Inmovilización de TiO2 sobre polímeros transparentes en el UV-A para la eliminación fotocatalítica de tricloroetileno en aire

El gran desarrollo industrial y demográfico de las últimas décadas ha dado lugar a un consumo crecientemente insostenible de energía y materias primas, que influye negativamente en el ambiente por la gran cantidad de contaminantes generados. Entre las emisiones tienen gran importancia los compuestos orgánicos volátiles (COV), y entre ellos los compuestos halogenados como el tricloroetileno, debido a su elevada toxicidad y resistencia a la degradación. Las tecnologías generalmente empleadas para la degradación de estos compuestos presentan inconvenientes derivados de la generación de productos tóxicos intermedios o su elevado coste. Dentro de los procesos avanzados de oxidación (Advanced Oxidation Processes AOP), la fotocatálisis resulta una técnica atractiva e innovadora de interés creciente en su aplicación para la eliminación de multitud de compuestos orgánicos e inorgánicos, y se ha revelado como una tecnología efectiva en la eliminación de compuestos orgánicos volátiles clorados como el tricloroetileno. Además, al poder aprovechar la luz solar como fuente de radiación UV permite una reducción significativa de costes energéticos y de operación. Los semiconductores más adecuados para su empleo como fotocatalizadores con aprovechamiento de la luz solar son aquellos que tienen una banda de energía comparable a la de los fotones de luz visible o, en su defecto, de luz ultravioleta A (Eg < 3,5 eV), siendo el más empleado el dióxido de titanio (TiO2). El objetivo principal de este trabajo es el estudio de polímeros orgánicos comerciales como soporte para el TiO2 en fotocatálisis heterogénea y su ensayo para la eliminación de tricloroetileno en aire. Para ello, se han evaluado sus propiedades ópticas y su resistencia a la fotodegradación, y se ha optimizado la fijación del fotocatalizador para conseguir un recubrimiento homogéneo, duradero y con elevada actividad fotocatalítica en diversas condiciones de operación. Los materiales plásticos ensayados fueron el polietileno (PE), copolímero de etil vinil acetato con distintos aditivos (EVA, EVA-H y EVA-SH), polipropileno (PP), polimetil (metacrilato) fabricado en colada y extrusión (PMMA-C y PMMA-E), policarbonato compacto y celular (PC-C y PC-Ce), polivinilo rígido y flexible (PVC-R y PVC-F), poliestireno (PS) y poliésteres (PET y PETG). En base a sus propiedades ópticas se seleccionaron el PP, PS, PMMA-C, EVA-SH y PVC-R, los cuales mostraron un valor de transmitancia superior al 80% en el entorno de la región estudiada (λ=365nm). Para la síntesis del fotocatalizador se empleó la tecnología sol-gel y la impregnación multicapa de los polímeros seleccionados por el método de dip-coating con secado intermedio a temperaturas moderadas. Con el fin de evaluar el envejecimiento de los polímeros bajo la radiación UV, y el efecto sobre éste del recubrimiento fotoactivo, se realizó un estudio en una cámara de exposición a la luz solar durante 150 días, evaluándose la resistencia química y la resistencia mecánica. Los resultados de espectroscopía infrarroja y del test de tracción tras el envejecimiento revelaron una mayor resistencia del PMMA y una degradación mayor en el PS, PVC-R y EVA SH, con una apreciable pérdida del recubrimiento en todos los polímeros. Los fotocatalizadores preparados sobre soportes sin tratamiento y con tres capas de óxido de titanio mostraron mejores resultados de actividad con PMMA-C, PET y PS, con buenos resultados de mineralización. Para conseguir una mayor y mejor fijación de la película al soporte se realizaron tratamientos químicos abrasivos con H2SO4 y NaOH y tratamientos de funcionalización superficial por tecnología de plasma a presión atmosférica (APP) y a baja presión (LPP). Con los tratamientos de plasma se consiguió una excelente mojabilidad de los soportes, que dio lugar a una distribución uniforme y más abundante del fotocatalizador, mientras que con los tratamientos químicos no se obtuvo una mejora significativa. Asimismo, se prepararon fotocatalizadores con una capa previa de dióxido de silicio con la intervención de surfactantes (PDDA-SiO2-3TiO2 y SiO2FC-3TiO2), consiguiéndose buenas propiedades de la película en todos los casos. Los mejores resultados de actividad con tratamiento LPP y tres capas de TiO2 se lograron con PMMA-C (91% de conversión a 30 ppm de TCE y caudal 200 ml·min-1) mejorando significativamente también la actividad fotocatalítica en PVC-R y PS. Sin embargo, el material más activo de todos los ensayados fue el PMMA-C con el recubrimiento SiO2FC-3TiO2, logrando el mejor grado de mineralización, del 45%, y una velocidad de 1,89 x 10-6 mol· m-2 · s-1, que dio lugar a la eliminación del 100 % del tricloroetileno en las condiciones anteriormente descritas. A modo comparativo se realizaron ensayos de actividad con otro contaminante orgánico tipo, el formaldehído, cuya degradación fotocatalítica fue también excelente (100% de conversión y 80% de mineralización con 24 ppm de HCHO en un caudal de aire seco de 200 ml·min-1). Los