18 resultados para heterogeneous Zn and Al catalysts
em Universidad Politécnica de Madrid
Resumo:
Extensive spatial and temporal surveys, over 15 years, have been conducted in soil in urban parks and street dusts in one of the most polluted cities in western Europe, Avilés (NW Spain). The first survey was carried out in 1996, and since then monitoring has been undertaken every five years. Whilst the sampling site is a relatively small town, industrial activities (mainly the steel industry and Zn and Al metallurgy) and other less significant urban sources, such as traffic, strongly affect the load of heavy metals in the urban aerosol. Elemental tracers have been used to characterise the influence of these sources on the composition of soil and dust. Although PM10 has decreased over these years as a result of environmental measures undertaken in the city, some of the “industrial” elements still remain in concentrations of concern for example, up to 4.6% and 0.5% of Zn in dust and soil, respectively. Spatial trends in metals such as Zn and Cd clearly reflect sources from the processing industries. The concentrations of these elements across Europe have reduced over time, however the most recent results from Avilés revealed an upward trend in concentration for Zn, Cd, Hg and As. A risk assessment of the soil highlighted As as an element of concern since its cancer risk in adults was more than double the value above which regulatory agencies deem it to be unacceptable. If children were considered to be the receptors, then the risk nearly doubles from this element.
Resumo:
In this work we present results of zinc diffusion in GaAs using the liquid phase epitaxy technique from liquid solutions of Ga‐As‐Zn and Ga‐As‐Al‐Zn. Using silicon‐doped n‐GaAs substrates, working at a diffusion temperature of 850 °C, and introducing a dopant concentration ranging 1018–1019 cm−3, the most important findings regarding the diffusion properties are as follows: (a) zinc concentration in the solid depends on the square root of zinc atomic fraction in the liquid; (b) the diffusion is dominated by the interstitial‐substitutional process; (c) the diffusivity D varies as about C3 in the form D=2.9×10−67C3.05; (d) aluminum plays the role of the catalyst of the diffusion process, if it is introduced in the liquid solution, since it is found that D varies as (γAsXlAs)−1; (e) the zinc interstitial is mainly doubly ionized (Zn++i); (f) the zinc diffusion coefficient in Al0.85 Ga0.15 As is about four times greater than in GaAs; (g) by means of all these results, it is possible to control zinc diffusion processes in order to obtain optimized depth junctions and doping levels in semiconductor device fabrication.
Resumo:
Sewage sludge gasification assays were performed in an atmospheric fluidised bed reactor using air and air–steam mixtures as the gasifying agents. Dolomite, olivine and alumina are three well known tar removal catalysts used in biomass gasification processing. However, little information is available regarding their performance in sewage sludge gasification. The aim of the current study was to learn about the influence of these three catalysts in the product distribution and tar production during sewage sludge gasification. To this end, a set of assays was performed in which the temperature (750–850 °C), the in-bed catalyst content (0, 10 and 15 wt.%) and the steam–biomass ratio (SB) in the range of 0–1 were varied with a constant equivalence ratio (ER) of 0.3. The results were compared to the results from gasification without a catalyst. We show that dolomite has the highest activity in tar elimination, followed by alumina and olivine. In addition to improving tar removal, the presence of water vapour and the catalysts increased the content of H2 in the gases by nearly 60%.
Resumo:
El Zn es un elemento esencial para el crecimiento saludable y reproducción de plantas, animales y humanos. La deficiencia de Zn es una de las carencias de micronutrientes más extendidas en muchos cultivos, afectando a grandes extensiones de suelos en diferentes áreas agrícolas. La biofortificación agronómica de diferentes cultivos, incrementando la concentración de micronutriente Zn en la planta, es un medio para evitar la deficiencia de Zn en animales y humanos. Tradicionalmente se han utilizado fertilizantes de Zn inorgánicos, como el ZnSO4, aunque en los últimos años se están utilizado complejos de Zn como fuentes de este micronutriente, obteniéndose altas concentraciones de Zn soluble y disponible en el suelo. Sin embargo, el envejecimiento de la fuente en el suelo puede causar cambios importantes en su disponibilidad para las plantas. Cuando se añaden al suelo fuentes de Zn inorgánicas, las formas de Zn más solubles pierden actividad y extractabilidad con el paso del tiempo, transformándose a formas más estables y menos biodisponibles. En esta tesis se estudia el efecto residual de diferentes complejos de Zn de origen natural y sintético, aplicados en cultivos previos de judía y lino, bajo dos condiciones de riego distintas (por encima y por debajo de la capacidad de campo, respectivamente) y en dos suelos diferentes (ácido y calizo). Los fertilizantes fueron aplicados al cultivo previo en tres dosis diferentes (0, 5 y 10 mg Zn kg-1 suelo). El Zn fácilmente lixiviable se estimó con la extracción con BaCl2 0,1M. Bajo condiciones de humedad por encima de la capacidad de campo se obtuvieron mayores porcentajes de Zn lixiviado en el suelo calizo que en el suelo ácido. En el caso del cultivo de judía realizado en condiciones de humedad por encima de la capacidad de campo se compararon las cantidades extraídas con el Zn lixiviado real. El análisis de correlación entre el Zn fácilmente lixiviable y el estimado sólo fue válido para complejos con alta movilidad y para cada suelo por separado. Bajo condiciones de humedad por debajo de la capacidad de campo, la concentración de Zn biodisponible fácilmente lixiviable presentó correlaciones positivas y altamente significativas con la concentración de Zn disponible en el suelo. El Zn disponible se estimó con varios métodos de extracción empleados habitualmente: DTPA-TEA, DTPA-AB, Mehlich-3 y LMWOAs. Estas concentraciones fueron mayores en el suelo ácido que en el calizo. Los diferentes métodos utilizados para estimar el Zn disponible presentaron correlaciones positivas y altamente significativas entre sí. La distribución del Zn en las distintas fracciones del suelo fue estimada con diferentes extracciones secuenciales. Las extracciones secuenciales mostraron un descenso entre los dos cultivos (el anterior y el actual) en la fracción de Zn más lábil y un aumento en la concentración de Zn asociado a fracciones menos lábiles, como carbonatos, óxidos y materia orgánica. Se obtuvieron correlaciones positivas y altamente significativas entre las concentraciones de Zn asociado a las fracciones más lábiles (WSEX y WS+EXC, experimento de la judía y lino, respectivamente) y las concentraciones de Zn disponible, estimadas por los diferentes métodos. Con respecto a la planta se determinaron el rendimiento en materia seca y la