Zooplankton abundance and size structure in the North Atlantic from M87/1_596-1

Data on zooplankton abundance and biovolume were collected in concert with data on the biophysical environment during the development of the phytoplankton spring bloom at 4 stations in the North Atlantic. Station 1 in the Icelandic Basin was visited four times (26 March, 8 April, 18 April, 27 April), Station 2 in the southern Norwegian Sea was visited three times (30 March, 13 April, 23 April), Station 3 in the North Sea was visited twice (2 April, 15 April) and one intermediate station was visited once. The data were sampled by a Laser Optical Plankton Counter (LOPC, Rolls Royce Canada Ltd.) that was mounted on a carousel water sampler together with a Conductivity-Temperature-Depth sensor (CTD, SBE19plusV2, Seabird Electronics, Inc., USA). Based on the LOPC data, abundance (individuals/m**3) and biovolume (mm3/m**3) were calculated as described in the LOPC Software Operation Manual [(Anonymous, 2006), http://www.brooke-ocean.com/index.html]. LOPC data were regrouped into 49 size groups of equal log10 (body volume) increments (Edvardsen et al., 2002, doi:10.3354/meps227205). LOPC data quality was checked as described in Basedow et al. (2013, doi:10.1016/j.pocean.2012.10.005). CTD data were screened for erroneous (out of range) values and then averaged to the same frequency as the LOPC data (2 Hz). All data were processed using especially developed scripts in the python programming language. The LOPC is an optical instrument designed to count and measure particles (0.1 to 30 mm equivalent spherical diameter) in the water column (Herman et al., 2004; doi:10.1093/plankt/fbh095). The size of particles as equivalent spherical diameter (ESD) was computed as described in the manual (Anonymous, 2006), and in more detail in Checkley et al. (2008, doi:10.4319/lo.2008.53.5_part_2.2123) and Gaardsted et al. (2010, doi:10.1111/j.1365-2419.2010.00558.x).

Zooplankton abundance and size structure in the North Atlantic from M87/1_506-1

Data on zooplankton abundance and biovolume were collected in concert with data on the biophysical environment during the development of the phytoplankton spring bloom at 4 stations in the North Atlantic. Station 1 in the Icelandic Basin was visited four times (26 March, 8 April, 18 April, 27 April), Station 2 in the southern Norwegian Sea was visited three times (30 March, 13 April, 23 April), Station 3 in the North Sea was visited twice (2 April, 15 April) and one intermediate station was visited once. The data were sampled by a Laser Optical Plankton Counter (LOPC, Rolls Royce Canada Ltd.) that was mounted on a carousel water sampler together with a Conductivity-Temperature-Depth sensor (CTD, SBE19plusV2, Seabird Electronics, Inc., USA). Based on the LOPC data, abundance (individuals/m**3) and biovolume (mm3/m**3) were calculated as described in the LOPC Software Operation Manual [(Anonymous, 2006), http://www.brooke-ocean.com/index.html]. LOPC data were regrouped into 49 size groups of equal log10 (body volume) increments (Edvardsen et al., 2002, doi:10.3354/meps227205). LOPC data quality was checked as described in Basedow et al. (2013, doi:10.1016/j.pocean.2012.10.005). CTD data were screened for erroneous (out of range) values and then averaged to the same frequency as the LOPC data (2 Hz). All data were processed using especially developed scripts in the python programming language. The LOPC is an optical instrument designed to count and measure particles (0.1 to 30 mm equivalent spherical diameter) in the water column (Herman et al., 2004; doi:10.1093/plankt/fbh095). The size of particles as equivalent spherical diameter (ESD) was computed as described in the manual (Anonymous, 2006), and in more detail in Checkley et al. (2008, doi:10.4319/lo.2008.53.5_part_2.2123) and Gaardsted et al. (2010, doi:10.1111/j.1365-2419.2010.00558.x).