buenos resultados de actividad obtenidos confirman las enormes posibilidades que ofrecen los polímeros transparentes en el UV-A como soportes del dióxido de titanio para la eliminación fotocatalítica de contaminantes en aire. ABSTRACT The great industrial and demographic development of recent decades has led to an unsustainable increase of energy and raw materials consumption that negatively affects the environment due to the large amount of waste and pollutants generated. Between emissions generated organic compounds (VOCs), specially the halogenated ones such as trichloroethylene, are particularly important due to its high toxicity and resistance to degradation. The technologies generally used for the degradation of these compounds have serious inconveniences due to the generation of toxic intermediates turn creating the problem of disposal besides the high cost. Among the advanced oxidation processes (AOP), photocatalysis is an attractive and innovative technique with growing interest in its application for the removal of many organic and inorganic compounds, and has emerged as an effective technology in eliminating chlorinated organic compounds such as trichloroethylene. In addition, as it allows the use of sunlight as a source of UV radiation there is a significant reduction of energy costs and operation. Semiconductors suitable to be used as photocatalyst activated by sunlight are those having an energy band comparable to that of the visible or UV-A light (Eg <3,5 eV), being titanium dioxide (TiO2), the most widely used. The main objective of this study is the test of commercial organic polymers as supports for TiO2 to be applied in heterogeneous photocatalysis and its assay for removing trichloroethylene in air. To accomplish that, its optical properties and resistance to photooxidation have been evaluated, and different operating conditions have been tested in order to optimize the fixation of the photocatalyst to obtain a homogeneous coating, with durable and high photocatalytic activity. The plastic materials tested were: polyethylene (PE), ethyl vinyl acetace copolymers with different additives (EVA, EVA-H and EVA -SH), polypropylene (PP), poly methyl (methacrylate) manufactured by sheet moulding and extrusion (PMMA-C and PMMA-E), compact and cellular polycarbonates (PC-C PC-Ce), rigid and flexible polyvinyl chloride (PVC-R and PVC-F), polystyrene (PS) and polyesters (PET and PETG). On the basis of their optical properties PP, PS, PMMA-C, EVA-SH and PVC-R were selected, as they showed a transmittance value greater than 80% in the range of the studied region (λ = 365nm). For the synthesis of the photocatalyst sol-gel technology was employed with multilayers impregnation of the polymers selected by dip-coating, with intermediate TiO2 drying at moderate temperatures. To evaluate the polymers aging due to UV radiation, and the effect of photoactive coating thereon, a study in an sunlight exposure chamber for 150 days was performed, evaluating the chemical resistance and the mechanical strength. The results of infrared spectroscopy and tensile stress test after aging showed the PMMA is the most resistant sample, but a greater degradation in PS, PVC-R and EVA SH, with a visible loss of the coating in all the polymers tested. The photocatalysts prepared on the untreated substrates with three layers of TiO2 showed better activity results when PMMA-C, PET and PS where used. To achieve greater and better fixation of the film to the support, chemical abrasive treatments, with H2SO4 and NaOH, as well as surface functionalization treatments with atmospheric pressure plasma (APP) and low pressure plasma (LPP) technologies were performed. The plasma treatment showed the best results, with an excellent wettability of the substrates that lead to a better and uniform distribution of the photocatalyst compared to the chemical treatments tested, in which no significant improvement was obtained. Also photocatalysts were prepared with the a silicon dioxide previous layer with the help of surfactants (SiO2- 3TiO2 PDDA-and-3TiO2 SiO2FC), obtaining good properties of the film in all cases. The best activity results for LPP-treated samples with three layers of TiO2 were achieved with PMMA-C (91% conversion, in conditions of 30 ppm of TCE and 200 ml·min-1 air flow rate), with a significant improvement of the photocatalytic activity in PVC-R and PS samples too. However, among all the materials assayed, PMMA-C with SiO2FC-3TiO2 coating was the most active one, achieving the highest mineralization grade (45%) and a reaction rate of 1,89 x 10-6 mol· m-2 · s-1, with total trichloroethylene elimination in the same conditions. As a comparative assay, an activity test was also performed with another typical organic contaminant, formaldehyde, also with good results (100% conversion with 24 ppm of HCHO and 200 ml·min-1 gas flow rate). The good activity results obtained in this study confirm the great potential of organic polymers which are transparent in the UV-A as supports for titanium dioxide for photocatalytic removal of air organic pollutants.