concentración de Zn en planta. Se observó un aumento del rendimiento y concentraciones con el efecto residual de la dosis mayores (10 mg Zn kg-1) con respecto a la dosis inferior (5 mg Zn 12 kg-1) y de ésta con respecto a la dosis 0 (control). El incremento de la concentración de Zn en todos los tratamientos fertilizantes, respecto al control, fue mayor en el suelo ácido que en el calizo. Las concentraciones de Zn en planta indicaron que, en el suelo calizo, serían convenientes nuevas aplicaciones de Zn en posteriores cultivos para mantener unas adecuadas concentraciones en planta. Las mayores concentraciones de Zn en la planta de judía, cultivada bajo condiciones de humedad por encima de la capacidad de campo, se obtuvieron en el suelo ácido con el efecto residual del Zn-HEDTA a la dosis de 10 mg Zn kg-1 (280,87 mg Zn kg-1) y en el suelo calizo con el efecto residual del Zn-DTPA-HEDTA-EDTA a la dosis de 10 mg Zn kg-1 (49,89 mg Zn kg-1). En el cultivo de lino, cultivado bajo condiciones de humedad por debajo de la capacidad de campo, las mayores concentraciones de Zn en planta ese obtuvieron con el efecto residual del Zn-AML a la dosis de 10 mg Zn kg-1 (224,75 mg Zn kg-1) y en el suelo calizo con el efecto residual del Zn-EDTA a la dosis de 10 mg Zn kg-1 (99,83 mg Zn kg-1). El Zn tomado por la planta fue determinado como combinación del rendimiento y de la concentración en planta. Bajo condiciones de humedad por encima de capacidad de campo, con lixiviación, el Zn tomado por la judía disminuyó en el cultivo actual con respecto al cultivo anterior. Sin embargo, en el cultivo de lino, bajo condiciones de humedad por debajo de la capacidad de campo, se obtuvieron cantidades de Zn tomado superiores en el cultivo actual con respecto al anterior. Esta tendencia también se observó, en ambos casos, con el porcentaje de Zn usado por la planta. Summary Zinc is essential for healthy growth and reproduction of plants, animals and humans. Zinc deficiency is one of the most widespread micronutrient deficiency in different crops, and affect different agricultural areas. Agronomic biofortification of crops produced by an increased of Zn in plant, is one way to avoid Zn deficiency in animals and humans Sources with inorganic Zn, such as ZnSO4, have been used traditionally. Although, in recent years, Zn complexes are used as sources of this micronutrient, the provide high concentrations of soluble and available Zn in soil. However, the aging of the source in the soil could cause significant changes in their availability to plants. When an inorganic source of Zn is added to soil, Zn forms more soluble and extractability lose activity over time, transforming into forms more stable and less bioavailable. This study examines the residual effect of different natural and synthetic Zn complexes on navy bean and flax crops, under two different moisture conditions (above and below field capacity, respectively) and in two different soils (acid and calcareous). Fertilizers were applied to the previous crop in three different doses (0, 5 y 10 mg Zn kg-1 soil). The easily leachable Zn was estimated by extraction with 0.1 M BaCl2. Under conditions of moisture above field capacity, the percentage of leachable Zn in the calcareous soil was higher than in acid soil. In the case of navy bean experiment, performed in moisture conditions of above field capacity, amounts extracted of easily leachable Zn were compared with the real leachable Zn. Correlation analysis between the leachable Zn and the estimate was only valid for complex with high mobility and for each soil separately. Under moisture conditions below field capacity, the concentration of bioavailable easily leachable Zn showed highly significant positive correlations with the concentration of available soil Zn. The available Zn was estimated with several commonly used extraction methods: DTPA-TEA, AB-DTPA, Mehlich-3 and LMWOAs. These concentrations were higher in acidic soil than in the calcareous. The different methods used to estimate the available Zn showed highly significant positive correlations with each other. The distribution of Zn in the different fractions of soil was estimated with different sequential extractions. The sequential extractions showed a decrease between the two crops (the previous and current) at the most labile Zn fraction and an increase in the concentration of Zn associated with the less labile fractions, such as carbonates, oxides and organic matter. A positive and highly significant correlation was obtained between the concentrations of Zn associated with more labile fractions (WSEX and WS + EXC, navy bean and flax experiments, respectively) and available Zn concentrations determined by the different methods. Dry matter yield and Zn concentration in plants were determined in plant. Yield and Zn concentration in plant were higher with the residual concentrations of the higher dose applied (10 mg Zn kg-1) than with the lower dose (5 mg Zn kg-1), also these parameters showed higher values with application of this dose than with not Zn application. The increase of Zn concentration in plant with Zn treatments, respect to the control, was greater in the acid soil than in the calcareous. The Zn concentrations in plant indicated that in the calcareous soil, new applications of Zn are desirable in subsequent crops to maintain suitable concentrations in plant. 15 The highest concentrations of Zn in navy bean plant, performed under moisture conditions above the field capacity, were obtained with the residual effect of Zn-HEDTA at the dose of 10 mg Zn kg-1 (280.87 mg Zn kg-1) in the acid soil, and with the residual effect of Zn- DTPA-HEDTA-EDTA at a dose of 10 mg Zn kg-1 (49.89 mg Zn kg-1) in the calcareous soil. In the flax crop, performed under moisture conditions below field capacity, the highest Zn concentrations in plant were obtained with the residual effect of Zn-AML at the dose of 10 mg Zn kg-1 (224.75 Zn mg kg-1) and with the residual effect of Zn-EDTA at a dose of 10 mg Zn kg-1 (99.83 mg Zn kg-1) in the calcareous soil. The Zn uptake was determined as a combination of yield and Zn concentration in plant. Under moisture conditions above field capacity, with leaching, Zn uptake by navy bean decreased in the current crop, respect to the previous crop. However, in the flax crop, under moisture conditions below field capacity, Zn uptake was higher in the current crop than in the previous. This trend is also observed in both cases, with the percentage of Zn used by the plant
Resumo:
The effects of fire ( Control burned soil) and two emergency stabilisation techniques (grass Seeding and straw Mulching ) on 20 chemical characteristics were evaluated on 0 – 5 cm top-soils sampled 1, 90, 180 and 365 days after an experimental fi re in a steep shrubland of a temperate-humid region (NW Spain). Most part of pH (in H 2 O and KCl) variance was explained by the sampling date. No clear temporal trends were identi fi able for total soil C and N content, likely due to the large SOM pool in these soils; however, changes on soil δ 13 C were explained by the deposition of 13 C-depleted ashes, followed by its progressive erosion, while those on soil δ 15 N were a consequence of fi re induced N outputs. After the fi re, NH 4 + – N, P, Na, K, Mg, Ca, Mn, Cu, Zn and B concentrations increased, while those of NO 3 − – N, Al, Fe and Co did not vary significantly. Despite a significant decline with time, concentrations of Mg, Ca and Mn at the end of the study were still higher than in unburned soil, while those of K, Cu, Zn and B were similar to the pre-fire levels and those of NH 4 + – N, P and Na were below pre-fire values. Mulching and Seeding treatments for burned soil emergency stabilisation had significant effects on soil δ 15 N and extractable K, Mg and Ca, while data were inconclusive for their possible effects on the extractable Al, Fe and Co
Availability and uptake of trace elements in a forage rotation under conservation and plough tillage
Resumo:
After 14 years under conventional plough tillage (CT) or conservation minimum tillage (MT), the soil available Al, Fe, Mn, Cu and Zn (0-5, 5-15 and 15-30 cm layers) and their plant uptake were evaluated during two years in a ryegrass-maize forage rotation in NW Spain (t emperate-humid region). The three-way ANOVA showed that trace element concentrations in soil were mainly influenced by sampling date, followed by soil depth and tillage system (35-73 %, 7-58 % and 3- 11 % of variance explained, respectively). Excepting for Fe (CT) and Al (CT and MT), the elemental concentrations decreased with depth, the stratification being stronger under MT. For soil available Al, Fe, Mn and Cu, the concentrations were higher in CT than in MT (5-15 and 15-30 cm layers) or were not affected by tillage system (0-5 cm). In contrast, the available Zn contents were higher in MT than CT at the soil surface and did not differ in deeper layers. The concentration of Al, Fe and Cu in crops were not influenced by tillage system, which explain 22 % of Mn variance in maize (CT > MT in the more humid year) and 18 % of Zn variance in ryegrass (MT > CT in both years). However, in the summer crop (maize) the concentrations of Fe, Mn and Zn tended to be higher in MT than in CT under drought conditions, while the opposite was true in the year without water limitation. Therefore, under the studied conditions of climate, soil, tillage and crop rotation, little influence of tillage system on crop nutritive value would be expected. To minimize the potential deficiency of Zn (maize) and Cu (maize and ryegrass) on crop yields the inclusion of these micro-nutrients in fertilization schedule is reco mmended, as well as liming to alleviate Al toxicity on maize crops.
Resumo:
Las transformaciones martensíticas (MT) se definen como un cambio en la estructura del cristal para formar una fase coherente o estructuras de dominio multivariante, a partir de la fase inicial con la misma composición, debido a pequeños intercambios o movimientos atómicos cooperativos. En el siglo pasado se han descubierto MT en diferentes materiales partiendo desde los aceros hasta las aleaciones con memoria de forma, materiales cerámicos y materiales inteligentes. Todos muestran propiedades destacables como alta resistencia mecánica, memoria de forma, efectos de superelasticidad o funcionalidades ferroicas como la piezoelectricidad, electro y magneto-estricción etc. Varios modelos/teorías se han desarrollado en sinergia con el desarrollo de la física del estado sólido para entender por qué las MT generan microstructuras muy variadas y ricas que muestran propiedades muy interesantes. Entre las teorías mejor aceptadas se encuentra la Teoría Fenomenológica de la Cristalografía Martensítica (PTMC, por sus siglas en inglés) que predice el plano de hábito y las relaciones de orientación entre la austenita y la martensita. La reinterpretación de la teoría PTMC en un entorno de mecánica del continuo (CM-PTMC) explica la formación de los dominios de estructuras multivariantes, mientras que la teoría de Landau con dinámica de inercia desentraña los mecanismos físicos de los precursores y otros comportamientos dinámicos. La dinámica de red cristalina desvela la reducción de la dureza acústica de las ondas de tensión de red que da lugar a transformaciones débiles de primer orden en el desplazamiento. A pesar de las diferencias entre las teorías estáticas y dinámicas dado su origen en diversas ramas de la física (por ejemplo mecánica continua o dinámica de la red cristalina), estas teorías deben estar inherentemente conectadas entre sí y mostrar ciertos elementos en común en una perspectiva unificada de la física. No obstante las conexiones físicas y diferencias entre las teorías/modelos no se han tratado hasta la fecha, aun siendo de importancia crítica para la mejora de modelos de MT y para el desarrollo integrado de modelos de transformaciones acopladas de desplazamiento-difusión. Por lo tanto, esta tesis comenzó con dos objetivos claros. El primero fue encontrar las conexiones físicas y las diferencias entre los modelos de MT mediante un análisis teórico detallado y simulaciones numéricas. El segundo objetivo fue expandir el modelo de Landau para ser capaz de estudiar MT en policristales, en el caso de transformaciones acopladas de desplazamiento-difusión, y en presencia de dislocaciones. Comenzando con un resumen de los antecedente, en este trabajo se presentan las bases físicas de los modelos actuales de MT. Su capacidad para predecir MT se clarifica mediante el ansis teórico y las simulaciones de la evolución microstructural de MT de cúbicoatetragonal y cúbicoatrigonal en 3D. Este análisis revela que el modelo de Landau con representación irreducible de la deformación transformada es equivalente a la teoría CM-PTMC y al modelo de microelasticidad para predecir los rasgos estáticos durante la MT, pero proporciona una mejor interpretación de los comportamientos dinámicos. Sin embargo, las aplicaciones del modelo de Landau en materiales estructurales están limitadas por su complejidad. Por tanto, el primer resultado de esta tesis es el desarrollo del modelo de Landau nolineal con representación irreducible de deformaciones y de la dinámica de inercia para policristales. La simulación demuestra que el modelo propuesto es consistente fcamente con el CM-PTMC en la descripción estática, y también permite una predicción del diagrama de fases con la clásica forma ’en C’ de los modos de nucleación martensítica activados por la combinación de temperaturas de enfriamiento y las condiciones de tensión aplicada correlacionadas con la transformación de energía de Landau. Posteriomente, el modelo de Landau de MT es integrado con un modelo de transformación de difusión cuantitativa para elucidar la relajación atómica y la difusión de corto alcance de los elementos durante la MT en acero. El modelo de transformaciones de desplazamiento y difusión incluye los efectos de la relajación en borde de grano para la nucleación heterogenea y la evolución espacio-temporal de potenciales de difusión y movilidades químicas mediante el acoplamiento de herramientas de cálculo y bases de datos termo-cinéticos de tipo CALPHAD. El modelo se aplica para estudiar la