Zooplankton abundance and size structure in the North Atlantic from M87/1_558-1

Data on zooplankton abundance and biovolume were collected in concert with data on the biophysical environment during the development of the phytoplankton spring bloom at 4 stations in the North Atlantic. Station 1 in the Icelandic Basin was visited four times (26 March, 8 April, 18 April, 27 April), Station 2 in the southern Norwegian Sea was visited three times (30 March, 13 April, 23 April), Station 3 in the North Sea was visited twice (2 April, 15 April) and one intermediate station was visited once. The data were sampled by a Laser Optical Plankton Counter (LOPC, Rolls Royce Canada Ltd.) that was mounted on a carousel water sampler together with a Conductivity-Temperature-Depth sensor (CTD, SBE19plusV2, Seabird Electronics, Inc., USA). Based on the LOPC data, abundance (individuals/m**3) and biovolume (mm3/m**3) were calculated as described in the LOPC Software Operation Manual [(Anonymous, 2006), http://www.brooke-ocean.com/index.html]. LOPC data were regrouped into 49 size groups of equal log10 (body volume) increments (Edvardsen et al., 2002, doi:10.3354/meps227205). LOPC data quality was checked as described in Basedow et al. (2013, doi:10.1016/j.pocean.2012.10.005). CTD data were screened for erroneous (out of range) values and then averaged to the same frequency as the LOPC data (2 Hz). All data were processed using especially developed scripts in the python programming language. The LOPC is an optical instrument designed to count and measure particles (0.1 to 30 mm equivalent spherical diameter) in the water column (Herman et al., 2004; doi:10.1093/plankt/fbh095). The size of particles as equivalent spherical diameter (ESD) was computed as described in the manual (Anonymous, 2006), and in more detail in Checkley et al. (2008, doi:10.4319/lo.2008.53.5_part_2.2123) and Gaardsted et al. (2010, doi:10.1111/j.1365-2419.2010.00558.x).

Zooplankton abundance and size structure in the North Atlantic from M87/1_435-1

Data on zooplankton abundance and biovolume were collected in concert with data on the biophysical environment during the development of the phytoplankton spring bloom at 4 stations in the North Atlantic. Station 1 in the Icelandic Basin was visited four times (26 March, 8 April, 18 April, 27 April), Station 2 in the southern Norwegian Sea was visited three times (30 March, 13 April, 23 April), Station 3 in the North Sea was visited twice (2 April, 15 April) and one intermediate station was visited once. The data were sampled by a Laser Optical Plankton Counter (LOPC, Rolls Royce Canada Ltd.) that was mounted on a carousel water sampler together with a Conductivity-Temperature-Depth sensor (CTD, SBE19plusV2, Seabird Electronics, Inc., USA). Based on the LOPC data, abundance (individuals/m**3) and biovolume (mm3/m**3) were calculated as described in the LOPC Software Operation Manual [(Anonymous, 2006), http://www.brooke-ocean.com/index.html]. LOPC data were regrouped into 49 size groups of equal log10 (body volume) increments (Edvardsen et al., 2002, doi:10.3354/meps227205). LOPC data quality was checked as described in Basedow et al. (2013, doi:10.1016/j.pocean.2012.10.005). CTD data were screened for erroneous (out of range) values and then averaged to the same frequency as the LOPC data (2 Hz). All data were processed using especially developed scripts in the python programming language. The LOPC is an optical instrument designed to count and measure particles (0.1 to 30 mm equivalent spherical diameter) in the water column (Herman et al., 2004; doi:10.1093/plankt/fbh095). The size of particles as equivalent spherical diameter (ESD) was computed as described in the manual (Anonymous, 2006), and in more detail in Checkley et al. (2008, doi:10.4319/lo.2008.53.5_part_2.2123) and Gaardsted et al. (2010, doi:10.1111/j.1365-2419.2010.00558.x).

Zooplankton abundance and size structure in the North Atlantic from M87/1_515-1

Data on zooplankton abundance and biovolume were collected in concert with data on the biophysical environment during the development of the phytoplankton spring bloom at 4 stations in the North Atlantic. Station 1 in the Icelandic Basin was visited four times (26 March, 8 April, 18 April, 27 April), Station 2 in the southern Norwegian Sea was visited three times (30 March, 13 April, 23 April), Station 3 in the North Sea was visited twice (2 April, 15 April) and one intermediate station was visited once. The data were sampled by a Laser Optical Plankton Counter (LOPC, Rolls Royce Canada Ltd.) that was mounted on a carousel water sampler together with a Conductivity-Temperature-Depth sensor (CTD, SBE19plusV2, Seabird Electronics, Inc., USA). Based on the LOPC data, abundance (individuals/m**3) and biovolume (mm3/m**3) were calculated as described in the LOPC Software Operation Manual [(Anonymous, 2006), http://www.brooke-ocean.com/index.html]. LOPC data were regrouped into 49 size groups of equal log10 (body volume) increments (Edvardsen et al., 2002, doi:10.3354/meps227205). LOPC data quality was checked as described in Basedow et al. (2013, doi:10.1016/j.pocean.2012.10.005). CTD data were screened for erroneous (out of range) values and then averaged to the same frequency as the LOPC data (2 Hz). All data were processed using especially developed scripts in the python programming language. The LOPC is an optical instrument designed to count and measure particles (0.1 to 30 mm equivalent spherical diameter) in the water column (Herman et al., 2004; doi:10.1093/plankt/fbh095). The size of particles as equivalent spherical diameter (ESD) was computed as described in the manual (Anonymous, 2006), and in more detail in Checkley et al. (2008, doi:10.4319/lo.2008.53.5_part_2.2123) and Gaardsted et al. (2010, doi:10.1111/j.1365-2419.2010.00558.x).

