Solidly Mounted Resonators with Carbon Nanotube Electrodes for Biosensing Applications

The work reported here shows a direct experimental comparison of the sensitivities of AlN solidly mounted resonators (SMR)-based biosensors fabricated with standard metal electrodes and with carbon nanotube electrodes. SMRs resonating at frequencies around 1.75 GHz have been fabricated, some devices using a thin film of multi-wall carbon nanotubes (CNTs) as the top electrode material and some identical devices using a chromium/gold electrode. Protein solutions with different concentrations were loaded on the top of the resonators and their responses to mass-load from physically adsorbed coatings were investigated. Results show that resonators using CNTs as the top electrode material exhibited higher frequency change for a given load due to the higher active surface area of a thin film of interconnecting CNTs compared to that of a metal thin film electrode and hence exhibited greater mass loading sensitivity. It is therefore concluded that the use of CNT electrodes on resonators for their use as gravimetric biosensors is viable and worthwhile.

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.

Polyaniline-coated carbon papers for supercapacitor electrodes

Graphene and carbon nanotubes are promising materials for supercapacitor electrodes because of their high specific surface area and excellent electrical, thermal, and mechanical properties. However, these materials suffer from a high manufacturing cost and some aggregation of graphene layers or the presence of toxic residual metallic impurities of carbon nanotubes.

Polymer interaction with macroscopic carbon nanotube fibres and fabrication of nanostructured composites