Bare-tether cathodic contact through thermoionic emission by low work-function materials

A new material, C12A7 : electride, which might present a work function as low as 0.6 eV and moderately high temperature stability, was recently proposed as coating for floating bare tethers. Arising from heating under space operation, current is emitted by thermionic emission along a thus coated cathodic segment. A preliminary study on the space-charge-limited (SCL) double layer in front of the cathodic segment is presented using Langmuir’s SCL electron current between cylindrical electrodes and orbital-motion-limited ion-collection sheath. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects and the transition from SCL to full Richardson-Dushman emission included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission leads to a short cathodic section and may eliminate the need for an active cathodic device and its corresponding gas feed requirements and power subsystem, which results in a truly “propellant-less” tether system for such basic applications as de-orbiting low earth orbit satellites.

Estudio experimental sobre la efectividad y la viabilidad de distintas soluciones constructivas para reducir la concentración de gas radón en edificaciones

El trabajo de investigación desarrollado que ha dado lugar a la realización de esta Tesis, aborda la protección de los edificios frente a la entrada de gas radón y su acumulación en los espacios habitados. Dicho gas (isótopo del radón Rn-222) es un elemento radiactivo que se genera, principalmente, en terrenos con altos contenidos de radio (terrenos graníticos por ejemplo). Su alto grado de movilidad permite que penetre en los edificios a través de los materiales de cerramiento del mismo (porosidad de los materiales, fisuras, grietas y juntas) y se acumule en su interior, donde puede ser inhalado en altas concentraciones. La Organización Mundial de la Salud, califica al radón como agente cancerígeno de grado 1. Según este Organismo, el radón es la segunda causa de contracción de cáncer pulmonar detrás del tabaco. Como respuesta a esta alarma, distintos estados ya han elaborado normativas en las que se proponen soluciones para que los niveles de concentración de radón no superen los valores recomendados por los organismos internacionales responsables de la protección radiológica. En España aún no existe normativa de protección frente a este agente cancerígeno causante de numerosas muertes, y es por tal motivo evidente la necesidad de aportar documentación técnica que ayude a las administraciones nacionales y locales a desarrollar dicha normativa para ajustarse a las recomendaciones europeas e internacionales sobre los niveles que no se deben superar y que, por otro lado, ya han contemplado una gran cantidad de países. Como principal aportación de este trabajo se muestran los resultados de reducción de concentración de gas radón de distintas soluciones constructivas enfocadas a frenar la entrada de gas radón al interior de los edificios haciendo uso de técnicas y materiales habituales en el ámbito de la construcción en España. Para ello, se han estudiado las efectividades de dichas soluciones, en lo referente a su capacidad para frenar la inmisión de radón, en un prototipo de vivienda construido al efecto en un terreno con altas concentraciones de radón. Las soluciones propuestas y ensayadas han sido el resultado de una labor de optimización de los sistemas estudiados en la bibliografía con el fin de adaptar las técnicas a los sistemas constructivos habituales en España y en concreto a la situación real del prototipo de vivienda construido en un lugar con contenidos de radón en terreno muy elevados. El trabajo incluye un capítulo inicial con los conceptos básicos necesarios para entender la problemática que supone habitar en espacios con altos contenidos de radón. ABSTRACT The research developed, which has led to the completion of this thesis, deal with the protection of