evolución microstructural de aceros al carbono policristalinos procesados por enfriamiento y partición (Q&P) en 2D. La microstructura y la composición obtenida mediante la simulación se comparan con los datos experimentales disponibles. Los resultados muestran el importante papel jugado por las diferencias en movilidad de difusión entre la fase austenita y martensita en la distibución de carbono en las aceros. Finalmente, un modelo multi-campo es propuesto mediante la incorporación del modelo de dislocación en grano-grueso al modelo desarrollado de Landau para incluir las diferencias morfológicas entre aceros y aleaciones con memoria de forma con la misma ruptura de simetría. La nucleación de dislocaciones, la formación de la martensita ’butterfly’, y la redistribución del carbono después del revenido son bien representadas en las simulaciones 2D del estudio de la evolución de la microstructura en aceros representativos. Con dicha simulación demostramos que incluyendo las dislocaciones obtenemos para dichos aceros, una buena comparación frente a los datos experimentales de la morfología de los bordes de macla, la existencia de austenita retenida dentro de la martensita, etc. Por tanto, basado en un modelo integral y en el desarrollo de códigos durante esta tesis, se ha creado una herramienta de modelización multiescala y multi-campo. Dicha herramienta acopla la termodinámica y la mecánica del continuo en la macroescala con la cinética de difusión y los modelos de campo de fase/Landau en la mesoescala, y también incluye los principios de la cristalografía y de la dinámica de red cristalina en la microescala. ABSTRACT Martensitic transformation (MT), in a narrow sense, is defined as the change of the crystal structure to form a coherent phase, or multi-variant domain structures out from a parent phase with the same composition, by small shuffles or co-operative movements of atoms. Over the past century, MTs have been discovered in different materials from steels to shape memory alloys, ceramics, and smart materials. They lead to remarkable properties such as high strength, shape memory/superelasticity effects or ferroic functionalities including piezoelectricity, electro- and magneto-striction, etc. Various theories/models have been developed, in synergy with development of solid state physics, to understand why MT can generate these rich microstructures and give rise to intriguing properties. Among the well-established theories, the Phenomenological Theory of Martensitic Crystallography (PTMC) is able to predict the habit plane and the orientation relationship between austenite and martensite. The re-interpretation of the PTMC theory within a continuum mechanics framework (CM-PTMC) explains the formation of the multivariant domain structures, while the Landau theory with inertial dynamics unravels the physical origins of precursors and other dynamic behaviors. The crystal lattice dynamics unveils the acoustic softening of the lattice strain waves leading to the weak first-order displacive transformation, etc. Though differing in statics or dynamics due to their origins in different branches of physics (e.g. continuum mechanics or crystal lattice dynamics), these theories should be inherently connected with each other and show certain elements in common within a unified perspective of physics. However, the physical connections and distinctions among the theories/models have not been addressed yet, although they are critical to further improving the models of MTs and to develop integrated models for more complex displacivediffusive coupled transformations. Therefore, this thesis started with two objectives. The first one was to reveal the physical connections and distinctions among the models of MT by means of detailed theoretical analyses and numerical simulations. The second objective was to expand the Landau model to be able to study MTs in polycrystals, in the case of displacive-diffusive coupled transformations, and in the presence of the dislocations. Starting with a comprehensive review, the physical kernels of the current models of MTs are presented. Their ability to predict MTs is clarified by means of theoretical analyses and simulations of the microstructure evolution of cubic-to-tetragonal and cubic-to-trigonal MTs in 3D. This analysis reveals that the Landau model with irreducible representation of the transformed strain is equivalent to the CM-PTMC theory and microelasticity model to predict the static features during MTs but provides better interpretation of the dynamic behaviors. However, the applications of the Landau model in structural materials are limited due its the complexity. Thus, the first result of this thesis is the development of a nonlinear Landau model with irreducible representation of strains and the inertial dynamics for polycrystals. The simulation demonstrates that the updated model is physically consistent with the CM-PTMC in statics, and also permits a prediction of a classical ’C shaped’ phase diagram of martensitic nucleation modes activated by the combination of quenching temperature and applied stress conditions interplaying with Landau transformation energy. Next, the Landau model of MT is further integrated with a quantitative diffusional transformation model to elucidate atomic relaxation and short range diffusion of elements during the MT in steel. The model for displacive-diffusive transformations includes the effects of grain boundary relaxation for heterogeneous nucleation and the spatio-temporal evolution of diffusion potentials and chemical mobility by means of coupling with a CALPHAD-type thermo-kinetic calculation engine and database. The model is applied to study for the microstructure evolution of polycrystalline carbon steels processed by the Quenching and Partitioning (Q&P) process in 2D. The simulated mixed microstructure and composition distribution are compared with available experimental data. The results show that the important role played by the differences in diffusion mobility between austenite and martensite to the partitioning in carbon steels. Finally, a multi-field model is proposed by incorporating the coarse-grained dislocation model to the developed Landau model to account for the morphological difference between steels and shape memory alloys with same symmetry breaking. The dislocation nucleation, the formation of the ’butterfly’ martensite, and the redistribution of carbon after tempering are well represented in the 2D simulations for the microstructure evolution of the representative steels. With the simulation, we demonstrate that the dislocations account for the experimental observation of rough twin boundaries, retained austenite within martensite, etc. in steels. Thus, based on the integrated model and the in-house codes developed in thesis, a preliminary multi-field, multiscale modeling tool is built up. The new tool couples thermodynamics and continuum mechanics at the macroscale with diffusion kinetics and phase field/Landau model at the mesoscale, and also includes the essentials of crystallography and crystal lattice dynamics at microscale.
