Integrated luminescent chemical microsensors based on GaN LEDs for security applications using smartphones

Development of PCB-integrateable microsensors for monitoring chemical species is a goal in areas such as lab-on-a-chip analytical devices, diagnostics medicine and electronics for hand-held instruments where the device size is a major issue. Cellular phones have pervaded the world inhabitants and their usefulness has dramatically increased with the introduction of smartphones due to a combination of amazing processing power in a confined space, geolocalization and manifold telecommunication features. Therefore, a number of physical and chemical sensors that add value to the terminal for health monitoring, personal safety (at home, at work) and, eventually, national security have started to be developed, capitalizing also on the huge number of circulating cell phones. The chemical sensor-enabled “super” smartphone provides a unique (bio)sensing platform for monitoring airborne or waterborne hazardous chemicals or microorganisms for both single user and crowdsourcing security applications. Some of the latest ones are illustrated by a few examples. Moreover, we have recently achieved for the first time (covalent) functionalization of p- and n-GaN semiconductor surfaces with tuneable luminescent indicator dyes of the Ru-polypyridyl family, as a key step in the development of innovative microsensors for smartphone applications. Chemical “sensoring” of GaN-based blue LED chips with those indicators has also been achieved by plasma treatment of their surface, and the micrometer-sized devices have been tested to monitor O2 in the gas phase to show their full functionality. Novel strategies to enhance the sensor sensitivity such as changing the length and nature of the siloxane buffer layer are discussed in this paper.

Highly correlated ab initio study of the far infrared spectra of methyl acetate

Highly correlated ab initio calculations (CCSD(T)) are used to compute gas phase spectroscopic parameters of three isotopologues of the methyl acetate (CH3COOCH3, CD3COOCH3, and CH3COOCD3), searching to help experimental assignments and astrophysical detections. The molecule shows two conformers cis and trans separated by a barrier of 4457 cm−1. The potential energy surface presents 18 minima that intertransform through three internal rotation motions. To analyze the far infrared spectrum at low temperatures, a three-dimensional Hamiltonian is solved variationally. The two methyl torsion barriers are calculated to be 99.2 cm−1 (C–CH3) and 413.1 cm−1 (O–CH3), for the cis-conformer. The three fundamental torsional band centers of CH3COOCH3 are predicted to lie at 63.7 cm−1 (C–CH3), 136.1 cm−1 (O–CH3), and 175.8 cm−1 (C–O torsion) providing torsional state separations. For the 27 vibrational modes, anharmonic fundamentals and rovibrational parameters are provided. Computed parameters are compared with those fitted using experimental data.

Numerical simulation of group combustion of pulverized coal

A mathematical model for the group combustion of pulverized coal particles was developed in a previous work. It includes the Lagrangian description of the dehumidification, devolatilization and char gasification reactions of the coal particles in the homogenized gaseous environment resulting from the three fuels, CO, H2 and volatiles, supplied by the gasification of the particles and their simultaneous group combustion by the gas phase oxidation reactions, which are considered to be very fast. This model is complemented here with an analysis of the particle dynamics, determined principally by the effects of aerodynamic drag and gravity, and its dispersion based on a stochastic model. It is also extended to include two other simpler models for the gasification of the particles: the first one for particles small enough to extinguish the surrounding diffusion flames, and a second one for particles with small ash content when the porous shell of ashes remaining after gasification of the char, non structurally stable, is disrupted. As an example of the applicability of the models, they are used in the numerical simulation of an experiment of a non-swirling pulverized coal jet with a nearly stagnant air at ambient temperature, with an initial region of interaction with a small annular methane flame. Computational algorithms for solving the different stages undergone by a coal particle during its combustion are proposed. For the partial differential equations modeling the gas phase, a second order finite element method combined with a semi-Lagrangian characteristics method are used. The results obtained with the three versions of the model are compared among them and show how the first of the simpler models fits better the experimental results.