buildings against entry of radon gas and its accumulation in the ocupated spaces. This gas (radon isotope Rn-222) is a radioactive element generated, mainly, in areas with high levels of radio (granitic terrain for example). Its high mobility allows entering in buildings through the enclosure materials of it (porosity of materials, cracks, crevices and joints) and accumulates inside, where it can be inhaled in high concentrations. The World Health Organization describes radon gas as a carcinogen agent in level 1. According to this Agency, radon is the second leading cause of lung cancer behind tobacco. In response to this alarm, some states have developed regulations that propose solutions to reduce radon concentration levels for not exceeding the values recommended by international agencies responsible in radiation protection. In Spain there is still no legislation to protect against this carcinogen element that cause numerous deaths, and for that reason it is evident the need to provide technical documentation to help the national and local governments to develop legislation for reaching the European and international levels recommendations. As the main contribution of this work are the results of reducing radon concentration using different constructive solutions aimed to stop radon entry in buildings, with techniques and materials common in Spain. To do this, effectiveness of such solutions, have been studied in terms of its ability to stop radon entry in a housing prototype built for this purpose in an area with high radon levels. The solutions proposed and tested have been the result of a process of optimization of systems studied in the literature in order to adapt the techniques to Spanish building material and, specifically, to the actual situation of housing prototype built in a place with high contents of radon in soil. The work includes an initial chapter with the basic concepts needed to understand the problem of living in areas with high levels of radon.

Characterization of the environmental performance of the insulating materials in the enveloping of the building.

Insulating materials in buildings are one of the main factors that should be taken into account when talking about sustainability since with a correct application it could imply important savings for the citizens. In the course of its life, a building requires a series of supplies to perform the duties it has been built for, generating an impact on the environment. The selection of one material or another will establish partly the global environmental impact of the building. Choosing the right insulating material will determine the building's general degree of sustainability, both in its heating savings (energy consumption) and in the environmental impacts caused by its LCA (greenhouse gas emissions). Therefore, we propose to establish guidelines to characterize the insulating material with a better environmental performance in all the stages of its life cycle, taking into account the construction system, the use of the building and its location.

Airplane materials compatibility with blends of fossil kerosene JET A1 with biokerosenes from babassu, palm kernel and coconut oils

The aviation companies are facing some problems that argue in favor of biofuels: Rising cost of traditional fuel: from 0.71 USD/gallon in May 2003 to 3.09 USD/gallon in January 2012. Environmental concerns: direct emissions from aviation account for about 3 % of the EU’s total greenhouse gas emissions. The International Civil Aviation Organization (ICAO) forecasts that by 2050 they could grow by a further 300-700 %. On December 20th 2006 the European Commission approved a law proposal to include the civil aviation sector in the European market of carbon dioxide emission rights (European Union Emissions Trading System, EUETS)

Development of an Elevated Temperature Loop Heat Pipe for Space Applications and Investigation of Non Condensable Gas Impact on its Performance