Zooplankton abundance and size structure in the North Atlantic from M87/1_494-1

Data on zooplankton abundance and biovolume were collected in concert with data on the biophysical environment during the development of the phytoplankton spring bloom at 4 stations in the North Atlantic. Station 1 in the Icelandic Basin was visited four times (26 March, 8 April, 18 April, 27 April), Station 2 in the southern Norwegian Sea was visited three times (30 March, 13 April, 23 April), Station 3 in the North Sea was visited twice (2 April, 15 April) and one intermediate station was visited once. The data were sampled by a Laser Optical Plankton Counter (LOPC, Rolls Royce Canada Ltd.) that was mounted on a carousel water sampler together with a Conductivity-Temperature-Depth sensor (CTD, SBE19plusV2, Seabird Electronics, Inc., USA). Based on the LOPC data, abundance (individuals/m**3) and biovolume (mm3/m**3) were calculated as described in the LOPC Software Operation Manual [(Anonymous, 2006), http://www.brooke-ocean.com/index.html]. LOPC data were regrouped into 49 size groups of equal log10 (body volume) increments (Edvardsen et al., 2002, doi:10.3354/meps227205). LOPC data quality was checked as described in Basedow et al. (2013, doi:10.1016/j.pocean.2012.10.005). CTD data were screened for erroneous (out of range) values and then averaged to the same frequency as the LOPC data (2 Hz). All data were processed using especially developed scripts in the python programming language. The LOPC is an optical instrument designed to count and measure particles (0.1 to 30 mm equivalent spherical diameter) in the water column (Herman et al., 2004; doi:10.1093/plankt/fbh095). The size of particles as equivalent spherical diameter (ESD) was computed as described in the manual (Anonymous, 2006), and in more detail in Checkley et al. (2008, doi:10.4319/lo.2008.53.5_part_2.2123) and Gaardsted et al. (2010, doi:10.1111/j.1365-2419.2010.00558.x).

Grain size distributions of the Bossons glacier (France)

The study presented in this PhD memory aim at better define and quantify the present timeerosion processes in glacial and proglacial domain. The Glacier des Bossons, situated in theMont-Blanc massif (Haute-Savoie, France), is a good example of a natural and nonanthropizedsystem which allows us to study this topic. This glacier lies on two mainlithologies (the Mont-Blanc granite and the metamorphic bedrock) and this peculiarity is usedto determine the origin of the glacial sediments. The sediments were sampled at the glaciersurface and at the glacier sole and also in the subglacial streams in order to understand themechanisms of mechanical erosion and particle transportation in glacial domain. The study ofthe granulometric distribution and the origin of the sediments were performed by a lithologicanalysis at macro-scale (naked-eye) and a geochemical analysis at micro-scale (U-Pb datingof zircons). These analyses allowed specifying the characteristics of glacial erosion andtransport. (1) the supraglacial sediments derived from the erosion of the rocky valley sides aremainly coarse and the glacial transport does not mix these clasts with those derived from thesub-glacial erosion, except in the lower tongue; (2) the sub-glacial erosion rates areinhomogeneous, erosion under the temperate glacier (0.4-0.8 mm/yr) is at least sixteen timesmore efficient than the erosion under the cold glacier (0.025-0.05 mm/yr); (3) the sub-glacialsediments contain a silty and sandy fraction, resulting from processes of abrasion andcrushing, which is evacuated by sub-glacial streams. The high-resolution temporal acquisitionof hydro-sedimentary data during the 2010 melt season, between the May 5th and theSeptember 17th, allowed defining the seasonal behavior of the hydrologic and sedimentaryfluxes. The sediment exportation occurs mainly during the melt season therefore, quantify thesediment fluxes in the Bossons stream and measure regularly the topographic evolution of thefluvio-glacial system allows to perform a sedimentary balance of the erosion of glacial andnon-glacial domains. During the year 2010, about 3000 tons of sediments were eroded with430 tons settled on the fluvio-glacial system. By analyzing the evolution of suspendedparticulate matter concentrations in the Bossons stream upstream and downstream the fluvioglacialsystem, the part of glacial erosion and non-glacial denudation in the sedimentarybalance could be proportioned. The erosion during the stormy events of the uncoveredmoraines, confining the fluvio-glacial system of the Bossons stream, furnishes at least 59% ofthe sediments exported by the Bossons stream and glacial erosion (41% of the flux) istherefore less efficient comparatively. The long-term evolution of the glacial systems inperiod of global warming would show a sustained erosion of proglacial environments(mountain sides and moraines) recently exposed and therefore an increasing of the detritalfluxes. The Glacier des Bossons protects the summit of the Mont-Blanc, the differentialerosion between zones under the ice and non-glacial could lead to an increase of thedifference of altitude between valleys and summits.