Flamelet structures in spray ignition

In typical liquid-fueled burners the fuel is injected as a high-velocity liquid jet that breaks up to form the spray. The initial heating and vaporization of the liquid fuel rely on the relatively large temperatures of the sourrounding gas, which may include hot combustion products and preheated air. The heat exchange between the liquid and the gas phases is enhanced by droplet dispersion arising from the turbulent motion. Chemical reaction takes place once molecular mixing between the fuel vapor and the oxidizer has occurred in mixing layers separating the spray flow from the hot air stream. Since in most applications the injection velocities are much larger than the premixed-flame propagation velocity, combustion stabilization relies on autoignition of the fuel-oxygen mixture, with the combustion stand-off distance being controlled by the interaction of turbulent transport, droplet heating and vaporization, and gas-phase chemical reactions. In this study, conditions are identified under which analyses of laminar flamelets canshed light on aspects of turbulent spray ignition. This study extends earlier fundamental work by Liñan & Crespo (1976) on ignition in gaseous mixing layers to ignition of sprays. Studies of laminar mixing layers have been found to be instrumental in developing un-derstanding of turbulent combustion (Peters 2000), including the ignition of turbulent gaseous diffusion flames (Mastorakos 2009). For the spray problem at hand, the configuration selected, shown in Figure 1, involves a coflow mixing layer formed between a stream of hot air moving at velocity UA and a monodisperse spray moving at velocity USUA. The boundary-layer approximation will be used below to describe the resulting sl ender flow, which exhibits different igniting behaviors depending on the characteristics of t he fuel. In this approximation, consideration of the case U A = U S enables laminar ignition distances to be related to ignition times of unstrained spray flamelets, thereby pro viding quantitative information of direct applicability in regions of low scala r dissipation-rate in turbulent reactive flows (see the discussion in pp. 181–186 of Peters (2000)) . This report is organized as follows. Effects of droplet dispersion dynamics on ignition of sprays in turbulent mixing layers are discussed in Section 2. The formulation f or ignition in laminar mixing layers is outlined in Sections 3 and 4. The results are presented in Section 5. In Section 6, the mixture-fraction field and associated scalar dissipat ion rates for spray ignition are discussed. Finally, some brief conclusions are drawn in Section 7.

A design-phase PSA of anuclear-powered hydrogen plant

A probabilistic safety assessment (PSA) is being developed for a steam-methane reforming hydrogenproduction plant linked to a high-temperature gas-cooled nuclear reactor (HTGR). This work is based on the Japan Atomic Energy Research Institute's (JAERI) High Temperature Engineering Test Reactor (HTTR) prototype in Japan. The objective of this paper is to show how the PSA can be used for improving the design of the coupled plants. A simplified HAZOP study was performed to identify initiating events, based on existing studies. The results of the PSA show that the average frequency of an accident at this complex that could affect the population is 7 × 10−8 year−1 which is divided into the various end states. The dominant sequences are those that result in a methane explosion and occur with a frequency of 6.5 × 10−8 year−1, while the other sequences are much less frequent. The health risk presents itself if there are people in the vicinity who could be affected by the explosion. This analysis also demonstrates that an accident in one of the plants has little effect on the other. This is true given the design base distance between the plants, the fact that the reactor is underground, as well as other safety characteristics of the HTGR.

Experimental analysis of direct thermal methane cracking

The analysis of the viability of Hydrogen production without CO2 emissions is one of the most challenging activities that have been initiated for a sustainable energy supply. As one of the tracks to fulfil such objective, direct methane cracking has been analysed experimentally to assess the scientific viability and reaction characterization in a broad temperature range, from 875 to 1700 ?C. The effect of temperature, sweeping/carrier gas fraction proposed in some concepts, methane flow rate, residence time, and tube material and porosity has been analysed. The aggregation of carbon black particles to the reaction tube is the main technological show-stopper that has been identified.