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The runtime management of the infrastructure providing service-based systems is a complex task, up to the point where manual operation struggles to be cost effective. As the functionality is provided by a set of dynamically composed distributed services, in order to achieve a management objective multiple operations have to be applied over the distributed elements of the managed infrastructure. Moreover, the manager must cope with the highly heterogeneous characteristics and management interfaces of the runtime resources. With this in mind, this paper proposes to support the configuration and deployment of services with an automated closed control loop. The automation is enabled by the definition of a generic information model, which captures all the information relevant to the management of the services with the same abstractions, describing the runtime elements, service dependencies, and business objectives. On top of that, a technique based on satisfiability is described which automatically diagnoses the state of the managed environment and obtains the required changes for correcting it (e.g., installation, service binding, update, or configuration). The results from a set of case studies extracted from the banking domain are provided to validate the feasibility of this proposa
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Profiting by the increasing availability of laser sources delivering intensities above 10 9 W/cm 2 with pulse energies in the range of several Joules and pulse widths in the range of nanoseconds, laser shock processing (LSP) is being consolidating as an effective technology for the improvement of surface mechanical and corrosion resistance properties of metals and is being developed as a practical process amenable to production engineering. The main acknowledged advantage of the laser shock processing technique consists on its capability of inducing a relatively deep compression residual stresses field into metallic alloy pieces allowing an improved mechanical behaviour, explicitly, the life improvement of the treated specimens against wear, crack growth and stress corrosion cracking. Following a short description of the theoretical/computational and experimental methods developed by the authors for the predictive assessment and experimental implementation of LSP treatments, experimental results on the residual stress profiles and associated surface properties modification successfully reached in typical materials (specifically steels and Al and Ti alloys) under different LSP irradiation conditions are presented
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We review the evolution, state of the art and future lines of research on the sources, transport pathways, and sinks of particulate trace elements in urban terrestrial environments to include the atmosphere, soils, and street and indoor dusts. Such studies reveal reductions in the emissions of some elements of historical concern such as Pb, with interest consequently focusing on other toxic trace elements such as As, Cd, Hg, Zn, and Cu. While establishment of levels of these elements is important in assessing the potential impacts of human society on the urban environment, it is also necessary to apply this knowledge in conjunction with information on the toxicity of those trace elements and the degree of exposure of human receptors to an assessment of whether such contamination represents a real risk to the city’s inhabitants and therefore how this risk can be addressed.
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The geochemical fingerprint of sediment retrieved from the banks of the River Manzanares as it passes through the City of Madrid is presented here. The river collects the effluent water from several Waste Water Treatment (WWT) plants in and around the city, such that, at low flows, up to 60% of the flow has been treated. A total of 18 bank-sediment cores were collected along the course of the river, down to its confluence with the Jarama river, to the south–east of Madrid. Trace and major elements in each sample were extracted following a double protocol: (a) “Total” digestion with HNO3, HClO4 and HF; (b) “Weak” digestion with sodium acetate buffered to pH=5 with acetic acid, under constant stirring. The digests thus obtained were subsequently analysed by ICP-AES, except for Hg which was extracted with aqua regia and sodium chloride-hydroxylamine sulfate, and analysed by Cold Vapour-AAS. X-ray diffraction was additionally employed to determine the mineralogical composition of the samples. Uni- and multivariate analyses of the chemical data reveal the influence of Madrid on the geochemistry of Manzanares' sediments, clearly manifested by a marked increase in the concentration of typically “urban” elements Ag, Cr, Cu, Pb and Zn, downstream of the intersection of the river with the city's perimeter. The highest concentrations of these elements appear to be associated with illegal or accidental dumping of waste materials, and with the uncontrolled incorporation of untreated urban runoff to the river. The natural matrix of the sediment is characterised by fairly constant concentrations of Ce, La and Y, whereas changes in the lithology intersected by the river cause corresponding variations in Ca–Mg and Al–Na contents. In the final stretch of the river, the presence of carbonate materials seems to exert a strong geochemical control on the amount of Zn and, to a lesser extent, Cu immobilised in the sediments. This fact suggests that a variable but significant proportion of both elements may be susceptible to reincorporation in the aqueous phase under realistic environmental conditions.
Resumo:
El gran desarrollo industrial y demográfico de las últimas décadas ha dado lugar a un consumo crecientemente insostenible de energía y materias primas, que influye negativamente en el ambiente por la gran cantidad de contaminantes generados. Entre las emisiones tienen gran importancia los compuestos orgánicos volátiles (COV), y entre ellos los compuestos halogenados como el tricloroetileno, debido a su elevada toxicidad y resistencia a la degradación. Las tecnologías generalmente empleadas para la degradación de estos compuestos presentan inconvenientes derivados de la generación de productos tóxicos intermedios o su elevado coste. Dentro de los procesos avanzados de oxidación (Advanced Oxidation Processes AOP), la fotocatálisis resulta una técnica atractiva e innovadora de interés creciente en su aplicación para la eliminación de multitud de compuestos orgánicos e inorgánicos, y se ha revelado como una tecnología efectiva en la eliminación de compuestos orgánicos volátiles clorados como el tricloroetileno. Además, al poder aprovechar la luz solar como fuente de radiación UV permite una reducción significativa de costes energéticos y de operación. Los semiconductores más adecuados para su empleo como fotocatalizadores con aprovechamiento de la luz solar son aquellos que tienen una banda de energía comparable a la de los fotones de luz visible o, en su defecto, de luz ultravioleta A (Eg < 3,5 eV), siendo el más empleado el dióxido de titanio (TiO2). El objetivo principal de este trabajo es el estudio de polímeros orgánicos comerciales como soporte para el TiO2 en fotocatálisis heterogénea y su ensayo para la eliminación de tricloroetileno en aire. Para ello, se han evaluado sus propiedades ópticas y su resistencia a la fotodegradación, y se ha optimizado la fijación del fotocatalizador para conseguir un recubrimiento homogéneo, duradero y con elevada actividad fotocatalítica en diversas condiciones de operación. Los materiales plásticos ensayados fueron el polietileno (PE), copolímero de etil vinil acetato con distintos aditivos (EVA, EVA-H y EVA-SH), polipropileno (PP), polimetil (metacrilato) fabricado en colada y extrusión (PMMA-C y PMMA-E), policarbonato