An approach for particle sinking velocity measurements in the 3-400 µm size range and considerations on the effect of temperature on sinking rates

The flux of organic particles below the mixed layer is one major pathway of carbon from the surface into the deep ocean. The magnitude of this export flux depends on two major processes-remineralization rates and sinking velocities. Here, we present an efficient method to measure sinking velocities of particles in the size range from approximately 3-400 µm by means of video microscopy (FlowCAM®). The method allows rapid measurement and automated analysis of mixed samples and was tested with polystyrene beads, different phytoplankton species, and sediment trap material. Sinking velocities of polystyrene beads were close to theoretical values calculated from Stokes' Law. Sinking velocities of the investigated phytoplankton species were in reasonable agreement with published literature values and sinking velocities of material collected in sediment trap increased with particle size. Temperature had a strong effect on sinking velocities due to its influence on seawater viscosity and density. An increase in 9 °C led to a measured increase in sinking velocities of 40 %. According to this temperature effect, an average temperature increase in 2 °C as projected for the sea surface by the end of this century could increase sinking velocities by about 6 % which might have feedbacks on carbon export into the deep ocean.

Diseño y síntesis de materiales nanoestructurados basados en aluminatos de estroncio con propiedades fotoluminiscentes

Durante la última década, se han llevado acabo numeroso estudios sobre la síntesis de materiales fotoluminiscentes sub-micrónicos, en gran medida, al amplio número de aplicaciones que demandan este tipo de materiales. En concreto dentro de los materiales fosforescentes o también denominados materiales con una prolongada persistencia de la luminiscencia, los estudios se han enfocado en la matriz de SrAl2O4 dopada con Europio (Eu2+) y Disprosio (Dy3+) dado que tiene mayor estabilidad y persistencia de la fosforescencia con respecto a otras matrices. Estos materiales se emplean mayoritariamente en pinturas luminiscentes, tintas, señalización de seguridad pública, cerámicas, relojes, textiles y juguetes fosforescentes. Dado al amplio campo de aplicación de los SrAl2O4:Eu, Dy, se han investigado múltiples rutas de síntesis como la ruta sol-gel, la síntesis hidrotermal, la síntesis por combustión, la síntesis láser y la síntesis en estado sólido con el fin de desarrollar un método eficiente y que sea fácilmente escalable. Sin embargo, en la actualidad el método que se emplea para el procesamiento a nivel industrial de los materiales basados en aluminato de estroncio es la síntesis por estado sólido, que requiere de temperaturas de entre 1300 a 1900oC y largos tiempos de procesamiento. Además el material obtenido tiene un tamaño de partícula de 20 a 100 μm; siendo este tamaño restrictivo para el empleo de este tipo de material en determinadas aplicaciones. Por tanto, el objetivo de este trabajo es el desarrollo de nuevas estrategias que solventen las actuales limitaciones. Dentro de este marco se plantean una serie de objetivos específicos: Estudio de los parámetros que gobiernan los procesos de reducción del tamaño de partícula mediante molienda y su relación en la respuesta fotoluminiscente. Estudio de la síntesis por combustión de SrAl2O4:Eu, Dy, evaluando el efecto de la temperatura y la cantidad de combustible (urea) en el proceso para la obtención de partículas cristalinas minimizando la presencia de fases secundarias. Desarrollo de nuevas rutas de síntesis de SrAl2O4:Eu, Dy empleando el método de sales fundidas. Determinación de los mecanismos de reacción en presencia de la sal fundida en función de los parámetros de proceso que comprende la relación de sales y reactivos, la naturaleza de la alúmina y su tamaño, la temperatura y atmósfera de tratamiento. Mejora de la eficiencia de los procesos de síntesis para obtener productos con propiedades finales óptimas en procesos factibles industrialmente para su transferencia tecnológica. Es este trabajo han sido evaluados los efectos de diferentes procesos de molienda para la reducción del tamaño de partícula del material de SrAl2O4:Eu, Dy comercial. En el proceso de molienda en medio húmedo por atrición se observa la alteración de la estructura cristalina del material debido a la reacción de hidrólisis generada incluso