Un caloducto en bucle cerrado o Loop Heat Pipe (LHP) es un dispositivo de transferencia de calor cuyo principio de operación se basa en la evaporación/condensación de un fluido de trabajo, que es bombeado a través de un circuito cerrado gracias a fuerzas de capilaridad. Gracias a su flexibilidad, su baja masa y su mínimo (incluso nulo) consumo de potencia, su principal aplicación ha sido identificada como parte del subsistema de control térmico de vehículos espaciales. En el presente trabajo se ha desarrollado un LHP capaz de funcionar eficientemente a temperaturas de hasta 125 oC, siguiendo la actual tendencia de los equipos a bordo de satélites de incrementar su temperatura de operación. En la selección del diseño optimo para dicho LHP, la compatibilidad entre materiales y fluido de trabajo se identificó como uno de los puntos clave. Para seleccionar la mejor combinación, se llevó a cabo una exhaustiva revisión del estado del arte, además de un estudio especifico que incluía el desarrollo de un banco de ensayos de compatibilidad. Como conclusión, la combinación seleccionada como la candidata idónea para ser integrada en el LHP capaz de operar hasta 125 oC fue un evaporador de acero inoxidable, líneas de titanio y amoniaco como fluido de trabajo. En esa línea se diseñó y fabricó un prototipo para ensayos y se desarrolló un modelo de simulación con EcosimPro para evaluar sus prestaciones. Se concluyó que el diseño era adecuado para el rango de operación definido. La incompatibilidad entre el fluido de trabajo y los materiales del LHP está ligada a la generación de gases no condensables. Para un estudio más detallado de los efectos de dichos gases en el funcionamiento del LHP se analizó su comportamiento con diferentes cantidades de nitrógeno inyectadas en su cámara de compensación, simulando un gas no condensable formado en el interior del dispositivo. El estudio se basó en el análisis de las temperaturas medidas experimentalmente a distintos niveles de potencia y temperatura de sumidero o fuente fría. Adicionalmente, dichos resultados se compararon con las predicciones obtenidas por medio del modelo en EcosimPro. Las principales conclusiones obtenidas fueron dos. La primera indica que una cantidad de gas no condensable más de dos veces mayor que la cantidad generada al final de la vida de un satélite típico de telecomunicaciones (15 años) tiene efectos casi despreciables en el funcionamiento del LHP. La segunda es que el principal efecto del gas no condensable es una disminución de la conductancia térmica, especialmente a bajas potencias y temperaturas de sumidero. El efecto es más significativo cuanto mayor es la cantidad de gas añadida. Asimismo, durante la campaña de ensayos se observó un fenómeno no esperado para grandes cantidades de gas no condensable. Dicho fenómeno consiste en un comportamiento oscilatorio, detectado tanto en los ensayos como en la simulación. Este efecto es susceptible de una investigación más profunda y los resultados obtenidos pueden constituir la base para dicha tarea. ABSTRACT Loop Heat Pipes (LHPs) are heat transfer devices whose operating principle is based on the evaporation/condensation of a working fluid, and which use capillary pumping forces to ensure the fluid circulation. Thanks to their flexibility, low mass and minimum (even null) power consumption, their main application has been identified as part of the thermal control subsystem in spacecraft. In the present work, an LHP able to operate efficiently up to 125 oC has been developed, which is in line with the current tendency of satellite on-board equipment to increase their operating temperatures. In selecting the optimal LHP design for the elevated temperature application, the compatibility between the materials and working fluid has been identified as one of the main drivers. An extensive literature review and a dedicated trade-off were performed, in order to select the optimal combination of fluids and materials for the LHP. The trade-off included the development of a dedicated compatibility test stand. In conclusion, the combination of stainless steel evaporator, titanium piping and ammonia as working fluid was selected as the best candidate to operate up to 125 oC. An LHP prototype was designed and manufactured and a simulation model in EcosimPro was developed to evaluate its performance. The first conclusion was that the defined LHP was suitable for the defined operational range. Incompatibility between the working fluid and LHP materials is linked to Non Condensable Gas (NCG) generation. Therefore, the behaviour of the LHP developed with different amounts of nitrogen injected in its compensation chamber to simulate NCG generation, was analyzed. The LHP performance was studied by analysis of the test results at different temperatures and power levels. The test results were also compared to simulations in EcosimPro. Two additional conclusions can be drawn: (i) the effects of an amount of more than two times the expected NCG at the end of life of a typical telecommunications satellite (15 years) is almost negligible on the LHP operation, and (ii) the main effect of the NCG is a decrease in the LHP thermal conductance, especially at low temperatures and low power levels. This decrease is more significant with the progressive addition of NCG. An unexpected phenomenon was observed in the LHP operation with large NCG amounts. Namely, an oscillatory behaviour, which was observed both in the tests and the simulation. This effect provides the basis for further studies concerning oscillations in LHPs.