El ensamblado de nanotubos de carbono (CNT) como una fibra macroscópica en la cual están orientados preferentemente paralelos entre sí y al eje de la fibra, ha dado como resultado un nuevo tipo de fibra de altas prestaciones derivadas de la explotación eficiente de las propiedades axiales de los CNTs, y que tiene un gran número de aplicaciones potenciales. Fibras continuas de CNTs se produjeron en el Instituto IMDEA Materiales mediante el proceso de hilado directo durante la reacción de síntesis por deposición química de vapores. Uno de los objetivos de esta tesis es el estudio de la estructura de estas fibras mediante técnicas del estado del arte de difracción de rayos X de sincrotrón y la elaboración de un modelo estructural de dicho material. Mediciones texturales de adsorción de gases, análisis de micrografías de electrones y dispersión de rayos X de ángulo alto y bajo (WAXS/SAXS) indican que el material tiene una estructura mesoporosa con una distribución de tamaño de poros ancha derivada del amplio rango de separaciones entre manojos de CNTs, así como una superficie específica de 170m2/g. Los valores de dimensión fractal obtenidos mediante SAXS y análisis Barrett-Joyner-Halenda (BJH) de mediciones texturales coinciden en 2.4 y 2.5, respectivamente, resaltando el carácter de red de la estructura de dichas fibras. La estructura mesoporosa y tipo hilo de las fibra de CNT es accesible a la infiltración de moléculas externas (líquidos o polímeros). En este trabajo se estudian los cambios en la estructura multiescala de las fibras de CNTs al interactuar con líquidos y polímeros. Los efectos de la densificación en la estructura de fibras secas de CNT son estudiados mediante WAXS/SAXS. El tratamiento de densificación junta los manojos de la fibra (los poros disminuyen de tamaño), resultando en un incremento de la densidad de la fibra. Sin embargo, los dominios estructurales correspondientes a la transferencia de esfuerzo mecánica y carga eléctrica en los nanotubos no son afectados durante este proceso de densificación; como consecuencia no se produce un efecto sustancial en las propiedades mecánicas y eléctricas. Mediciones de SAXS and fibra de CNT antes y después de infiltración de líquidos confirman la penetración de una gran cantidad de líquidos que llena los poros internos de la fibra pero no se intercalan entre capas de nanotubos adyacentes. La infiltración de cadenas poliméricas de bajo peso molecular tiende a expandir los manojos en la fibra e incrementar el ángulo de apertura de los poros. Los resultados de SAXS indican que la estructura interna de la fibra en términos de la organización de las capas de tubos y su orientación no es afectada cuando las muestras consisten en fibras infiltradas con polímeros de alto peso molecular. La cristalización de varios polímeros semicristalinos es acelerada por la presencia de fibras de CNTs alineados y produce el crecimiento de una capa transcristalina normal a la superficie de la fibra. Esto es observado directamente mediante microscopía óptica polarizada, y detectado mediante calorimetría DSC. Las lamelas en la capa transcristalina tienen orientación de la cadena polimérica paralela a la fibra y por lo tanto a los nanotubos, de acuerdo con los patrones de WAXS. Esta orientación preferencial se sugiere como parte de la fuerza impulsora en la nucleación. La nucleación del dominio cristalino polimérico en la superficie de los CNT no es epitaxial. Ocurre sin haber correspondencia entre las estructuras cristalinas del polímero y los nanotubos. Estas observaciones contribuyen a la compresión del fenómeno de nucleación en CNTs y otros nanocarbonos, y sientan las bases para el desarrollo de composites poliméricos de gran escala basados en fibra larga de CNTs alineados. ABSTRACT The assembly of carbon nanotubes into a macroscopic fibre material where they are preferentially aligned parallel to each other and to the fibre axis has resulted in a new class of high-performance fibres, which efficiently exploits the axial properties of the building blocks and has numerous applications. Long, continuous CNT fibres were produced in IMDEA Materials Institute by direct fibre spinning from a chemical vapour deposition reaction. These fibres have a complex hierarchical structure covering multiple length scales. One objective of this thesis is to reveal this structure by means of state-of-the-art techniques such as synchrotron X-ray diffraction, and to build a model to link the fibre structural elements. Texture and gas absorption measurements, using electron microscopy, wide angle and small angle X-ray scattering (WAXS/SAXS), and pore size distribution analysis by Barrett-Joyner-Halenda (BJH), indicate that the material has a mesoporous structure with a wide pore size distribution arising from the range of fibre bundle separation, and a high surface area _170m2/g. Fractal dimension values of 2.4_2.5 obtained from the SAXS and BJH measurements highlight the network structure of the fibre. Mesoporous and yarn-like structure of CNT fibres make them accessible to the infiltration of foreign molecules (liquid or polymer). This work studies multiscale structural changes when CNT fibres interact with liquids and polymers. The effects of densification on the structure of dry CNT fibres were measured by WAXS/SAXS. The densification treatment brings the fibre bundles closer (pores become smaller), leading to an increase in fibre density. However, structural domains made of the load and charge carrying nanotubes are not affected; consequently, it has no substantial effect on mechanical and electrical properties. SAXS measurements on the CNT fibres before and after liquid infiltration imply that most liquids are able to fill the internal pores but not to intercalate between nanotubes. Successful infiltration of low molecular weight polymer chains tends to expand the fibre bundles and increases the pore-opening angle. SAXS results indicate that the inner structure of the fibre, in terms of the nanotube layer arrangement and the fibre alignment, are not largely affected when infiltrated with polymers of relatively high molecular weight. The crystallisation of a variety of semicrystalline polymers is accelerated by the presence of aligned fibres of CNTs and results in the growth of a transcrystalline layer perpendicular to the fibre surface. This can be observed directly under polarised optical microscope, and detected by the exothermic peaks during differential scanning calorimetry. The discussion on the driving forces for the enhanced nucleation points out the preferential chain orientation of polymer lamella with the chain axis parallel to the fibre and thus to the nanotubes, which is confirmed by two-dimensional WAXS patterns. A non-epitaxial polymer crystal growth habit at the CNT-polymer interface is proposed, which is independent of lattice matching between the polymer and nanotubes. These findings contribute to the discussion on polymer nucleation on CNTs and other nanocarbons, and their implication for the development of large polymer composites based on long and aligned fibres of CNTs.