compacto y celular (PC-C y PC-Ce), polivinilo rígido y flexible (PVC-R y PVC-F), poliestireno (PS) y poliésteres (PET y PETG). En base a sus propiedades ópticas se seleccionaron el PP, PS, PMMA-C, EVA-SH y PVC-R, los cuales mostraron un valor de transmitancia superior al 80% en el entorno de la región estudiada (λ=365nm). Para la síntesis del fotocatalizador se empleó la tecnología sol-gel y la impregnación multicapa de los polímeros seleccionados por el método de dip-coating con secado intermedio a temperaturas moderadas. Con el fin de evaluar el envejecimiento de los polímeros bajo la radiación UV, y el efecto sobre éste del recubrimiento fotoactivo, se realizó un estudio en una cámara de exposición a la luz solar durante 150 días, evaluándose la resistencia química y la resistencia mecánica. Los resultados de espectroscopía infrarroja y del test de tracción tras el envejecimiento revelaron una mayor resistencia del PMMA y una degradación mayor en el PS, PVC-R y EVA SH, con una apreciable pérdida del recubrimiento en todos los polímeros. Los fotocatalizadores preparados sobre soportes sin tratamiento y con tres capas de óxido de titanio mostraron mejores resultados de actividad con PMMA-C, PET y PS, con buenos resultados de mineralización. Para conseguir una mayor y mejor fijación de la película al soporte se realizaron tratamientos químicos abrasivos con H2SO4 y NaOH y tratamientos de funcionalización superficial por tecnología de plasma a presión atmosférica (APP) y a baja presión (LPP). Con los tratamientos de plasma se consiguió una excelente mojabilidad de los soportes, que dio lugar a una distribución uniforme y más abundante del fotocatalizador, mientras que con los tratamientos químicos no se obtuvo una mejora significativa. Asimismo, se prepararon fotocatalizadores con una capa previa de dióxido de silicio con la intervención de surfactantes (PDDA-SiO2-3TiO2 y SiO2FC-3TiO2), consiguiéndose buenas propiedades de la película en todos los casos. Los mejores resultados de actividad con tratamiento LPP y tres capas de TiO2 se lograron con PMMA-C (91% de conversión a 30 ppm de TCE y caudal 200 ml·min-1) mejorando significativamente también la actividad fotocatalítica en PVC-R y PS. Sin embargo, el material más activo de todos los ensayados fue el PMMA-C con el recubrimiento SiO2FC-3TiO2, logrando el mejor grado de mineralización, del 45%, y una velocidad de 1,89 x 10-6 mol· m-2 · s-1, que dio lugar a la eliminación del 100 % del tricloroetileno en las condiciones anteriormente descritas. A modo comparativo se realizaron ensayos de actividad con otro contaminante orgánico tipo, el formaldehído, cuya degradación fotocatalítica fue también excelente (100% de conversión y 80% de mineralización con 24 ppm de HCHO en un caudal de aire seco de 200 ml·min-1). Los buenos resultados de actividad obtenidos confirman las enormes posibilidades que ofrecen los polímeros transparentes en el UV-A como soportes del dióxido de titanio para la eliminación fotocatalítica de contaminantes en aire. ABSTRACT The great industrial and demographic development of recent decades has led to an unsustainable increase of energy and raw materials consumption that negatively affects the environment due to the large amount of waste and pollutants generated. Between emissions generated organic compounds (VOCs), specially the halogenated ones such as trichloroethylene, are particularly important due to its high toxicity and resistance to degradation. The technologies generally used for the degradation of these compounds have serious inconveniences due to the generation of toxic intermediates turn creating the problem of disposal besides the high cost. Among the advanced oxidation processes (AOP), photocatalysis is an attractive and innovative technique with growing interest in its application for the removal of many organic and inorganic compounds, and has emerged as an effective technology in eliminating chlorinated organic compounds such as trichloroethylene. In addition, as it allows the use of sunlight as a source of UV radiation there is a significant reduction of energy costs and operation. Semiconductors suitable to be used as photocatalyst activated by sunlight are those having an energy band comparable to that of the visible or UV-A light (Eg <3,5 eV), being titanium dioxide (TiO2), the most widely used. The main objective of this study is the test of commercial organic polymers as supports for TiO2 to be applied in heterogeneous photocatalysis and its assay for removing trichloroethylene in air. To accomplish that, its optical properties and resistance to photooxidation have been evaluated, and different operating conditions have been tested in order to optimize the fixation of the photocatalyst to obtain a homogeneous coating, with durable and high photocatalytic activity. The plastic materials tested were: polyethylene (PE), ethyl vinyl acetace copolymers with different additives (EVA, EVA-H and EVA -SH), polypropylene (PP), poly methyl (methacrylate) manufactured by sheet moulding and extrusion (PMMA-C and PMMA-E), compact and cellular polycarbonates (PC-C PC-Ce), rigid and flexible polyvinyl chloride (PVC-R and PVC-F), polystyrene (PS) and polyesters (PET and PETG). On the basis of their optical properties PP, PS, PMMA-C, EVA-SH and PVC-R were selected, as they showed a transmittance value greater than 80% in the range of the studied region (λ = 365nm). For the synthesis of the photocatalyst sol-gel technology was employed with multilayers impregnation of the polymers selected by dip-coating, with intermediate TiO2 drying at moderate temperatures. To evaluate the polymers aging due to UV radiation, and the effect of photoactive coating thereon, a study in an sunlight exposure chamber for 150 days was performed, evaluating the chemical resistance and the mechanical strength. The results of infrared spectroscopy and tensile stress test after aging showed the PMMA is the most resistant sample, but a greater degradation in PS, PVC-R and EVA SH, with a visible loss of the coating in all the polymers tested. The photocatalysts prepared on the untreated substrates with three layers of TiO2 showed better activity results when PMMA-C, PET and PS where used. To achieve greater and better fixation of the film to the support, chemical abrasive treatments, with H2SO4 and NaOH, as well as surface functionalization treatments with atmospheric pressure plasma (APP) and low pressure plasma (LPP) technologies were performed. The plasma treatment showed the best results, with an excellent wettability of the substrates that lead to a better and uniform distribution of the photocatalyst compared to the chemical treatments tested, in which no significant improvement was obtained. Also photocatalysts were prepared with the a silicon dioxide previous layer with the help of surfactants (SiO2- 3TiO2 PDDA-and-3TiO2 SiO2FC), obtaining good properties of the film in all cases. The best activity results for LPP-treated samples with three layers of TiO2 were achieved with PMMA-C (91% conversion, in conditions of 30 ppm of TCE and 200 ml·min-1 air flow rate), with a significant improvement of the photocatalytic activity in PVC-R and PS samples too. However, among all the materials assayed, PMMA-C with SiO2FC-3TiO2 coating was the most active one, achieving the highest mineralization grade (45%) and a reaction rate of 1,89 x 10-6 mol· m-2 · s-1, with total trichloroethylene elimination in the same conditions. As a comparative assay, an activity test was also performed with another typical organic contaminant, formaldehyde, also with good results (100% conversion with 24 ppm of HCHO and 200 ml·min-1 gas flow rate). The good activity results obtained in this study confirm the great potential of organic polymers which are transparent in the UV-A as supports for titanium dioxide for photocatalytic removal of air organic pollutants.