empleando como medio líquido etanol absoluto. Con el fin de solventar las desventajas de la molienda en medio húmedo se llevo a cabo un estudio de la molturación en seco del material. La molturación en seco de alta energía reduce significativamente el tamaño medio de partícula. Sin embargo, procesos de molienda superiores a una duración de 10 minutos ocasionan un aumento del estado de aglomeración de las partículas y disminuyen drásticamente la respuesta fotoluminiscente del material. Por tanto, se lleva a cabo un proceso de molienda en seco de baja energía. Mediante este método se consigue reducir el tamaño medio de partícula, d50=2.8 μm, y se mejora la homogeneidad de la distribución del tamaño de partícula evitando la amorfización del material. A partir de los resultados obtenidos mediante difracción de rayos X y microscopia electrónica de barrido se infiere que la disminución de la intensidad de la fotoluminiscencia después de la molienda en seco de alta energía con respecto al material inicial se debe principalmente a la reducción del tamaño de cristalito. Se observan menores variaciones en la intensidad de la fotoluminiscencia cuando se emplea un método de molienda de baja de energía ya que en estos procesos se preserva el dominio cristalino y se reduce la amorfización significativamente. Estos resultados corroboran que la intensidad de la fotoluminiscencia y la persistencia de la luminiscencia de los materiales de SrAl2O4:Eu2+, Dy3+ dependen extrínsecamente de la morfología de las partículas, del tamaño de partícula, el tamaño de grano, los defectos superficiales e intrínsecamente del tamaño de cristalito. Siendo las características intrínsecas las que dominan con respecto a las extrínsecas y por tanto tienen mayor relevancia en la respuesta fotoluminiscente. Mediante síntesis por combustión se obtuvieron láminas nanoestructuradas de SrAl2O4:Eu, Dy de ≤1 μm de espesor. La cantidad de combustible, urea, en la reacción influye significativamente en la formación de determinadas fases cristalinas. Para la síntesis del material de SrAl2O4:Eu, Dy es necesario incluir un contenido de urea mayor que el estequiométrico (siendo m=1 la relación estequiométrica). La incorporación de un exceso de urea (m>1) requiere de la presencia de un agente oxidante interno, HNO3, para que la reacción tenga lugar. El empleo de un mayor contenido de urea como combustible permite una quelación efectiva de los cationes en el sistema y la creación de las condiciones reductoras para obtener un material de mayor cristalinidad y con mejores propiedades fotoluminiscentes. El material de SrAl2O4:Eu, Dy sintetizado a una temperatura de ignición de 600oC tiene un tamaño medio 5-25 μm con un espesor de ≤1 μm. Mediante procesos de molturación en seco de baja energía es posible disminuir el tamaño medio de partícula ≈2 μm y homogenizar la distribución del tamaño de partícula pero hay un deterioro asociado de la respuesta luminiscente. Sin embargo, se puede mejorar la respuesta fotoluminiscente empleando un tratamiento térmico posterior a 900oC N2-H2 durante 1 hora que no supone un aumento del tamaño de partícula pero si permite aumentar el tamaño de cristalito y la reducción del Eu3+ a Eu2+. Con respecto a la respuesta fotoluminiscente, se obtiene valores de la intensidad de la fotoluminiscencia entre un 35%-21% con respecto a la intensidad de un material comercial de referencia. Además la intensidad inicial del decaimiento de la fosforescencia es un 20% de la intensidad del material de referencia. Por tanto, teniendo en cuenta estos resultados, es necesario explorar otros métodos de síntesis para la obtención de los materiales bajo estudio. Por esta razón, en este trabajo se desarrollo una ruta de síntesis novedosa para sintetizar SrAl2O4:Eu, Dy mediante el método de sales fundidas para la obtención de materiales de gran cristalinidad con tamaños de cristalito del orden nanométrico. Se empleo como sal fundente la mezcla eutéctica de NaCl y KCl, denominada (NaCl-KCl)e. La principal ventaja de la incorporación de la mezcla es el incremento la reactividad del sistema, reduciendo la temperatura de formación del SrAl2O4 y la duración del tratamiento térmico en comparación con la síntesis en estado sólido. La formación del SrAl2O4 es favorecida ya que se aumenta la difusión de los cationes de Sr2+ en el medio líquido. Se emplearon diferentes tipos de Al2O3 para evaluar el papel del tamaño de partícula y su naturaleza en la reacción asistida por sales fundidas y por