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.

Adaptive liquid-crystal phase-only passive devices

This PhD work is focused on liquid crystal based tunable phase devices with special emphasis on their design and manufacturing. In the course of the work a number of new manufacturing technologies have been implemented in the UPM clean room facilities, leading to an important improvement in the range of devices being manufactured in the laboratory. Furthermore, a number of novel phase devices have been developed, all of them including novel electrodes, and/or alignment layers. The most important manufacturing progress has been the introduction of reactive ion etching as a tool for achieving high resolution photolithography on indium-tin-oxide (ITO) coated glass and quartz substrates. Another important manufacturing result is the successful elaboration of a binding protocol of anisotropic conduction adhesives. These have been employed in high density interconnections between ITO-glass and flexible printed circuits. Regarding material characterization, the comparative study of nonstoichiometric silicon oxide (SiOx) and silica (SiO2) inorganic alignment layers, as well as the relationship between surface layer deposition, layer morphology and liquid crystal electrooptical response must be highlighted, together with the characterization of the degradation of liquid crystal devices in simulated space mission environment. A wide variety of phase devices have been developed, with special emphasis on beam steerers. One of these was developed within the framework of an ESA project, and consisted of a high density reconfigurable 1D blaze grating, with a spatial separation of the controlling microelectronics and the active, radiation exposed, area. The developed devices confirmed the assumption that liquid crystal devices with such a separation of components, are radiation hard, and can be designed to be both vibration and temperature sturdy. In parallel to the above, an evenly variable analog beam steering device was designed, manufactured and characterized, providing a narrow cone diffraction free beam steering. This steering device is characterized by a very limited number of electrodes necessary for the redirection of a light beam. As few as 4 different voltage levels were needed in order to redirect a light beam. Finally at the Wojskowa Akademia Techniczna (Military University of Technology) in Warsaw, Poland, a wedged analog tunable beam steering device was designed, manufactured and characterized. This beam steerer, like the former one, was designed to resist the harsh conditions both in space and in the context of the shuttle launch. Apart from the beam steering devices, reconfigurable vortices and modal lens devices have been manufactured and characterized. In summary, during this work a large number of liquid crystal devices and liquid crystal device manufacturing technologies have been developed. Besides their relevance in scientific publications and technical achievements, most of these new devices have demonstrated their usefulness in the actual work of the research group where this PhD has been completed. El presente trabajo de Tesis se ha centrado en el diseño, fabricación y caracterización de nuevos dispositivos de fase basados en cristal líquido. Actualmente se están desarrollando dispositivos basados en cristal líquido para aplicaciones diferentes a su uso habitual como displays. Poseen la ventaja de que los dispositivos pueden ser controlados por bajas tensiones y no necesitan elementos mecánicos para su funcionamiento. La fabricación de todos los dispositivos del presente trabajo se ha realizado en la cámara limpia del grupo. La cámara limpia ha sido diseñada por el grupo de investigación, es de dimensiones reducidas pero muy versátil. Está dividida en distintas áreas de trabajo dependiendo del tipo de proceso que se lleva a cabo. La cámara limpia está completamente cubierta de un material libre de polvo. Todas las entradas de suministro de gas y agua están selladas. El aire filtrado es constantemente bombeado dentro de la zona limpia, a fin de crear una sobrepresión evitando así la entrada de aire sin filtrar. Las personas que trabajan en esta zona siempre deben de estar protegidas con un traje especial. Se utilizan trajes especiales que constan de: mono, máscara, guantes de látex, gorro, patucos y gafas de protección UV, cuando sea necesario. Para introducir material dentro de la cámara limpia se debe limpiar con alcohol y paños especiales y posteriormente secarlos con nitrógeno a presión. La fabricación debe seguir estrictamente unos pasos determinados, que pueden cambiar dependiendo de los requerimientos de cada dispositivo. Por ello, la fabricación de dispositivos requiere la formulación de varios protocolos de fabricación. Estos protocolos deben ser estrictamente respetados a fin de obtener repetitividad en los experimentos, lo que lleva siempre asociado un proceso de fabricación fiable. Una célula de cristal líquido está compuesta (de forma general) por dos vidrios ensamblados (sándwich) y colocados a una distancia determinada. Los vidrios se han sometido a una serie de procesos para acondicionar las superficies internas. La célula se llena con cristal líquido. De forma resumida, el proceso de fabricación general es el siguiente: inicialmente, se cortan los vidrios (cuya cara interna es conductora) y se limpian. Después se imprimen las pistas sobre el vidrio formando los píxeles. Estas pistas conductoras provienen del vidrio con la capa conductora de ITO (óxido de indio y estaño). Esto se hace a través de un proceso de fotolitografía con una resina fotosensible, y un desarrollo y ataque posterior del ITO sin protección. Más tarde, las caras internas de los vidrios se acondicionan depositando una capa, que puede ser orgánica o inorgánica (un polímero o un óxido). Esta etapa es crucial para el funcionamiento del dispositivo: induce la orientación de las moléculas de cristal líquido. Una vez que las superficies están acondicionadas, se depositan espaciadores en las mismas: son pequeñas esferas o cilindros de tamaño calibrado (pocos micrómetros) para garantizar un espesor homogéneo del dispositivo. Después en uno de los sustratos se deposita un adhesivo (gasket). A continuación, los sustratos se ensamblan teniendo en cuenta que el gasket debe dejar una boca libre para que el cristal líquido se introduzca posteriormente dentro de la célula. El llenado de la célula se realiza en una cámara de vacío y después la boca se sella. Por último, la conexión de los cables a la célula y el montaje de los polarizadores se realizan fuera de la sala limpia (Figura 1). Dependiendo de la aplicación, el cristal líquido empleado y los demás componentes de la célula tendrán unas características particulares. Para el diseño de los dispositivos de este trabajo se ha realizado un estudio de superficies inorgánicas de alineamiento del cristal líquido, que será de gran importancia para la preparación de los dispositivos de fase, dependiendo de las condiciones ambientales en las que vayan a trabajar. Los materiales inorgánicos que se han estudiado han sido en este caso SiOx y SiO2. El estudio ha comprendido tanto los factores de preparación influyentes en el alineamiento, el comportamiento del cristal líquido al variar estos factores y un estudio de la morfología de las superficies obtenidas.

