimentation in the Weddell Sea, the South Orkney Island Plateau and the Powell Basin, the fine grained material from Bransfield Strait mainly relies on marine currents in the shelf area. In addition, the direct sediment input of coarse shelf sediments from the Bransfield Strait into the Powell Basin through submarine canyons could be proven. Variations in the grain-size composition with sediment depth are smalI. The mineral composition of the clay and fine silt fractions is quite uniform in all samples. There are (in decreasing order): illite, montmorillonite, chlorite, smectite, mixed-Iayers, as well as detrital quartz and feldspars. A petrographically based sediment stratigraphy can be established in using the considerable changes in the chlorite- and Ca-plagioclase portions in samples from Core 224. For this sedimentation area a mean sedimentation rate of 7 cm/1000 a is assumed. Remarkable changes in the portions of amorphous silica components - diatom skeletons and volcanic glass shards - appear all over the area of investigation. They contribute between 4-83 % to the clay and fine silt fraction. Several provinces according to the heavy mineral assemblages in the fine sand fraction can be distinguished: (i) a province remarkably influenced by minerals of volcanic origin south and north of the South Shetland Islands; (ii) a small strip with sediment dominated by plutonic material along the western coast of the Antarctic Peninsula and (iii) a sediment controlled by metamorphic minerals and rock fragments in the area of the Weddell Sea and Elephant Island. While taking the whole grain-size spectrum into account a more comprehensive interpretation can be given: the accessoric but distinct appearance of tourmaline, rutile and zircon in the heavy mineral assembly along the northwestern coast of the Antarctic Peninsula is in agreement with the occurrence of acid volcanic rock pieces in the coarse fraction of the ice load detritus in this region. In the vicinity of the South Shetland Islands chlorite appears in remarkable portions in the clay fraction in combination with leucoxene, sphene and olivine, and pumice as well as pyroclastic rocks in the medium and coarse grain fractions, respectively. Amphiboles and amphibole-schists are dominant on the South Orkney Island Plateau. In the sediments of the northwestern Weddell Sea the heavy mineral phases of red spinel, garnet, kyanite and sillimanite in connection with medium to highgrade metamorphic rocks especially granulitic gneisses, are more abundant. A good conformity between the ice rafted rock sampIes and the rocks in the island outcrops could be proven, especially in the vicinity of offshore islands nearby. On the continent enrichments of rock societies and groups appear in spacious outlines: acid effusive rocks in the west of the ice divide on the Antarctic Peninsula, clastic sedimentites at the tip of the Antarctic Peninsula and granoblastic gneisses in central and eastern Antarctica. Coarse grain detritus with more than 1 cm of diameter must have been rafted by icebergs. These rock fragments are classified as rock types, groups and societies. The spacial distribution of their statistically determined weight relations evidently shows the paths of the iceberg drift and in nexus with already known iceberg routes also point to the possible areas of provenance, provided that the density of sample locations and the number of rock pieces are sufficient.

Myanmar Sugar SMEs: History, Technology, Location and Government Policy

Small and medium enterprises (SMEs) engaged in sugar processing in Myanmar appeared in the last decade of the socialist era. An acute sugar deficit, restricted trade in white sugar, and high demand from the conventional dairy business led to the growth of sugar SMEs by appropriate blending of semi-finished products (syrup) in the fields, which were then processed in vacuum pans and centrifugals to obtain white sugar. This became a tradable commodity and sugar SMEs grew in clusters in big cities. They are family-owned businesses. However, they lack the bagasse-based power generation. In recent years, large modern sugar factories operated by private and military companies have emerged as key players. The current shortage of fuel feedstock and competition for raw materials have become driving forces that shift sugar SMEs from market-oriented to raw material-oriented locations. Internal competition among key players made sugar price highly volatile, too. Being placed on a level playing field, the whole industry should be upgraded in terms of price and quality to become export-oriented.