tanto en la morfología y propiedades del producto final. Se obtuvieron partículas de morfología pseudo-esférica de tamaño ≤0.5 μm al emplear como alúmina precursora partículas sub-micrónicas ( 0.5 μm Al2O3, 0.1 μm Al2 O3 y γ-Al2O3). El mecanismo de reacción que tiene lugar se asocia a procesos de disolución-precipitación que dominan al emplear partículas de alúmina pequeñas y reactivas. Mientras al emplear una alúmina de 6 μm Al2O3 prevalecen los procesos de crecimiento cristalino siguiendo un patrón o plantilla debido a la menor reactividad del sistema. La nucleación y crecimiento de nanocristales de SrAl2O4:Eu, Dy se genera sobre la superficie de la alúmina que actúa como soporte. De esta forma se desarrolla una estructura del tipo coraza-núcleo («core-shell» en inglés) donde la superficie externa está formada por los cristales fosforescentes de SrAl2O4 y el núcleo está formado por alúmina. Las partículas obtenidas tienen una respuesta fotoluminiscente diferente en función de la morfología final obtenida. La optimización de la relación Al2O3/SrO del material de SrAl2O4:Eu, Dy sintetizado a partir de la alúmina de 6 μm permite reducir las fases secundarias y la concentración de dopantes manteniendo la respuesta fotoluminiscente. Comparativamente con un material comercial de SrAl2O4:Eu, Dy de referencia, se han alcanzado valores de la intensidad de la emisión de hasta el 90% y de la intensidad inicial de las curvas de decaimiento de la luminiscencia de un 60% para el material sintetizado por sales fundidas que tiene un tamaño medio ≤ 10μm. Por otra parte, es necesario tener en cuenta que el SrAl2O4 tiene dos polimorfos, la fase monoclínica que es estable a temperaturas inferiores a 650oC y la fase hexagonal, fase de alta temperatura, estable a temperaturas superiores de 650oC. Se ha determinado que fase monoclínica presenta propiedades luminiscentes, sin embargo existen discordancias a cerca de las propiedades luminiscentes de la fase hexagonal. Mediante la síntesis por sales fundidas es posible estabilizar la fase hexagonal empleando como alúmina precursora γ-Al2O3 y un exceso de Al2O3 (Al2O3/SrO:2). La estabilización de la fase hexagonal a temperatura ambiente se produce cuando el tamaño de los cristales de SrAl2O4 es ≤20 nm. Además se observó que la fase hexagonal presenta respuesta fotoluminiscente. El diseño de materiales de SrAl2O4:Eu,Dy nanoestructurados permite modular la morfología del material y por tanto la intensidad de la de la fotoluminiscencia y la persistencia de la luminiscencia. La disminución de los materiales precursores, la temperatura y el tiempo de tratamiento significa la reducción de los costes económicos del material. De ahí la viabilidad de los materiales de SrAl2O4:Eu,Dy obtenidos mediante los procesos de síntesis propuestos en esta memoria de tesis para su posterior escalado industrial. ABSTRACT The synthesis of sub-micron photoluminescent particles has been widely studied during the past decade because of the promising industrial applications of these materials. A large number of matrices has been developed, being SrAl2O4 host doped with europium (Eu2+) and dysprosium (Dy3+) the most extensively studied, because of its better stability and long-lasting luminescence. These functional inorganic materials have a wide field of application in persistent luminous paints, inks and ceramics. Large attention has been paid to the development of an efficient method of preparation of SrAl2O4 powders, including solgel method, hydrothermal synthesis, laser synthesis, combustion synthesis and solid state reaction. Many of these techniques are not compatible with large-scale production and with the principles of sustainability. Moreover, industrial processing of highly crystalline powders usually requires high synthesis temperatures, typically between 1300 a 1900oC, with long processing times, especially for solid state reaction. As a result, the average particle size is typically within the 20-100 μm range. This large particle size is limiting for current applications that demand sub-micron particles. Therefore, the objective of this work is to develop new approaches to overcome these limitations. Within this frame, it is necessary to undertake the following purposes: To study the parameters that govern the particle size reduction by milling and their relation with the photoluminescence properties. To obtain SrAl2O4:Eu, Dy by combustion synthesis, assessing the effect of the temperature and the amount of fuel (urea) to