Asphalt rubber mixtures with warm mix asphalt additives

En los últimos años, debido a la creciente preocupación por el calentamiento global y el cambio climático, uno de los retos más importantes a los que se enfrenta nuestra sociedad es el uso eficiente y económico de energía así como la necesidad correspondiente de reducir los gases de efecto invernadero (GEI). Las tecnologías de mezclas semicalientes se han convertido en un nuevo e importante tema de investigación en el campo de los materiales para pavimentos ya que ofrece una solución potencial para la reducción del consumo energético y las emisiones de GEI durante la producción y puesta en obra de las mezclas bituminosas. Por otro lado, los pavimentos que contienen polvo de caucho procedente de neumático fuera de uso, al hacer uso productos de desecho, ahorran energía y recursos naturales. Estos pavimentos ofrecen una resistencia mejorada a la formación de roderas, a la fatiga y a la fisuración térmica, reducen los costes de mantenimiento y el ruido del tráfico así como prolongan la vida útil del pavimento. Sin embargo, estas mezclas presentan un importante inconveniente: la temperatura de fabricación se debe aumentar en comparación con las mezclas asfálticas convencionales, ya que la incorporación de caucho aumenta la viscosidad del ligante y, por lo tanto, se producen mayores cantidades de emisiones de GEI. En la presente Tesis, la tecnología de mezclas semicalientes con aditivos orgánicos (Sasobit, Asphaltan A, Asphaltan B, Licomont) se incorporó a la de betunes de alta viscosidad modificados con caucho (15% y 20% de caucho) con la finalidad de dar una solución a los inconvenientes de mezclas con caucho gracias a la utilización de aditivos reductores de la viscosidad. Para este fin, se estudió si sería posible obtener una producción más sostenible de mezclas con betunes de alto contenido en caucho sin afectar significativamente su nivel de rendimiento mecánico. La metodología aplicada para evaluar y comparar las características de las mezclas consistió en la realización de una serie de ensayos de laboratorio para betunes y mezclas con caucho y con aditivos de mezclas semicalientes y de un análisis del ciclo de vida híbrido de la producción de mezclas semicalientes teniendo en cuenta la papel del aditivo en la cadena de suministro con el fin de cuantificar con precisión los beneficios de esta tecnología. Los resultados del estudio indicaron que la incorporación de los aditivos permite reducir la viscosidad de los ligantes y, en consecuencia, las temperaturas de producción y de compactación de las mezclas. Por otro lado, aunque la adición de caucho mejoró significativamente el comportamiento mecánico de los ligantes a baja temperatura reduciendo la susceptibilidad al fenómeno de fisuración térmica, la adición de las ceras aumentó ligeramente la rigidez. Los resultados del estudio reológico mostraron que la adición de porcentajes crecientes de caucho mejoraban la resistencia del pavimento con respecto a la resistencia a la deformación permanente a altas temperaturas y a la fisuración térmica a bajas temperaturas. Además, se observó que los aditivos mejoran la resistencia a roderas y la elasticidad del pavimento al aumentar el módulo complejo a altas temperaturas y al disminuir del ángulo de fase. Por otra parte, el estudio reológico confirmó que los aditivos estudiados aumentan ligeramente la rigidez a bajas temperaturas. Los ensayos de fluencia llevados a cabo con el reómetro demostraron una vez más la mejora en la elasticidad y en la resistencia a la deformación permanente dada por la adición de las ceras. El estudio de mezclas con caucho y aditivos de mezclas semicalientes llevado a cabo demostró que las temperaturas de producción/compactación se pueden disminuir, que las mezclas no experimentarían escurrimiento, que los aditivos no cambian significativamente la resistencia conservada y que cumplen la sensibilidad al agua exigida. Además, los aditivos aumentaron el módulo de rigidez en algunos casos y mejoraron significativamente la resistencia a la deformación permanente. Asimismo, a excepción de uno de los aditivos, las mezclas con ceras tenían la misma o mayor resistencia a la fatiga en comparación con la mezcla control. Los resultados del análisis de ciclo de vida híbrido mostraron que la tecnología de mezclas semicalientes es capaz de ahorrar significativamente energía y reducir las emisiones de GEI, hasta un 18% y 20% respectivamente, en comparación con las mezclas de control. Sin embargo, en algunos de los casos