Sewage sludge gasification. Dolomite performance under different operating conditions

Gasification is a technology that can replace traditional management alternatives used up to date to deal with this waste (landfilling, composting and incineration) and which fulfils the social, environmental and legislative requirements. The main products of sewage sludge gasification are permanent gases (useful to generate energy or to be used as raw material in chemical synthesis processes), liquids (tars) and char. One of the main problems to be solved in gasification is tar production. Tars are organic impurities which can condense at relatively high temperatures making impossible to use the produced gases for most applications. This work deals with the effect of some primary tar removal processes (performed inside the gasifier) on sewage sludge gasification products. For this purpose, analysis of the gas composition, tar production, cold gas efficiency and carbon conversion were carried out. The tests were performed with air in a laboratory scale plant consisting mainly of a bubbling bed gasifier. No catalyzed and catalyzed (10% wt of dolomite in the bed and in the feeding) tests were carried out at different temperatures (750ºC, 800ºC and 850ºC) in order to know the effect of these parameters in the gasification products. As far as tars were concerned, qualitative and quantitative tar composition was determined. In all tests the Equivalence Ratio (ER) was kept at 0.3. Temperature is one of the most influential variables in sewage sludge gasification. Higher temperatures favoured hydrogen and CO production while CO2 content decreased, which might be partially explained by the effect of the cracking, Boudouard and CO2 reforming reactions. At 850ºC, cold gas efficiency and carbon conversion reached 49% and 76%, respectively. The presence of dolomite as catalyst increased the production of H2 reaching contents of 15.5% by volume at 850 °C. Similar behaviour was found for CO whereas CO2 and CnHm (light hydrocarbons) production decreased. In the presence of dolomite, a tar reduction of up to 51% was reached in comparison with no catalyzed tests, as well as improvements on cold gas efficiency and carbon conversion. Several assays were developed in order to test catalyst performance under more rough gasification conditions. For this purpose, the throughput value (TR), defined as kg sludge “as received” fed to the gasifier per hour and per m2 of cross sectional area of the gasifier, was modified. Specifically, the TR values used were 110 (reference value), 215 and 322 kg/h·m2. When TR increased, the H2, CO and CH4 production decreased while the CO2 and the CnHm production increased. Tar production increased drastically with TR during no catalysed tests what is related to the lower residence time of the gas inside the reactor. Nevertheless, even at TR=322 kg/h·m2, tar production decreased by nearly 50% with in-bed use of dolomite in comparison with no catalyzed assays under the same operating conditions. Regarding relative tar composition, there was an increase in benzene and naphthalene content when temperature increased while the content of the rest of compounds decreased. The dolomite seemed to be effective all over the range of molecular weight studied showing tar removal efficiencies between 35-55% in most cases. High values of the TR caused a significant increase in tar production but a slight effect on tar composition.

The Influence of Different Surface Treatments on the Mechanical Strength of Silicon Wafers

The implementation of photovoltaic solar energy based on silicon is being slowed down by the shortage of raw material. In this context, the use of thinner wafers arises as a solution reducing the amount of silicon in the photovoltaic modules. On the other hand, the manufacturing process with thinner wafers can become complicated with traditional tools. The high number of damaged wafers reduces the global yield. It’s known that edge and surface cracks and defects determine the mechanical strength of wafers. There are several ways of removing these defects e. g. subjecting wafers to a mechanical polishing or to a chemical etching. This paper shows a comparison between different surface treatments and their influence on the mechanical strength.

EMBT haciendo (casi) nada en Mercaders = EMBT doing (almost) nothing in Mercaders