AlN-based BAW resonators with CNT electrodes for gravimetric biosensing

Solidly mounted resonators (SMRs) with a top carbon nanotubes (CNTs) surface coating that doubles as an electrode and as a sensing layer have been fabricated. The influence of the CNTs on the frequency response of the resonators was studied by direct comparison to identical devices with a top metallic electrode. It was found that the CNTs introduced significantly less mass load on the resonators and these devices exhibited a greater quality factor, Q (>2000, compared to ∼1000 for devices with metal electrodes), which increases the gravimetric sensitivity of the devices by allowing the tracking of smaller frequency shifts. Protein solutions with different concentrations were loaded on the top of the resonators and their responses to mass-load from physically adsorbed coatings were investigated. Results show that resonators using CNTs as the top electrode exhibited a higher frequency change for a given load (∼0.25 MHz cm2 ng−1) compared to that of a metal thin film electrode (∼0.14 MHz cm2 ng−1), due to the lower mass of the CNTelectrodes and their higher active surface area compared to that of a thin film metal electrode. It is therefore concluded that the use of CNTelectrodes on resonators for their use as gravimetric biosensors is a significant improvement over metallic electrodes that are normally employed.

Remote sensing of LAI, chlorophyll and leaf nitrogen pools of crop- and grasslands in five European landscapes.

Leaf nitrogen and leaf surface area influence the exchange of gases between terrestrial ecosystems and the atmosphere, and play a significant role in the global cycles of carbon, nitrogen and water. The purpose of this study is to use field-based and satellite remote-sensing-based methods to assess leaf nitrogen pools in five diverse European agricultural landscapes located in Denmark, Scotland (United Kingdom), Poland, the Netherlands and Italy. REGFLEC (REGularized canopy reFLECtance) is an advanced image-based inverse canopy radiative transfer modelling system which has shown proficiency for regional mapping of leaf area index (LAI) and leaf chlorophyll (CHLl) using remote sensing data. In this study, high spatial resolution (10–20 m) remote sensing images acquired from the multispectral sensors aboard the SPOT (Satellite For Observation of Earth) satellites were used to assess the capability of REGFLEC for mapping spatial variations in LAI, CHLland the relation to leaf nitrogen (Nl) data in five diverse European agricultural landscapes. REGFLEC is based on physical laws and includes an automatic model parameterization scheme which makes the tool independent of field data for model calibration. In this study, REGFLEC performance was evaluated using LAI measurements and non-destructive measurements (using a SPAD meter) of leaf-scale CHLl and Nl concentrations in 93 fields representing crop- and grasslands of the five landscapes. Furthermore, empirical relationships between field measurements (LAI, CHLl and Nl and five spectral vegetation indices (the Normalized Difference Vegetation Index, the Simple Ratio, the Enhanced Vegetation Index-2, the Green Normalized Difference Vegetation Index, and the green chlorophyll index) were used to assess field data coherence and to serve as a comparison basis for assessing REGFLEC model performance. The field measurements showed strong vertical CHLl gradient profiles in 26% of fields which affected REGFLEC performance as well as the relationships between spectral vegetation indices (SVIs) and field measurements. When the range of surface types increased, the REGFLEC results were in better agreement with field data than the empirical SVI regression models. Selecting only homogeneous canopies with uniform CHLl distributions as reference data for evaluation, REGFLEC was able to explain 69% of LAI observations (rmse = 0.76), 46% of measured canopy chlorophyll contents (rmse = 719 mg m−2) and 51% of measured canopy nitrogen contents (rmse = 2.7 g m−2). Better results were obtained for individual landscapes, except for Italy, where REGFLEC performed poorly due to a lack of dense vegetation canopies at the time of satellite recording. Presence of vegetation is needed to parameterize the REGFLEC model. Combining REGFLEC- and SVI-based model results to minimize errors for a "snap-shot" assessment of total leaf nitrogen pools in the five landscapes, results varied from 0.6 to 4.0 t km−2. Differences in leaf nitrogen pools between landscapes are attributed to seasonal variations, extents of agricultural area, species variations, and spatial variations in nutrient availability. In order to facilitate a substantial assessment of variations in Nl pools and their relation to landscape based nitrogen and carbon cycling processes, time series of satellite data are needed. The upcoming Sentinel-2 satellite mission will provide new multiple narrowband data opportunities at high spatio-temporal resolution which are expected to further improve remote sensing capabilities for mapping LAI, CHLl and Nl.

