Polymer-solvent interaction parameters of SBS rubbers by inverse gas chromatography measurements

The solubility parameters of two SBS commercial rubbers with different structures (lineal and radial), and with slightly different styrene content have been determined by inverse gas chromatography technique. The Flory–Huggins interaction parameters of several polymer–solvent mixtures have also been calculated. The influence of the polymer composition, the solvent molecular weight and the temperature over these parameters have been discussed; besides, these parameters have been compared with previous ones, obtained by intrinsic viscosity measurements. From the Flory–Huggins interaction parameters, the infinite dilution activity coefficients of the solvents have been calculated and fitted to the well-known NRTL model. These NRTL binary interaction parameters have a great importance in modelling the separation steps in the process of obtaining the rubber.

Aspectos de la medición dinámica instantánea de emisiones de motores. Aplicación al desarrollo de un equipo portátil y una metodología para estudios de contaminación de vehículos en tráfico real.

Esta Tesis Doctoral se encuadra en el ámbito de la medida de emisiones contaminantes y de consumo de combustible en motores de combustión interna alternativos cuando se utilizan como plantas de potencia para propulsión de vehículos ligeros de carretera, y más concretamente en las medidas dinámicas con el vehículo circulando en tráfico real. En este ámbito, el objetivo principal de la Tesis es estudiar los problemas asociados a la medición en tiempo real con equipos embarcados de variables medioambientales, energéticas y de actividad, de vehículos ligeros propulsados por motores térmicos en tráfico real. Y como consecuencia, desarrollar un equipo y una metodología apropiada para este objetivo, con el fin de realizar consiguientemente un estudio sobre los diferentes factores que influyen sobre las emisiones y el consumo de combustible de vehículos turismo en tráfico real. La Tesis se comienza realizando un estudio prospectivo sobre los trabajos de otros autores relativos al desarrollo de equipos portátiles de medida de emisiones (Portable Emission Measurement Systems – PEMS), problemas asociados a la medición dinámica de emisiones y estudios de aplicación en tráfico real utilizando este tipo de equipos. Como resultado de este estudio se plantea la necesidad de disponer de un equipo específicamente diseñado para ser embarcado en un vehículo que sea capaz de medir en tiempo real las concentraciones de emisiones y el caudal de gases de escape, al mismo tiempo que se registran variables del motor, del vehículo y del entorno como son la pendiente y los datos meteorológicos. De esta forma se establecen las especificaciones y condiciones de diseño del equipo PEMS. Aunque al inicio de esta Tesis ya existían en el mercado algunos sistemas portátiles de medida de emisiones (PEMS: Portable Emissions Measurement Systems), en esta Tesis se investiga, diseña y construye un nuevo sistema propio, denominado MIVECO – PEMS. Se exponen, discuten y justifican todas las soluciones técnicas incorporadas en el sistema que incluyen los subsistema de análisis de gases, subsistemas de toma de muestra incluyendo caudalímetro de gases de escape, el subsistema de medida de variables del entorno y actividad del vehículo y el conjunto de sistemas auxiliares. El diseño final responde a las hipótesis y necesidades planteadas y se valida en uso real, en banco de rodillos y en comparación con otro equipos de medida de emisiones estacionarios y portátiles. En esta Tesis se presenta también toda la investigación que ha conducido a establecer la metodología de tratamiento de las señales registradas en tiempo real que incluye la sincronización, cálculos y propagación de errores. La metodología de selección y caracterización de los recorridos y circuitos y de las pautas de conducción, preparación del vehículo y calibración de los equipos forma también parte del legado de esta Tesis. Para demostrar la capacidad de medida del equipo y el tipo de resultados que pueden obtenerse y que son útiles para la comunidad científica, y las autoridades medioambientales en la parte final de esta Tesis se plantean y se presentan los resultados de varios estudios de variables endógenas y exógenas que afectan a las emisiones instantáneas y a los factores de emisión y consumo (g/km) como: el estilo de conducción, la infraestructura vial, el nivel de congestión del tráfico, tráfico urbano o extraurbano, el contenido de biocarburante, tipo de motor (diesel y encendido provocado), etc. Las principales conclusiones de esta Tesis son que es posible medir emisiones másicas y consumo de motores de vehículos en uso real y que los resultados permiten establecer políticas de reducción de impacto medio ambiental y de eficiencia energética, pero, se deben establecer unas metodologías precisas y se debe tener mucho cuidado en todo el proceso de calibración, medida y postratamientos de los datos. Abstract This doctoral thesis is in the field of emissions and fuel consumption measurement of reciprocating internal combustion engines when are used as power-trains for light-duty road vehicles, and especially in the real-time dynamic measurements procedures when the vehicle is being driven in real traffic. In this context, the main objective of this thesis is to study the problems associated with on-board real-time measuring systems of environmental, energy and activity variables of light vehicles powered by internal combustion engines in real traffic, and as a result, to develop an instrument and an appropriate methodology for this purpose, and consequently to make a study of the different factors which influence the emissions and the fuel consumption of passenger cars in real traffic. The thesis begins developing a prospective study on other authors’ works about development of Portable Emission Measurement Systems (PEMS), problems associated with dynamic emission measurements and application studies on actual traffic using PEMS. As a result of this study, it was shown that a measuring system specifically designed for being on-board on a vehicle, which can measure in real time emission concentrations and exhaust flow, and at the same time to record motor vehicle and environment variables as the slope and atmospheric data, is needed; and the specifications and design parameters of the equipment are proposed. Although at the beginning of this research work there were already on the market some PEMS, in this Thesis a new system is researched, designed and built, called MIVECO – PEMS, in order to meet such measurements needs. Following that, there are presented, discussed and justify all technical solutions incorporated in the system, including the gas analysis subsystem, sampling and exhaust gas flowmeter subsystem, the subsystem for measurement of environment variables and of the vehicle activity and the set of auxiliary subsystems. The final design meets the needs and hypotheses proposed, and is validated in real-life use and chassis dynamometer testing and is also compared with other stationary and on-board systems. This thesis also presents all the research that has led to the methodology of processing the set of signals recorded in real time including signal timing, calculations and error propagation. The methodology to select and characterize of the routes and circuits, the driving patterns, and the vehicle preparation and calibration of the instruments and sensors are part of the legacy of this thesis. To demonstrate the measurement capabilities of the system and the type of results that can be obtained and that are useful for the scientific community and the environmental authorities, at the end of this Thesis is presented the results of several studies of endogenous and exogenous variables that affect the instantaneous and averaged emissions and consumption factors (g/km), as: driving style, road infrastructure, the level of traffic congestion, urban and extra-urban traffic, biofuels content, type of engine (diesel or spark ignition) etc. The main conclusions of this thesis are that it is possible to measure mass emissions and consumption of vehicle engines in actual use and that the results allow us to establish policies to reduce environmental impact and improve energy efficiency, but, to establish precise methodologies and to be very careful in the entire process of calibration, measurement and data post-treatment is necessary.