Cualquier indagación sobre proyectos representativos en la historia contemporánea de la vivienda, nos lleva inevitablemente a darnos cuenta como predomina en gran parte de ellos una actitud que tiene que ver con producir indiscriminadamente nuevos productos arquitectónicos. EMBT construyen su propia casa en la calle Mercaders de Barcelona, e inciden en entender la arquitectura no como la creación de nuevos productos sino como una capa más dentro de un sustrato ya informado(materia no prima), una característica puramente postproductiva. Como ellos apuntan su nueva capa de información se ‘instala’, añade sólo información precisa de su tiempo, pero no intenta volver hacia atrás ni rehabilitar o restaurar el edificio existente. Esta comunicación persigue poner de manifiesto la existencia velada de esta otra actitud dentro del campo de la vivienda, una actitud no opuesta y si complementaria, que opera desde una voluntad de no ser, de hacer con (casi) nada. ABSTRACT: Any inquiry about representative projects in the contemporary history of housing, lead us to inevitably understand how in lots of them dominates an attitude related to the indiscriminate production of new architectural products. EMBT build their own house on Mercaders street of Barcelona, and promote the understanding of architecture not as the creation of new products but as a new layer within a substrate already full of information (not a raw material), a feature purely postproductive. As they point, the new information layer is ‘installed’, adds only precise information of its time, but does not try to get back or restore the existing building. This paper aims to demonstrate the veiled existence of this different attitude within the housing field, an attitude not opposed but complementary, that works from a desire of not to do, a desire to do with (almost) nothing.

La financiación y la inversión inmobiliaria : repercusiones en el urbanismo y la arquitectura