Resumo:
Pot experiments were performed to evaluate the phytoremediation capacity of plants of Atriplex halimus grown in contaminated mine soils and to investigate the effects of organic amendments on the metal bioavailability and uptake of these metals by plants. Soil samples collected from abandoned mine sites north of Madrid (Spain) were mixed with 0, 30 and 60 Mg ha?1 of two organic amendments, with different pH and nutrients content: pine-bark compost and horse- and sheep-manure compost. The increasing soil organic matter content and pH by the application of manure amendment reduced metal bioavailability in soil stabilising them. The proportion of Cu in the most bioavailable fractions (sum of the water-soluble, exchangeable, acid-soluble and Fe?Mn oxides fractions) decreased with the addition of 60 Mg ha?1 of manure from 62% to 52% in one of the soils studied and from 50% to 30% in the other. This amendment also reduced Zn proportion in water-soluble and exchangeable fractions from 17% to 13% in one of the soils. Manure decreased metal concentrations in shoots of A. halimus, from 97 to 35 mg kg?1 of Cu, from 211 to 98 mg kg?1 of Zn and from 1.4 to 0.6 mg kg?1 of Cd. In these treatments there was a higher plant growth due to the lower metal toxicity and the improvement of nutrients content in soil. This higher growth resulted in a higher total metal accumulation in plant biomass and therefore in a greater amount of metals removed from soil, so manure could be useful for phytoextraction purposes. This amendment increased metal accumulation in shoots from 37 to 138 mg pot?1 of Cu, from 299 to 445 mg pot?1 of Zn and from 1.8 to 3.7 mg pot?1 of Cd. Pine bark amendment did not significantly alter metal availability and its uptake by plants. Plants of A. halimus managed to reduce total Zn concentration in one of the soils from 146 to 130 mg kg?1, but its phytoextraction capacity was insufficient to remediate contaminated soils in the short-to-medium term. However, A. halimus could be, in combination with manure amendment, appropriate for the phytostabilization of metals in mine soils.
Resumo:
Cuando una colectividad de sistemas dinámicos acoplados mediante una estructura irregular de interacciones evoluciona, se observan dinámicas de gran complejidad y fenómenos emergentes imposibles de predecir a partir de las propiedades de los sistemas individuales. El objetivo principal de esta tesis es precisamente avanzar en nuestra comprensión de la relación existente entre la topología de interacciones y las dinámicas colectivas que una red compleja es capaz de mantener. Siendo este un tema amplio que se puede abordar desde distintos puntos de vista, en esta tesis se han estudiado tres problemas importantes dentro del mismo que están relacionados entre sí. Por un lado, en numerosos sistemas naturales y artificiales que se pueden describir mediante una red compleja la topología no es estática, sino que depende de la dinámica que se desarrolla en la red: un ejemplo son las redes de neuronas del cerebro. En estas redes adaptativas la propia topología emerge como consecuencia de una autoorganización del sistema. Para conocer mejor cómo pueden emerger espontáneamente las propiedades comúnmente observadas en redes reales, hemos estudiado el comportamiento de sistemas que evolucionan según reglas adaptativas locales con base empírica. Nuestros resultados numéricos y analíticos muestran que la autoorganización del sistema da lugar a dos de las propiedades más universales de las redes complejas: a escala mesoscópica, la aparición de una estructura de comunidades, y, a escala macroscópica, la existencia de una ley de potencias en la distribución de las interacciones en la red. El hecho de que estas propiedades aparecen en dos modelos con leyes de evolución cuantitativamente distintas que siguen unos mismos principios adaptativos sugiere que estamos ante un fenómeno que puede ser muy general, y estar en el origen de estas propiedades en sistemas reales. En segundo lugar, proponemos una medida que permite clasificar los elementos de una red compleja en función de su relevancia para el mantenimiento de dinámicas colectivas. En concreto, estudiamos la vulnerabilidad de los distintos elementos de una red frente a perturbaciones o grandes fluctuaciones, entendida como una medida del impacto que estos acontecimientos externos tienen en la interrupción de una dinámica colectiva. Los resultados que se obtienen indican que la vulnerabilidad dinámica es sobre todo dependiente de propiedades locales, por tanto nuestras conclusiones abarcan diferentes topologías, y muestran la existencia de una dependencia no trivial entre la vulnerabilidad y la conectividad de los elementos de una red. Finalmente, proponemos una estrategia de imposición de una dinámica objetivo genérica en una red dada e investigamos su validez en redes con diversas topologías que mantienen regímenes dinámicos turbulentos. Se obtiene como resultado que las redes heterogéneas (y la amplia mayora de las redes reales estudiadas lo son) son las más adecuadas para nuestra estrategia de targeting de dinámicas deseadas, siendo la estrategia muy efectiva incluso en caso de disponer de un conocimiento muy imperfecto de la topología de la red. Aparte de la relevancia teórica para la comprensión de fenómenos colectivos en sistemas complejos, los métodos y resultados propuestos podrán dar lugar a aplicaciones en sistemas experimentales y tecnológicos, como por ejemplo los sistemas neuronales in vitro, el sistema nervioso central (en el estudio de actividades síncronas de carácter patológico), las redes eléctricas o los sistemas de comunicaciones. ABSTRACT The time evolution of an ensemble of dynamical systems coupled through an irregular interaction scheme gives rise to dynamics of great of complexity and emergent phenomena that cannot be predicted from the properties of the individual systems. The main objective of this thesis is precisely to increase our understanding of the interplay between the interaction topology and the collective dynamics that a complex network can support. This is a very broad subject, so in this thesis we will limit ourselves to the study of three relevant problems that have strong connections among them. First, it is a well-known fact that in many natural and manmade systems that can be represented as complex networks the topology is not static; rather, it depends on the dynamics taking place on the network (as it happens, for instance, in the neuronal networks in the brain). In these adaptive networks the topology itself emerges from the self-organization in the system. To better understand how the properties that are commonly observed in real networks spontaneously emerge, we have studied the behavior of systems that evolve according to local adaptive rules that are empirically motivated. Our