Bifurcation diagrams for polymer blends with diffuse interfaces in confined and adaptive geometries

Dynamics of binary mixtures such as polymer blends, and fluids near the critical point, is described by the model-H, which couples momentum transport and diffusion of the components [1]. We present an extended version of the model-H that allows to study the combined effect of phase separation in a polymer blend and surface structuring of the film itself [2]. We apply it to analyze the stability of vertically stratified base states on extended films of polymer blends and show that convective transport leads to new mechanisms of instability as compared to the simpler diffusive case described by the Cahn- Hilliard model [3, 4]. We carry out this analysis for realistic parameters of polymer blends used in experimental setups such as PS/PVME. However, geometrically more complicated states involving lateral structuring, strong deflections of the free surface, oblique diffuse interfaces, checkerboard modes, or droplets of a component above of the other are possible at critical composition solving the Cahn Hilliard equation in the static limit for rectangular domains [5, 6] or with deformable free surfaces [6]. We extend these results for off-critical compositions, since balanced overall composition in experiments are unusual. In particular, we study steady nonlinear solutions of the Cahn-Hilliard equation for bidimensional layers with fixed geometry and deformable free surface. Furthermore we distinguished the cases with and without energetic bias at the free surface. We present bifurcation diagrams for off-critical films of polymer blends with free surfaces, showing their free energy, and the L2-norms of surface deflection and the concentration field, as a function of lateral domain size and mean composition. Simultaneously, we look at spatial dependent profiles of the height and concentration. To treat the problem of films with arbitrary surface deflections our calculations are based on minimizing the free energy functional at given composition and geometric constraints using a variational approach based on the Cahn-Hilliard equation. The problem is solved numerically using the finite element method (FEM).

Thermodynamics of zinc insertion in CuGaS2:Ti, used as a modulator agent in an intermediate-band photovoltaic material

An intermediate-bandphotovoltaicmaterial, which has an isolated metallic band located between the top of the valence band and bottom of the conduction band of some semiconductors, has been proposed as third generation solar cell to be used in photovoltaic applications. Density functional theory calculations of Zn in CuGaS2:Ti have previously shown that, the intermediate-band position can be modulated in proportion of Zn insertion in such a way that increasing Zn concentration can lead to aband-gap reduction, and an adjustment of the intermediate-band position. This could be interesting in the formation of an intermediate-bandmaterial, that has the maximum efficiency theoretically predicted for the intermediate-band solar cell. In this work, the energetics of several reaction schemes that could lead to the decomposition of the modulated intermediate-bandphotovoltaicmaterial, CuGaS2:Ti:Zn, is studied in order to assess the thermodynamic stability of this material. Calculations of the total free energy and disorder entropy have been taken into account, to get the reaction energy and free energy of the compound decomposition, which is found to be thermodynamically favorable

Biokerosene from Babassu and Camelina Oils: production and properties of their blends with fossil kerosene

Babassu and camelina oils have been transesterified with methanol by the classical homogeneous basic catalysis method with good yields. The babassu fatty acid methyl ester (FAME) has been subjected to fractional distillation at vacuum, and the low boiling point fraction has been blended with two types of fossil kerosene, a straight-run atmospheric distillation cut (hydrotreated) and a commercial Jet-A1. The camelina FAME has been blended with the fossil kerosene without previous distillation. The blends of babassu biokerosene and Jet-A1 have met some of the specifications selected for study of the ASTM D1655 standard: smoke point, density, flash point, cloud point, kinematic viscosity, oxidative stability and lower heating value. On the other hand, the blends of babassu biokerosene and atmospheric distillation cut only have met the density parameter and the oxidative stability. The blends of camelina FAME and atmospheric distillation cut have met the following specifications: density, kinematic viscosity at −20 °C, and lower heating value. With these preliminary results, it can be concluded that it would be feasible to blend babassu and camelina biokerosenes prepared in this way with commercial Jet-A1 up to 10 vol % of the former, if these blends prove to accomplish all the ASTM D1655-09 standards.