A methodology for territorial distribution of CO2 emission reductions in transport sector

Greenhouse gas emission reduction is the pillar of the Kyoto Protocol and one of the main goals of the European Union (UE) energy policy. National reduction targets for EU member states and an overall target for the EU-15 (8%) were set by the Kyoto Protocol. This reduction target is based on emissions in the reference year (1990) and must be reached by 2012. EU energy policy does not set any national targets, only an overall reduction target of 20% by 2020. This paper transfers global greenhouse gas emission reduction targets in both these documents to the transport sector and specifically to CO2 emissions. It proposes a nonlinear distribution method with objective, dynamic targets for reducing CO2 emissions in the transport sector, according to the context and characteristics of each geographical area. First, we analyse CO2 emissions from transport in the reference year (1990) and their evolution from 1990 to 2007. We then propose a nonlinear methodology for distributing dynamic CO2 emission reduction targets. We have applied the proposed distribution function for 2012 and 2020 at two territorial levels (EU member states and Spanish autonomous regions). The weighted distribution is based on per capita CO2 emissions and CO2 emissions per gross domestic product. Finally, we show the weighted targets found for each EU member state and each Spanish autonomous region, compare them with the real achievements to date, and forecast the situation for the years the Kyoto and EU goals are to be met. The results underline the need for ?weighted? decentralised decisions to be made at different territorial levels with a view to achieving a common goal, so relative convergence of all the geographical areas is reached over time. Copyright © 2011 John Wiley & Sons, Ltd.

Diffuse Soil Co2 Flux To Assess The Reliability Of Co2 Storage In The Mazarrón-Gañuelas Tertiary Basin (Spain)

Geological storage of CO2 is nowadays internationally considered as the most effective method for greenhouse gas emission mitigation, in order to minimize its effects on the global climatology. One of the main options is to store the CO2 in deep saline aquifers at more than 800 m depth, because it achieves its supercritical state. Among the most important aspects concerning the performance assessment of a deep CO2 geological repository is the evaluation of the CO2 leakage rate from the chosen storage geological formation. Therefore, it is absolutely necessary to increase the knowledge on the interaction among CO2, storage and sealing formations, as well as on the flow paths for CO2 and the physico-mechanical resistance of the sealing formation. Furthermore, the quantification of the CO2 leakage rate is essential to evaluate its effects on the environment. One way to achieve this objective is to study of CO2 leakage on natural analogue systems, because they can provide useful information about the natural performance of the CO2, which can be applied to an artificial CO2 geological storage. This work is focused on the retention capacity of the cap-rock by measuring the diffuse soil CO2 flux in a site selected based on: i) the presence of a natural and deep CO2 accumulation; ii) its structural geological characteristics; and iii) the nature of the cap-rocks. This site is located in the so-called Mazarrón-Gañuelas Tertiary Basin, in the Guadalentin Valley, province of Murcia (Spain) Therefore the main objective of this investigation has been to detect the possible leakages of CO2 from a deep saline aquifer to the surface in order to understand the capability of this area as a natural analogue for Carbon Capture and Sequestration (CCS). The results obtained allow to conclude that the geological sealing formation of the basin seems to be appropriate to avoid CO2 leakages from the storage formation.