synthesize highly crystalline particles minimizing the presence of secondary phases. To develop new synthesis methods to obtain SrAl2O4:Eu, Dy powders. The molten salt synthesis has been proposed. As the method is a novel route, the reaction mechanism should be determine as a function of the salt mixture, the ratio of the salt, the kind of Al2O3 and their particle size and the temperature and the atmosphere of the thermal treatment. To improve the efficiency of the synthesis process to obtain SrAl2O4:Eu, Dy powders with optimal final properties and easily scalable. On the basis of decreasing the particle size by using commercial product SrAl2O4:Eu2+, Dy3+ as raw material, the effects of different milling methods have been evaluated. Wet milling can significantly alter the structure of the material through hydrolysis reaction even in ethanol media. For overcoming the drawbacks of wet milling, a dry milling-based processes are studied. High energy dry milling process allows a great reduction of the particle size, however milling times above 10 min produce agglomeration and accelerates the decrease of the photoluminescence feature. To solve these issues the low energy dry milling process proposed effectively reduces the particle size to d50=2.8 μm, and improves the homogeneity avoiding the amorphization in comparison with previous methods. The X-ray diffraction and scanning electron microscope characterization allow to infer that the large variations in PL (Photoluminescence) values by high energy milling process are a consequence mainly of the crystallite size reduction. The lesser variation in PL values by low energy milling proces is related to the coherent crystalline domain preservation and the unnoticeable amorphization. These results corroborate that the photoluminescence intensity and the persistent luminescence of the SrAl2O4:Eu2+, Dy3+ powders depend extrinsically on the morphology of the particles such as particle size, grain size, surface damage and intrinsically on the crystallinity (crystallite size); being the intrinsically effects the ones that have a significant influence on the photoluminescent response. By combustion method, nanostructured SrAl2O4:Eu2+, Dy3+ sheets with a thickness ≤1 μm have been obtained. The amount of fuel (urea) in the reaction has an important influence on the phase composition; urea contents larger than the stoichiometric one require the presence of an oxidant agent such as HNO3 to complete the reaction. A higher amount of urea (excess of urea: denoted m>1, being m=1 the stoichiometric composition) including an oxidizing agent produces SrAl2O4:Eu2+,Dy3+ particles with persistent luminescence due to the effective chelation of the cations and the creation of suitable atmospheric conditions to reduce the Eu3+ to Eu2+. Therefore, optimizing the synthesis parameters in combustion synthesis by using a higher amount of urea and an internal oxidizing agent allows to complete the reaction. The amount of secondary phases can be significantly reduced and the photoluminescence response can be enhanced. This situation is attributed to a higher energy that improves the crystallinity of the powders. The powders obtained have a particle size c.a. 5-25 μm with a thickness ≤1 μm and require relatively low ignition temperatures (600oC). It is possible to reduce the particle size by a low energy dry milling but this process implies the decrease of the photoluminescent response. However, a post-thermal treatment in a reducing atmosphere allows the improvement of the properties due to the increment of crystallinity and the reduction of Eu3+ to Eu2+. Compared with the powder resulted from solid state method (commercial reference: average particle size, 20 μm and heterogeneous particle size distribution) the emission intensity of the powder prepared by combustion method achieve the values between 35% to 21% of the reference powder intensity. Moreover, the initial intensity of the decay curve is 20% of the intensity of the reference powder. Taking in account these results, it is necessary to explore other methods to synthesize the powders For that reason, an original synthetic route has been developed in this study: the molten salt assisted process to obtain highly crystalline SrAl2O4 powders with nanometric sized crystallites. The molten salt was composed of a mixture of NaCl and KCl using a 0.5:0.5 molar ratio (eutectic mixture hereafter abbreviated as (NaCl-KCl)e). The main advantages of salt addition is the