Biokerosene from coconut, babassu, camelina and palm kernel oils: production and properties of their blends with fossil kerosene

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). On July 8th 2009, the European Parliament and Conseil agreed that all flights leaving or landing in the EU airports starting from January 1st 2012 should be included in the EUETS. On November 19th 2008, the EU Directive 2008/101/CE [1] included the civil aviation activities in the EUETS, and this directive was transposed by the Spanish law 13/2010 of July 5th 2010 [2]. Thus, in 2012 the aviation sector should reduce their emissions to 97 % of the mean values registered in the period 2004-2006, and for 2013 these emission reductions should reach 95 % of the mean values for that same period. Trying to face this situation, the aviation companies are planning seriously the use of alternative jet fuels to reduce their greenhouse gas emissions and to lower their costs. However, some US airlines have issued a lawsuit before the European Court of Justice based in that this EU action violates a long standing worldwide aviation treaty, the Chicago convention of 1944, and also the Chinese aviation companies have rejected to pay any EU carbon dioxide tax [3]. Moreover, the USA Departments of Agriculture and Energy and the Navy will invest a total of up to $150 million over three years to spur production of aviation and marine biofuels for commercial and military applications [4]. However, the jet fuels should fulfill a set of extraordinarily sensitive properties to guarantee the safety of planes and passengers during all the flights.

Oxygen extended sooting index of FAME blends with aviation kerosene

The use of biofuels in the aviation sector has economic and environmental benefits. Among the options for the production of renewable jet fuels, hydroprocessed esters and fatty acids (HEFA) have received predominant attention in comparison with fatty acid methyl esters (FAME), which are not approved as additives for jet fuels. However, the presence of oxygen in methyl esters tends to reduce soot emissions and therefore particulate matter emissions. This sooting tendency is quantified in this work with an oxygen-extended sooting index, based on smoke point measurements. Results have shown considerable reduction in the sooting tendency for all biokerosenes (produced by transesterification and eventually distillation) with respect to fossil kerosenes. Among the tested biokerosenes, that made from palm kernel oil was the most effective one, and nondistilled methyl esters (from camelina and linseed oils) showed lower effectiveness than distilled biokerosenes to reduce the sooting tendency. These results may constitute an additional argument for the use of FAME’s as blend components of jet fuels. Other arguments were pointed out in previous publications, but some controversy has aroused over the use of these components. Some of the criticism was based on the fact that the methods used in our previous work are not approved for jet fuels in the standard methods and concluded that the use of FAME in any amount is, thus, inappropriate. However, some of the standard methods are not updated for considering oxygenated components (like the method for obtaining the lower heating value), and others are not precise enough (like the methods for measuring the freezing point), whereas some alternative methods may provide better reproducibility for oxygenated fuels.

Polarization properties of polymer-based photonic crystal fibers

Selectively filled photonic crystal fibers with polydimethylsiloxane (PDMS), a silicon-type material, have been studied. Is has been demonstrated that polarization properties of these hybrid devices and the properties of the guided light in relation with the temperature changes, finding that the state of polarization (SOP) change with the increasing temperature but remains constant for a wide spectrum of wavelengths for a determinate temperature.

Long Term Performance Study of a Direct Methanol Fuel Cell Fed with Alcohol Blends

The use of alcohol blends in direct alcohol fuel cells may be a more environmentally friendly and less toxic alternative to the use of methanol alone in direct methanol fuel cells. This paper assesses the behaviour of a direct methanol fuel cell fed with aqueous methanol, aqueous ethanol and aqueous methanol/ethanol blends in a long term experimental study followed by modelling of polarization curves. Fuel cell performance is seen to decrease as the ethanol content rises, and subsequent operation with aqueous methanol only partly reverts this loss of performance. It seems that the difference in the oxidation rate of these alcohols may not be the only factor affecting fuel cell performance.

Airplane materials compatibility with blends of fossil kerosene jet a1 with biokerosenes from babassu, palm kernel and coconut oils

El desarrollo de bioqueroseno de diferentes orígenes y su uso creciente, hacen necesario el estudio de la compatibilidad estos nuevos combustibles con los materiales y recubrimientos con los que se encuentra en contacto. Por tanto, el presente proyecto estudia la compatibilidad de los bioquerosenos mezclados en diferentes proporciones con queroseno mineral, para evaluar posteriormente su compatibilidad con diferentes polímeros y composites presentes en la estructura de un avión.Currently there is a big interest to increase the sources of alternative fuels for aviation to get a reduction of their carbon footprint and the deep energetic dependence from fossil fuels of different countries. Although there are studies about how to produce this alternative fuel and how to accomplish the standards for a good performance in the aircraft turbines, there are no studies about how these fuels could affect the different materials of airplanes. In this context this work describes the compatibility of biokerosene blends of coconut, babassu and palm kernel with commercial Jet A-1 testing airplane polymeric materials, metals and composites. As a conclusion, all material samples show a good compatibility with the fuel blends tested.