Volume, Surface, Connectivity and Size Distribution of Soil Pore Space in CT Images: Comparison of Samples at Different Depths from Nearby Natural and Tillage Areas

The study of soil structure, i.e., the pores, is of vital importance in different fields of science and technology. Total pore volume (porosity), pore surface, pore connectivity and pore size distribution are some (probably the most important) of the geometric measurements of pore space. The technology of X-ray computed tomography allows us to obtain 3D images of the inside of a soil sample enabling study of the pores without disturbing the samples. In this work we performed a set of geometrical measures, some of them from mathematical morphology, to assess and quantify any possible difference that tillage may have caused on the soil. We compared samples from tilled soil with samples from a soil with natural vegetation taken in a very close area. Our results show that the main differences between these two groups of samples are total surface area and pore connectivity per unit pore volume.

Graphene foam functionalized with electrodeposited nickel hydroxide for energy applications

The need of new systems for the storage and conversion of renewable energy sources is fueling the research in supercapacitors. In this work, we propose a low temperature route for the synthesis of electrodes for these supercapacitors: electrodeposition of a transition metal hydroxide–Ni(OH)2 on a graphene foam. This electrode combines the superior mechanical and electrical properties of graphene, the large specific surface area of the foam and the large pseudocapacitance of Ni(OH)2. We report a specific capacitance up to 900 F/g as well as specific power and energy comparable to active carbon electrodes. These electrodes are potential candidates for their use in energy applications.

Comportamiento térmico y mecánico del yeso con adiciones de aerogel de sílice granulado