numerical and analytical results show that self-organization brings about two of the most universally found properties in complex networks: at the mesoscopic scale, the appearance of a community structure, and, at the macroscopic scale, the existence of a power law in the weight distribution of the network interactions. The fact that these properties show up in two models with quantitatively different mechanisms that follow the same general adaptive principles suggests that our results may be generalized to other systems as well, and they may be behind the origin of these properties in some real systems. We also propose a new measure that provides a ranking of the elements in a network in terms of their relevance for the maintenance of collective dynamics. Specifically, we study the vulnerability of the elements under perturbations or large fluctuations, interpreted as a measure of the impact these external events have on the disruption of collective motion. Our results suggest that the dynamic vulnerability measure depends largely on local properties (our conclusions thus being valid for different topologies) and they show a non-trivial dependence of the vulnerability on the connectivity of the network elements. Finally, we propose a strategy for the imposition of generic goal dynamics on a given network, and we explore its performance in networks with different topologies that support turbulent dynamical regimes. It turns out that heterogeneous networks (and most real networks that have been studied belong in this category) are the most suitable for our strategy for the targeting of desired dynamics, the strategy being very effective even when the knowledge on the network topology is far from accurate. Aside from their theoretical relevance for the understanding of collective phenomena in complex systems, the methods and results here discussed might lead to applications in experimental and technological systems, such as in vitro neuronal systems, the central nervous system (where pathological synchronous activity sometimes occurs), communication systems or power grids.
Resumo:
A raíz de la aparición de los procesadores dotados de varios “cores”, la programación paralela, un concepto que, por otra parte no era nada nuevo y se conocía desde hace décadas, sufrió un nuevo impulso, pues se creía que se podía superar el techo tecnológico que había estado limitando el rendimiento de esta programación durante años. Este impulso se ha ido manteniendo hasta la actualidad, movido por la necesidad de sistemas cada vez más potentes y gracias al abaratamiento de los costes de fabricación. Esta tendencia ha motivado la aparición de nuevo software y lenguajes con componentes orientados precisamente al campo de la programación paralela. Este es el caso del lenguaje Go, desarrollado por Google y lanzado en 2009. Este lenguaje se basa en modelos de concurrencia que lo hacen muy adecuados para abordar desarrollos de naturaleza paralela. Sin embargo, la programación paralela es un campo complejo y heterogéneo, y los programadores son reticentes a utilizar herramientas nuevas, en beneficio de aquellas que ya conocen y les son familiares. Un buen ejemplo son aquellas implementaciones de lenguajes conocidos, pero orientadas a programación paralela, y que siguen las directrices de un estándar ampliamente reconocido y aceptado. Este es el caso del estándar OpenMP, un Interfaz de Programación de Aplicaciones (API) flexible, portable y escalable, orientado a la programación paralela multiproceso en arquitecturas multi-core o multinucleo. Dicho estándar posee actualmente implementaciones en los lenguajes C, C++ y Fortran. Este proyecto nace como un intento de aunar ambos conceptos: un lenguaje emergente con interesantes posibilidades en el campo de la programación paralela, y un estándar reputado y ampliamente extendido, con el que los programadores se encuentran familiarizados. El objetivo principal es el desarrollo de un conjunto de librerías del sistema (que engloben directivas de compilación o pragmas, librerías de ejecución y variables de entorno), soportadas por las características y los modelos de concurrencia propios de Go; y que añadan funcionalidades propias del estándar OpenMP. La idea es añadir funcionalidades que permitan programar en lenguaje Go utilizando la sintaxis que OpenMP proporciona para otros lenguajes, como Fortan y C/C++ (concretamente, similar a esta última), y, de esta forma, dotar al usuario de Go de herramientas para programar estructuras de procesamiento paralelo de forma sencilla y transparente, de la misma manera que lo haría utilizando C/C++.---ABSTRACT---As a result of the appearance of processors equipped with multiple "cores ", parallel programming, a concept which, moreover, it was not new and it was known for decades, suffered a new impulse, because it was believed they could overcome the technological ceiling had been limiting the performance of this program for years. This impulse has been maintained until today, driven by the need for ever more powerful systems and thanks to the decrease in manufacturing costs. This trend has led to the emergence of new software and languages with components guided specifically to the field of parallel programming. This is the case of Go language, developed by Google and released in 2009. This language is based on concurrency models that make it well suited to tackle developments in parallel nature. However, parallel programming is a complex and heterogeneous field, and developers are reluctant to use new tools to benefit those who already know and are familiar. A good example are those implementations from well-known languages, but parallel programming oriented, and witch follow the guidelines of a standard widely recognized and accepted. This is the case of the OpenMP standard, an application programming interface (API), flexible, portable and scalable, parallel programming oriented, and designed for multi-core architectures. This standard currently has implementations in C, C ++ and Fortran. This project was born as an attempt to combine two concepts: an emerging language, with interesting possibilities in the field of parallel programming, and a reputed and widespread standard, with which programmers are familiar with. The main objective is to develop a set of system libraries (which includes compiler directives or pragmas, runtime libraries and environment variables), supported by the characteristics and concurrency patterns of Go; and that add custom features from the OpenMP standard. The idea is to add features that allow programming in Go language using the syntax OpenMP provides for other languages, like Fortran and C / C ++ (specifically, similar to the latter ), and, in this way, provide Go users with tools for programming parallel structures easily and, in the same way they would using C / C ++.