El presente trabajo de tesis doctoral tiene por finalidad demostrar que las decisiones de financiación y de inversión inmobiliaria en España influyen de manera determinante en la configuración del proceso urbanístico y arquitectónico. Este planteamiento inicial obliga a formular las siguientes cuestiones: - En una primera fase, la situación en España del sector inmobiliario y su relación con el sector financiero en el contexto de la actual crisis financiera, iniciada en el año 2008. - Los métodos de análisis y selección de inversiones y su aplicación a los proyectos de inversión en función de la naturaleza de los activos inmobiliarios. - La valoración inmobiliaria para determinadas entidades financieras. - Características de la gestión financiera empresarial y de las empresas inmobiliarias. - El origen de fondos para financiar el proceso urbanístico y arquitectónico mediante las instituciones de inversión colectiva inmobiliaria y el mercado inmobiliario. - La regulación actual en España, a nivel estatal, del suelo como materia prima del sector inmobiliario. - La edificación residencial y el mercado inmobiliario en el actual contexto económico. - La posibilidad de crear en España un mercado de derivados basado en activos inmobiliarios. - Cómo repercute la actividad económica, a través de la inversión y la financiación, en los activos inmobiliarios, en el urbanismo y la arquitectura. Las cuestiones precedentes se resuelven de forma sistemática y metodológica en esta tesis doctoral estructurada en tres grandes bloques (inversión, financiación y repercusiones en el urbanismo y la arquitectura), obteniendo una serie de respuestas reflejadas en el desarrollo del presente trabajo que se sintetizan en las siguientes líneas: - La actual crisis financiera iniciada en el año 2008 ha provocado en España el colapso del sector inmobiliario y una nueva concepción en la naturaleza de los activos inmobiliarios. El sector inmobiliario trae causa del sector financiero, en especial del crédito bancario. - Dependencia y vinculación del sector inmobiliario español de la política monetaria europea: la incorporación de España a la moneda única transforma por completo el sector inmobiliario español. - Los métodos de análisis y selección de inversiones se conforman como instrumentos relevantes que nos permiten jerarquizar nuestros proyectos. No obstante, presentan una serie de limitaciones y dificultades de aplicación práctica, por lo que no deben considerarse como herramientas que nos aporten una única solución irrefutable. - La valoración de activos inmobiliarios se constituye en un pilar básico que fundamenta la correcta aplicación de los fondos. - La inversión en activos inmobiliarios puede realizarse de forma directa o indirecta. En este último supuesto, con una influencia relevante de las innovaciones financieras surgidas en los últimos años. - Las instituciones de inversión colectiva y el mercado hipotecario constituyen instituciones fundamentales capaces de captar importantes cantidades de fondos que impulsan y financian el proceso urbanístico y arquitectónico. - El complejo y cambiante sistema jurídico español en materia de suelo, dificulta la implementación de los procesos urbanísticos y arquitectónicos. - Tras la crisis financiera de 2008, los activos inmobiliarios tienen un comportamiento similar a otros activos en cuanto a subidas y bajadas de precios. En el actual sistema económico, la especulación forma parte inherente a la naturaleza de los activos inmobiliarios. - Desde una perspectiva teórica, existe la posibilidad de crear un mercado de derivados que tenga como subyacente activos de naturaleza inmobiliaria. - Sin actividad económica, el proceso urbanístico y arquitectónico carecerá finalmente de sentido y tenderá a desaparecer. No obstante, son las innovaciones tecnológicas, a nivel de producto y proceso, las principales causantes del impulso de la actividad económica. - A pesar de lo expresado en los documentos urbanísticos internacionales, la transformación del urbanismo y la arquitectura dependen principalmente de la actividad económica y la tecnología. En un segundo nivel, la inversión y la financiación condicionan y definen el urbanismo y la arquitectura, incluso a nivel de proyecto si se pretende su materialización. En base al desarrollo previo, el objetivo fundamental de esta tesis doctoral ha sido demostrar que las decisiones de financiación y de inversión tienen una importancia capital y determinan la configuración de los activos inmobiliario, del urbanismo y la arquitectura, por lo que deben ser tenidas en cuenta no sólo en su materialización sino incluso en la propia concepción del proceso creativo. ABSTRACT The present dissertation aims to show that real estate financing and investment decisions in Spain play a predominant role in structuring urban development and architectural solutions. The issues addressed to support that contention include: - As a preliminary study, the situation of the real estate industry in Spain and its relationship to the financial sector in the context of the 2008 financial crisis. - The methods used to analyse and select investments and their application to investment projects, by type of real estate asset. - Appraisal of certain financial institutions’ real estate asset holdings. - Characteristics of financial institution and real estate company corporate management. - Sourcing funds for financing urban development and architecture through real estate investment trusts and the real estate market. - Present nation-wide regulations on landed property in Spain as a raw material for the real estate industry. - Residential building construction and the real estate market in the present economic context. - The possibility of creating a real estate asset-based derivatives market in Spain - The impact of economic activity, through investment and financing, on real estate assets, urban development and architecture. The aforementioned issues are addressed systematically and methodically in this dissertation, which is divided into three major units: investment, financing, and impact on urban development and architecture. The conclusions drawn are summarised below. - The financial crisis that began in 2008 has induced the collapse of the Spanish real estate industry and spawned a new perception of the nature of real estate assets. The real estate industry is dependent upon the financial sector, in particular on bank loans. - The Spanish real estate industry also depends on and is related to European monetary policy: Spain’s adherence to the single currency ushered in a thorough overhaul of its real estate industry. - Investment analysis and selection methods constitute highly suitable tools for project evaluation and ranking. Nonetheless, inasmuch as their practical implementation is subject to a series of limitations and difficulties, they should not be thought able to deliver a single irrefutable solution. - Real estate asset appraisal is a mainstay to the rightful application of funds. - Real estate asset investments can be made directly or indirectly. The latter approach is heavily influenced by the financial innovations forthcoming in recent years. - Investment trusts and the mortgage market are key institutions able to raise substantial funding, thereby driving and financing urban development and architecture. - Spain’s complex and changing legal provisions on land management are an obstacle to urban development and architecture. - Since the 2008 crisis, real estate assets have behaved much like other assets in terms of rising and falling prices. In the present economic context, speculation is indivisible from real estate assets. - Theoretically speaking, a derivatives market with real estate holdings as the underlying assets lies within the realm of possibility. - In the absence of economic activity, urban development and architecture are senseless pursuits and tend to disappear. Technological innovation in products and processes are the main drivers of economic activity. - Despite the opinion expressed in international papers on the subject, the transformation of urban development and architecture depend primarily on economic activity and technology. In a second dimension, investment and financing condition and define urban development and architecture, even at the design level for projects aspiring to actual construction. Pursuant to the foregoing, the primary aim of this dissertation is to show that financial and investment decisions are of cardinal importance and determine the structure of real estate assets, urban development and architecture. They must consequently be borne in mind not only in connection with implementation, but also with conceptual design and the creative process itself. I

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.