La presente tesis doctoral aborda el estudio de un nuevo material mineral, compuesto principalmente por una matriz de yeso (proveniente de un conglomerante industrial basado en sulfato de calcio multifase) y partículas de aerogel de sílice hidrófugo mesoporoso, compatibilizadas mediante un surfactante polimérico, debido a su alto carácter hidrófugo. La investigación se centra en conocer los factores que influyen en las propiedades mecánicas y conductividad térmica del material compuesto generado. Este estudio pretende contribuir al conocimiento sobre el desarrollo de nuevos morteros de elevado aislamiento térmico que puedan ser utilizados en la rehabilitación energética de edificios de viviendas existentes, debido a que estos representan gran parte del consumo energético del parque de viviendas de España, aunque también a nivel internacional. De los materiales utilizados para desarrollar los morteros estudiados, el yeso, además de ser un material muy abundante, especialmente en España, requiere una menor cantidad de energía para la fabricación de un conglomerante (debido a una menor temperatura de fabricación), en comparación con el cemento o la cal, por lo que presenta una menor huella de carbono que estos últimos. Por otro lado, el aerogel de sílice hidrófugo mesoporoso es, de acuerdo con la documentación disponible, el material que posee actualmente la mayor capacidad de aislamiento térmico en el mercado. El desarrollo de nuevos morteros minerales con una capacidad de aislamiento térmico mayor que los materiales aislantes utilizados tradicionalmente, tiene una aplicación relevante en los casos de rehabilitación energética de edificios históricos y patrimoniales, en los que se requiere la aplicación del aislamiento por el interior de la fachada, ya que este tipo de soluciones tienen el inconveniente de reducir el espacio habitable de las áreas involucradas, especialmente en zonas climáticas en las que el aislamiento térmico puede suponer un espesor considerable, por lo que es ideal utilizar materiales de altas prestaciones de aislamiento térmico capaces de aportar el mismo nivel de aislamiento (o incluso mayor), pero en un espesor considerablemente menor. La investigación se desarrolla en tres etapas: bibliográfica, experimental y de simulación. La primera etapa, parte del estudio de la bibliografía existente, relacionada con materiales aislantes, incluyendo soluciones basadas, tanto en morteros aislantes, como en paneles de aislamiento térmico. La segunda, de carácter experimental, se centra en estudiar la influencia de la microestrucrura y macroestructura, del nuevo material mineral, en las propiedades físicas elementales, mecánicas y conductividad térmica del compuesto. La tercera etapa, mediante una simulación del consumo energético, consiste en cuantificar teóricamente el potencial ahorro energético que puede aportar este material en un caso de rehabilitación energética en particular. La investigación experimental se centró principalmente en conocer los factores principales que influyen en las propiedades mecánicas y conductividad térmica de los materiales compuestos minerales desarrollados en esta tesis. Para ello, se llevó a cabo una caracterización de los materiales de estudio, así como el desarrollo de distintas muestras de ensayo, de tal forma que se pudo estudiar, tanto la hidratación del yeso en los compuestos, como su posterior microestructura y macroestructura, aspectos fundamentales para el entendimiento de las propiedades mecánicas y conductividad térmica del compuesto aislante. De este modo, se pudieron conocer y cuantificar, los factores que influyen en las propiedades estudiadas, aportando una base de conocimiento y entendimiento de este tipo de compuestos minerales con aerogel de sílice hidrófugo, no existiendo estudios publicados hasta el momento de finalización de esta tesis, con la aproximación al material propuesta en este estudio, ni con yeso (basado en sulfato de calcio multifase), ni con otro tipo de conglomerantes. Particularmente, se determinó la influencia que tiene la incorporación de partículas de aerogel de sílice hidrófugo, en grandes proporciones en volumen, en un compuesto mineral basado en distintas fases de sulfato de calcio. No obstante, para llevar a cabo las mezclas, fue necesario utilizar un surfactante para compatibilizar este tipo de partículas, con el conglomerante basado en agua. El uso de este tipo de aditivos tiene una influencia, no solo en el aerogel, sino en las propiedades del compuesto en general, dependiendo de su concentración, por lo que se establecieron dos porcentajes de adición: la primera, determinada a partir de la cantidad mínima necesaria para compatibilizar las mezclas (0,1% del agua de amasado), y la segunda, como límite superior, la concentración utilizada habitualmente a nivel industrial para estabilizar burbujas de aire en hormigones espumados (5%). El surfactante utilizado mostró la capacidad de modificar la superficie del aerogel, cambiando el comportamiento de las partículas frente al agua, permitiendo una invasión parcial de su estructura porosa, por parte del agua de amasado. Este comportamiento supone un aumento muy importante en la relación agua/yeso, afectando el hábito cristalino e influenciando negativamente las propiedades mecánicas de la matriz de yeso, presentando un efecto aún notable a mayor concentración de surfactante (5%). En cuanto a las propiedades finales alcanzadas, fue posible lograr un compuesto mineral ultraligero (200 kg/m3), con alrededor de un 60% de aerogel en volumen y de alta capacidad aislante (0,028 W/m•K), presentando una conductividad térmica notablemente menor que los morteros aislantes del mercado, e incluso también menor que la de los aislantes tradicionales basado en las lanas minerales o EPS; no obstante, con la limitante de presentar bajas propiedades mecánicas, condicionando su posible aplicación futura. Entre los factores principales relacionados con las propiedades mecánicas, se encontró que estas dependen exponencialmente del volumen de yeso en el compuesto; no obstante, factores de segundo orden, como el grado de hidratación, o una mejor distribución del conglomerante entre las partículas de aerogel, debido al aumento de la superficie específica del polvo mineral, pueden aumentar las propiedades mecánicas entre el doble y el triple, dependiendo del volumen de aerogel en cuestión. Además, se encontró que el aerogel, en conjunto con el surfactante, es capaz de introducir una gran cantidad de aire (0,70 m3 por cada m3 de aerogel), que unido al agua evaporada (no consumida por el conglomerante durante la hidratación), el volumen de aire total alcanza, generalmente, un 40%, independientemente de la cantidad de aerogel en la mezcla. De este modo, el aire introducido en la matriz desplaza las proporciones en volumen del aerogel y del yeso, disminuyendo, tanto las propiedades mecánicas, como la capacidad aislante de compuesto mineral. Por otro lado, la conductividad térmica mostró tener una dependencia directa de la contribución de las tres fases principales en el compuesto: yeso, aerogel y aire ocluido. De este modo, se pudo desarrollar un modelo matemático, adaptado de uno existente, capaz de calcular, con bastante precisión, la relación de los tres componentes mencionados, en la conductividad térmica de los compuestos, para el rango de volúmenes y materiales utilizados en esta tesis. Finalmente, la simulación del consumo energético realizada a una vivienda típica de España, de los años 1900 a 1959 (basada en muros de ladrillo macizo), para las zonas climáticas estudiadas (A, D y E), permitió observar el potencial ahorro energético que puede aportar este material, dependiendo de su espesor, como aislamiento interior de los muros de fachada. Particularmente, para la zona A, se determinó