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.

An eco-friendly way to fire retardant flexible polyurethane foam: layer-by-layer assembly of fully bio-based substances

The objective of the present study is to develop fully renewable and environmentally benign techniques for improving the fire safety of flexible polyurethane foams (PUFs). A multilayered coating made from cationic chitosan (CS) and anionic alginate (AL) was deposited on PUFs through layer-by-layer assembly. This coating system exhibits a slight influence on the thermal stability of PUF, but significantly improves the char formation during combustion. Cone calorimetry reveals that 10 CS-AL bilayers (only 5.7% of the foams weight) lead to a 66% and 11% reduction in peak heat release rate and total heat release, respectively, compared with those of the uncoated control. The notable decreased fire hazards of PUF are attributed to the CS-AL coatings being beneficial to form an insulating protective layer on the surface of burning materials that inhibits the oxygen and heat permeation and slows down the flammable gases in the vapor phase, and thereby improves the flame resistance. This water-based, environmentally benign natural coating will stimulate further efforts in improving fire safety for a variety of polymer substrates.

Investigación de mezclas de caucho, con bajo contenido en cloro, para bandas transportadoras con características ignífugas

El objeto de la tesis doctoral se centra en la obtención de una banda transportadora de minería exenta de halógenos o al menos con el menor contenido posible, es por ello que se ha realizado un estudio de diferentes matrices poliméricas sin halógenos y se han evaluado diferentes sistemas ignifugantes. Se ha partido de mezclas con base polimérica de caucho natural y de estireno butadieno ya que son cauchos sin halógenos y con los que se pueden obtener mezclas de buenas propiedades mecánicas. Los resultados obtenidos durante el desarrollo de la tesis han sido muy satisfactorios, ya que se fabricaron bandas a gran escala para poder realizar los ensayos descritos en la normativa UNE EN 14973. La clasificación adquirida, categoría B1, alcanza dos de los objetivos marcados al inicio de los trabajos de investigación, y por tanto puede dar lugar a: - La fabricación a nivel industrial - La comercialización de una banda retardante de llama para minería y obra subterránea, formulada con un nuevo aditivo que reduce notablemente el contenido en cloro. - Disminución de la contaminación derivada de los humos tóxicos producidos cuando una banda transportadora arde accidentalmente. Los aditivos retardantes de llama sin halógenos, son muy efectivos en dosis elevadas, para la obtención de mezclas con propiedades ignífugas, pero las propiedades mecánicas de las mezclas se debilitan. Se ha buscado un compromiso entre las propiedades ignífugas y mecánicas, por lo que resulta adecuado obtener aditivos que posean un tamaño de partícula tal que actúen como cargas semi-reforzantes para poder utilizarlos en mayor proporción y así poder conseguir las propiedades ignífugas deseadas sin alterar de forma significativa las demás propiedades de la mezcla. ABSTRACT The purpose of this thesis is to obtain a mining conveyor belt with minimal halogen content, with the final objective of being halogen-free. Several polymer matrices without halogen and as well as fireproof systems have been analyzed to achieve this goal. The polymer mixtures studied are based on natural rubber and styrene butadiene, due to the fact that are rubbers without halogens and which their mixtures have good mechanical properties. The outcome of the thesis research is satisfactory, since the results are manufactured conveyor belts that comply with the tests described in the UNE EN 14973. The obtained B1 classification achieves two objectives set at the beginning of the research, and therefore can lead to: - Manufacturing at industrial level - Marketing of a flame retardant conveyor belt for mining and underground works formulated with a new additive that significantly reduces the chlorine content - Reduce pollution produced of the toxic fumes generated when a conveyor accidentally burns Additive flame retardant halogen-free are very effective in high doses to obtain blends with flame retardant properties, but the mechanical properties of the blends are below standards. A compromise between the fire retardant and mechanical properties has been successfully obtained, making possible to obtain additives that show a particle size that act as semi-reinforcing load in order to use a greater extent and thus be able to achieve the pursued fire retardant properties without altering significant other properties of mixture.