Analytical bearing capacity of strip footing in weightless materials with power-law failure criteria

Sokolovskii’s method of characteristics is extended to provide analytical solutions for the ultimate load at the moment of plastic failure under plane-strain conditions of shallow strip foundations on weightless rigid-plastic media with a noncohesive power-law failure envelope. The formulation is made parametrically in terms of the instantaneous friction angle, and the key idea to obtain the bearing capacity is that information can be transmitted from the free surface (where external loads are known) to the contact plane of the foundation. The methodology can consider foundations adjacent to a slope, external surcharges at the free surface, and inclined loads (both on the slope and on the foundation). Sensitivity analyses illustrate the influence on bearing capacity of changes in the different geometrical parameters involved. An application example is presented and design plots are provided, and model predictions are compared with results of bearing capacity tests under low gravity.

Life cycle assessment of concentrated solar power (CSP) and the influence of hybridising with natural gas

Purpose Concentrating Solar Power (CSP) plants based on parabolic troughs utilize auxiliary fuels (usually natural gas) to facilitate start-up operations, avoid freezing of HTF and increase power output. This practice has a significant effect on the environmental performance of the technology. The aim of this paper is to quantify the sustainability of CSP and to analyse how this is affected by hybridisation with different natural gas (NG) inputs. Methods A complete Life Cycle (LC) inventory was gathered for a commercial wet-cooled 50 MWe CSP plant based on parabolic troughs. A sensitivity analysis was conducted to evaluate the environmental performance of the plant operating with different NG inputs (between 0 and 35% of gross electricity generation). ReCiPe Europe (H) was used as LCA methodology. CML 2 baseline 2000 World and ReCiPe Europe E were used for comparative purposes. Cumulative Energy Demands (CED) and Energy Payback Times (EPT) were also determined for each scenario. Results and discussion Operation of CSP using solar energy only produced the following environmental profile: climate change 26.6 kg CO2 eq/KWh, human toxicity 13.1 kg 1,4-DB eq/KWh, marine ecotoxicity 276 g 1,4-DB eq/KWh, natural land transformation 0.005 m2/KWh, eutrophication 10.1 g P eq/KWh, acidification 166 g SO2 eq/KWh. Most of these impacts are associated with extraction of raw materials and manufacturing of plant components. The utilization NG transformed the environmental profile of the technology, placing increasing weight on impacts related to its operation and maintenance. Significantly higher impacts were observed on categories like climate change (311 kg CO2 eq/MWh when using 35 % NG), natural land transformation, terrestrial acidification and fossil depletion. Despite its fossil nature, the use of NG had a beneficial effect on other impact categories (human and marine toxicity, freshwater eutrophication and natural land transformation) due to the higher electricity output achieved. The overall environmental performance of CSP significantly deteriorated with the use of NG (single score 3.52 pt in solar only operation compared to 36.1 pt when using 35 % NG). Other sustainability parameters like EPT and CED also increased substantially as a result of higher NG inputs. Quasilinear second-degree polynomial relationships were calculated between various environmental performance parameters and NG contributions. Conclusions Energy input from auxiliary NG determines the environmental profile of the CSP plant. Aggregated analysis shows a deleterious effect on the overall environmental performance of the technology as a result of NG utilization. This is due primarily to higher impacts on environmental categories like climate change, natural land transformation, fossil fuel depletion and terrestrial acidification. NG may be used in a more sustainable and cost-effective manner in combined cycle power plants, which achieve higher energy conversion efficiencies.