un espesor óptimo de 1 cm, mientras que para la zona D y E, 3,5 y 3,9 cm respectivamente. En este sentido, el nuevo material estudiado es capaz de disminuir, entre un 35% y un 80%, el espesor de la capa aislante, en comparación con paneles de lana de roca o los morteros minerales de mayor capacidad aislante del mercado español respectivamente. ABSTRACT The present doctoral thesis studies a new mineral-based composite material, composed by a gypsum matrix (based on an industrial multiphase gypsum binder) and mesoporous hydrophobic silica aerogel particles, compatibilized with a polymeric surfactant due to the high hydrophobic character of the insulating particles. This study pretends to contribute to the development of new composite insulating materials that could be used in energy renovation of existing dwellings, in order to reduce their high energy consumption, as they represent a great part of the total energy consumed in Spain, but also internationally. Between the materials used to develop de studied insulating mortars, gypsum, besides being an abundant material, especially in Spain, requires less energy for the manufacture of a mineral binder (due to lower manufacturing temperatures), compared to lime or cement, thus presenting lower carbon footprint. In other hand, the hydrophobic mesoporous silica aerogel, is, according to the existing references, the material with the highest know insulating capacity in the market. The development of new mineral mortars with higher thermal insulation capacity than traditional insulating materials, presents a relevant application in energy retrofitting of historic and cultural heritage buildings, in which implies that the insulating material should be installed as an internal layer, rather than as an external insulating system. This type of solution involves a reduced internal useful area, especially in climatic zones where the demand for thermal insulation is higher, and so the insulating layer thickness, being idealistic to use materials with very high insulating properties, in order to reach same insulating level (or higher), but in lower thickness than the provided by traditional insulating materials. This research is developed in three main stages: bibliographic, experimental and simulation. The first stage starts by studying the existing references regarding thermally insulating materials, including existing insulating mortars and insulating panels. The second stage, mainly experimental, is centered in the study of the the influence of the microstructure and macrostructure in the physical and mechanical properties, and also in the thermal conductivity of the new mineral-based material. The thirds stage, through energy simulation, consists in theoretically quantifying the energy savings potential that can provide this type of insulating material, in a particular energy retrofitting case study. The experimental research is mainly focused in the study of the factors that influence the mechanical properties and the thermal conductivity of the thermal insulating mineral composites developed in this thesis. For this, the characterization of the studied materials has been performed, as well as the development of several experimental samples, in order to study the hydration of the mineral binder within the composites, but also the final microstructure and macrostructure, fundamental aspects for the understanding of the composite’s mechanical and insulating properties. Thus, is was possible to determine and quantify the factors that influence the studied material properties, providing a knowledge base and understanding of mineral composites that comprises mesoporous hydrophobic silica aerogel particles, being the first study up to date regarding the specific approach of the present study, regarding not just multiphase calcium sulfate plaster, but also other mineral binders. Particularly, the influence of the incorporation of hydrophobic silica aerogel particles, in high volume ratios into a mineral compound, based on different phases of calcium sulfate has been determined. However, to perform mixing, it is necessary to use a surfactant in order to compatibilize these particles with the water-based mineral binder. The use of such additives has an influence, not only in the aerogel, but the overall properties of the compound, so two different surfactant concentration has been studied: the first, the minimum amount of surfactant (used in this thesis) in order to develop the slurries (0.1% concentration of the mixing water), and the second, as the upper limit, the concentration usually used industrially to stabilize air bubbles in foamed concrete (5%). One of the side effects of using such additive, was the modification of the aerogel particles, by changing their behavior in respect to water, generating a partial invasion of the aerogel’s porous structure, by the mixing water. This behavior produces a very important increase in water/binder ratios, affecting the crystal habit and negatively influencing the mechanical properties of the gypsum matrix. This effect further increased when a higher concentration of surfactant (5%) is used. Regarding final materials properties, it was possible to achieve an ultra-lightweight mineral composite (200 kg/m3), with around 60% by volume of aerogel, presenting a very high insulating capacity (0.028 W/m•K), a noticeable lower thermal conductivity compared to the insulating mortars and traditional thermal insulating panels on the market, such as mineral wool or EPS; however, the limiting factor for future’s material application in buildings, is related to the very low mechanical properties achieved. Among the main factors related to the mechanical properties, it has been found an exponential correlation to the volume of gypsum in the composite. However, second-order factors such as the degree of hydration, or a better distribution of the binder between the aerogel particles, due to the increased surface area of the mineral powder, can increase the mechanical properties between two to three times, depending aerogel volume involved. In addition, it was found that the aerogel, together with the surfactant, is able to entrain a large amount of air volume (around 0.70 m3 per m3 of aerogel), which together with the evaporated water (not consumed by the binder during hydration), can reach generally around 40% of entrained air within the gypsum matrix, regardless of the amount of aerogel in the mixture. Thus, the entrained air into the matrix displaces the volume proportions of the aerogel and gypsum, reducing both mechanical and insulating properties of the mineral composite. On the other hand, it has been observed a direct contribution of three main phases into the thermal conductivity of the composite: gypsum, aerogel and entrained air. Thus, it was possible to develop a mathematical model (adapted from an existing one), capable of calculating quite accurate the thermal conductivity of such mineral composites, from the ratio these three components and for the range of volumes and materials used in this thesis. Finally, the energy simulation performed to a typical Spanish dwelling, from the years 1900 to 1959 (mainly constructed with massive clay bricks), within three climatic zones of Spain (A, D and E), showed the energy savings potential that can provide this type of insulating material, depending on the thickness of the applied layer. Particularly, for the climatic A zone, it has been found an optimal layer thickness of 1 cm, while for zone D and E, 3.5 and 3.9 cm respectively. In this manner, the new studied materials is capable of decreasing the thickness of the insulating layer by 35% and 80%, compared with rock wool panels or mineral mortars with the highest insulating performance of the Spanish market respectively.