estudiados, debido a la presencia de la cera, la temperatura de fabricación debe reducirse en un promedio de 8 ºC antes de que los beneficios de la reducción de emisiones y el consumo de combustible puedan ser obtenidos. Los principales sectores contribuyentes a los impactos ambientales generados en la fabricación de mezclas semicalientes fueron el sector de los combustibles, el de la minería y el de la construcción. Due to growing concerns over global warming and climate change in recent years, one of the most important challenges facing our society is the efficient and economic use of energy, and with it, the corresponding need to reduce greenhouse gas (GHG) emissions. The Warm Mix Asphalt (WMA) technology has become an important new research topic in the field of pavement materials as it offers a potential solution for the reduction of energy consumption and GHG emissions during the production and placement of asphalt mixtures. On the other hand, pavements containing crumb-rubber modified (CRM) binders save energy and natural resources by making use of waste products. These pavements offer an improved resistance to rutting, fatigue and thermal cracking; reduce traffic noise and maintenance costs and prolong pavement life. These mixtures, however, present one major drawback: the manufacturing temperature is higher compared to conventional asphalt mixtures as the rubber lends greater viscosity to the binder and, therefore, larger amounts of GHG emissions are produced. In this dissertation the WMA technology with organic additives (Sasobit, Asphaltan A, Asphaltan B and Licomont) was applied to CRM binders (15% and 20% of rubber) in order to offer a solution to the drawbacks of asphalt rubber (AR) mixtures thanks to the use of fluidifying additives. For this purpose, this study sought to determine if a more sustainable production of AR mixtures could be obtained without significantly affecting their level of mechanical performance. The methodology applied in order to evaluate and compare the performance of the mixtures consisted of carrying out several laboratory tests for the CRM binders and AR mixtures with WMA additives (AR-WMA mixtures) and a hybrid input-output-based life cycle assessment (hLCA) of the production of WMA. The results of the study indicated that the incorporation of the organic additives were able to reduce the viscosity of the binders and, consequently, the production and compaction temperatures. On the other hand, although the addition of rubber significantly improved the mechanical behaviour of the binders at low temperatures reducing the susceptibility to thermal cracking phenomena, the addition of the waxes slightly increased the stiffness. Master curves showed that the addition of increasing percentages of rubber improved the resistance of the pavement regarding both resistance to permanent deformation at high temperatures and thermal cracking at low temperatures. In addition, the waxes improved the rutting resistance and the elasticity as they increased the complex modulus at high temperatures and decreased the phase angle. Moreover, master curves also attest that the WMA additives studied increase the stiffness at low temperatures. The creep tests carried out proved once again the improvement in the elasticity and in the resistance to permanent deformation given by the addition of the waxes. The AR-WMA mixtures studied have shown that the production/compaction temperatures can be decreased, that the mixtures would not experience binder drainage, that the additives did not significantly change the retained resistance and fulfilled the water sensitivity required. Furthermore, the additives increased the stiffness modulus in some cases and significantly improved the permanent deformation resistance. Except for one of the additives, the waxes had the same or higher fatigue resistance compared to the control mixture. The results of the hLCA demonstrated that the WMA technology is able to significantly save energy and reduce GHG emissions, up to 18% and 20%, respectively, compared to the control mixtures. However, in some of the case studies, due to the presence of wax, the manufacturing temperature at the asphalt plant must be reduced by an average of 8ºC before the benefits of reduced emissions and fuel usage can be obtained. The results regarding the overall impacts generated using a detailed production layer decomposition indicated that fuel, mining and construction sectors are the main contributors to the environmental impacts of manufacturing WMA mixtures.