Effects on the shallow aquifers by CO2 leakages in a tertiary basin (province of Murcia, Spain)

Geological storage of CO2 is nowadays internationally considered as the most effective method for greenhouse gas emission mitigation, in order to minimize its effects on the global climatology. One of the main options is to store CO2 in deep saline aquifers at more than 800m depth, because it reaches its supercritical state. Study of the CO2 natural accumulations as natural analogues of an artificial CO2 storage is very useful in order to understand the CO2 long term behaviour and thus to predict its possible impact on the surficial environment and life. Therefore the main objective of this work is to detect the affection of the CO2 leakages from a deep saline aquifer on the shallow aquifers, all of them located in the Gañuelas-Mazarrón Tertiary basin (Province of Murcia, Spain). This CO2 storage and leakage natural system can be analogous to an artificial CO2 storage with leakage phenomena. In order to reach these objectives, groundwaters from different aquifers in the site have been sampled and analysed for major elements, free and dissolved gases and stable isotopes, particularly ∂ 13 C and 3 He/ 4 He. The results obtained allow to conclude that this natural system is an interesting example of natural analogue for an artificial CO2 storage affected by leakage processes because the shallow fresh aquifers in the site are polluted by CO2 from the deep saline aquifer as a consequence of an intensive over-exploitation of these freshwater aquifers

Influence of driving style on fuel consumption and Emissions in diesel-powered passenger car

This paper presents the main results of a study on the influence of driving style on fuel consumption and pollutant emissions of diesel passenger car in urban traffic. Driving styles (eco, normal or aggressive) patterns were based on the “eco-driving” criteria. The methodology is based on on-board emission measurements in real urban traffic in the city of Madrid. Five diesel passenger cars, have been tested. Through a statistical analysis, a Dynamic Performance Index was defined for diesel passenger cars. Likewise, the CO, NOX and HC emissions were compared for each driving style for the tested vehicles. Eco-driving reduces by 14% fuel consumption and CO2 emissions, but aggressive driving increase consumption by 40%. Aggressive driving increases NOX emission by more than 40%. CO and HC, show different trends, but being increased in eco-driving style.

Gasification technology assessment of sterile coal to clean electrical power generation.

Sterile coal is a low-value residue associated to the coal extraction and mining activity. According to the type and origin of the coal bed configuration, sterile coal production can mainly vary on quantity, calorific value and presence of sulphur compounds. In addition, the potential availability of sterile coal within Spain is apparently high and its contribution to the local power generation would be of interest playing a significant role. The proposed study evaluates the availability and deployment of gasification technologies to drive clean electricity generation from waste coal and sterile rock coal, incorporating greenhouse gas emission mitigation systems, like CO2, H2S and NOx removal systems. It establishes the target facility and its conceptual basic design proposal. The syngas obtained after the gasification of sterile coal is processed through specific conditioning units before entering into the combustion chamber of a gas turbine. Flue gas leaving the gas turbine is ducted to a heat recovery steam generation boiler; the steam produced within the boilerdrives a steam turbine. The target facility resembles a singular Integrated Gasification in Combined Cycle (IGCC) power station. The evaluation of the conceptual basic design according to the power output set for a maximum sterile contribution, established that rates over 95% H2S and 90% CO2 removal can be achieved. Noticeable decrease of NOx compounds can be also achieved by the use of commercial technology. A techno-economic approach of the conceptual basic design is made evaluating the integration of potential unitsand their implementation within the target facility aiming toachieve clean power generation. The criterion to be compliant with the most restrictive regulation regarding environmental emissions is setting to carry out this analysis.

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.

Gas monitoring methodology and application to CCS projects as defined by atmospheric and remote sensing survey in the natural analogue of Campo de Calatrava

CO2 capture and storage (CCS) projects are presently developed to reduce the emission of anthropogenic CO2 into the atmosphere. CCS technologies are expected to account for the 20% of the CO2 reduction by 2050. Geophysical, ground deformation and geochemical monitoring have been carried out to detect potential leakage, and, in the event that this occurs, identify and quantify it. This monitoring needs to be developed prior, during and after the injection stage. For a correct interpretation and quantification of the leakage, it is essential to establish a pre-injection characterization (baseline) of the area affected by the CO2 storage at reservoir level as well as at shallow depth, surface and atmosphere, via soil gas measurements. Therefore, the methodological approach is important because it can affect the spatial and temporal variability of this flux and even jeopardize the total value of CO2 in a given area. In this sense, measurements of CO2 flux were done using portable infrared analyzers (i.e., accumulation chambers) adapted to monitoring the geological storage of CO2, and other measurements of trace gases, e.g. radon isotopes and remote sensing imagery were tested in the natural analogue of Campo de Calatrava (Ciudad Real, Spain) with the aim to apply in CO2 leakage detection; thus, observing a high correlation between CO2 and radon (r=0,858) and detecting some vegetation indices that may be successfully applied for the leakage detection.