Comportamiento electroquímico y en pila de combustible de cátodos fabricados mediante evaporacion electrónica de Pt frente a electrodos comerciales

(SPA) Con el objetivo de disminuir el coste de los electrodos utilizados en las pilas de combustible de membrana polimérica se ha llevado a cabo un estudio de la influencia sobre la respuesta electroquímica y en ensayos en monocelda de pila de combustible de alcohol directo, de la deposición por evaporación electrónica de platino sobre tela de carbón. Se han estudiado en las mismas condiciones dos electrodos comerciales con distinta carga de catalizador y dos electrodos preparados por evaporación electrónica de platino. Se encuentra que la evaporación electrónica de platino sobre tela de carbón ahorra carga de catalizador, aumenta la superficie electroactiva y permite alcanzar rendimientos comparables a los de los electrodos comerciales, mejorando mucho la potencia obtenida por unidad de masa de material catalítico. (ENG) In order to diminish the cost of the electrodes used in polymer membrane fuel cells a study of the influence on the electrochemical response and essays in a single direct methanol fuel cell of the deposition by electronic evaporation of Platinum on carbon cloth has been carried out. Two commercial electrodes with different catalyst loading and two electrodes prepared by electronic evaporation of Platinum have been studied in the same conditions. It can be concluded that electronic evaporation of Platinum on carbon cloth saves catalyst load, increases the electroactive surface area and reaches fuel cell performances comparable with those obtained using commercial electrodes, improving clearly the power obtained per unit mass of catalytic material.