Simultaneous determination of multiclass emerging contaminants in aquatic plants by ultrasound assisted matrix solid phase dispersion and GC-MS

A multiresidue method was developed for the simultaneous determination of 31 emerging contaminants (pharmaceutical compounds, hormones, personal care products, biocides and flame retardants) in aquatic plants. Analytes were extracted by ultrasound assisted-matrix solid phase dispersion (UA-MSPD) and determined by gas chromatography-mass spectrometry after sylilation. The method was validated for different aquatic plants (Typha angustifolia, Arundo donax and Lemna minor) and a semiaquatic cultivated plant (Oryza sativa) with good recoveries at concentrations of 100 and 25 ng g-1 wet weight, ranging from 70 to 120 %, and low method detection limits (0.3 to 2.2 ng g-1 wet weight). A significant difference of the chromatographic response was observed for some compounds in neat solvent versus matrix extracts and therefore quantification was carried out using matrix-matched standards in order to overcome this matrix effect. Aquatic plants taken from rivers located at three Spanish regions were analyzed and the compounds detected were parabens, bisphenol A, benzophenone-3, cyfluthrin and cypermethrin. The levels found ranged from 6 to 25 ng g-1 wet weight except for cypermethrin that was detected at 235 ng g-1 wet weight in Oryza sativa samples.