increase of the reaction rate, the significant reduction of the synthesis temperature and the duration of the thermal treatment in comparison with classic solid state method. The SrAl2O4 formation is promoted due to the high mobility of the Sr2+ cations in the liquid medium. Different kinds of Al2O3 have been employed to evaluate the role of the size and the nature of this precursor on the kinetics of reaction, on the morphology and the final properties of the product. The SrAl2O4:Eu2+, Dy3+ powders have pseudo-spherical morphology and particle size ≤0.5 μm when a sub-micron Al2O3 ( 0.5 μm Al2O3, 0.1 μm Al2O3 and γ-Al2O3) has been used. This can be attributed to a higher reactivity in the system and the dominance of dissolution-precipitation mechanism. However, the use of larger alumina (6 μm Al2O3) modifies the reaction pathway leading to a different reaction evolution. More specifically, the growth of SrAl2O4 sub-micron particles on the surface of hexagonal platelets of 6μm Al2O3 is promoted. The particles retain the shape of the original Al2O3 and this formation process can be attributed to a «core-shell» mechanism. The particles obtained exhibit different photoluminescent response as a function of the final morphology of the powder. Therefore, through this study, it has been elucidated the reaction mechanisms of SrAl2O4 formation assisted by (NaCl-KCl)e that are governed by the diffusion of SrCO3 and the reactivity of the alumina particles. Optimizing the Al2O3/SrO ratio of the SrAl2O4:Eu, Dy powders synthesized with 6 μm Al2O3 as a precursor, the secondary phases and the concentration of dopant needed can be reduced keeping the photoluminescent response of the synthesized powder. Compared with the commercial reference powder, up to 90% of the emission intensity of the reference powder has been achieved for the powder prepared by molten salt method using 6μm Al2O3 as alumina precursor. Concerning the initial intensity of the decay curve, 60% of the initial intensity of the reference powder has been obtained. Additionally, it is necessary to take into account that SrAl2O4 has two polymorphs: monoclinic symmetry that is stable at temperatures below 650oC and hexagonal symmetry that is stable above this temperature. Monoclinic phase shows luminescent properties. However, there is no clear agreement on the emission of the hexagonal structure. By molten salt, it is possible to stabilize the hexagonal phase of SrAl2O4 employing an excess of Al2O3 (Al2O3/SrO: 2) and γ-Al2O3 as a precursor. The existence of nanometric crystalline domains with lower size (≤20 nm) allows the stabilization of the hexagonal phase. Moreover, it has been evidenced that the hexagonal polymorph exhibits photoluminescent response. To sum up, the design of nanostructured SrAl2O4:Eu2+, Dy3+ materials allows to obtain different morphologies and as consequence different photoluminescent responses. The reduction of temperature, duration of the thermal treatment and the precursors materials needed imply the decrease of the economic cost of the material. Therefore, the viability, suitability and scalability of the synthesis strategy developed in this work to process SrAl2O4:Eu2+, Dy3+ are demonstrated.

Estudo da substituição da fluorita por alumina ou sodalita e de cal por resíduo de mármore em escórias sintéticas dessulfurantes.

A siderurgia vem sofrendo transformações que buscam inovação e matérias-primas alternativas. Dentro deste contexto, o uso de resíduos industriais para a formação de escórias sintéticas é tido como alternativa na busca de novos materiais e rotas de reaproveitamento de resíduos. Portanto, este trabalho teve como objetivo estudar o uso de escórias sintéticas na etapa de dessulfuração do ferro-gusa, aço e ferro fundido. Assim como, propor a utilização da sodalita e da alumina em substituição à fluorita e o resíduo de mármore em substituição à cal convencional. Inicialmente, o resíduo foi caracterizado utilizando as seguintes técnicas: análise química, análise granulométrica, área de superfície específica, difração de raios-X, microscopia eletrônica de varredura (MEV) e análise de espectroscopia por energia dispersiva (EDS). Os resultados da caracterização mostraram que aproximadamente 90% das partículas do resíduo de mármore estão abaixo de 100m e sua área superficial foi de 0,24m²/g. Através da difração de raios-X foi observado que o resíduo é composto por CaCO3, MgCO3 e SiO2. Na sequência, foram feitas simulações com o software Thermo-Calc para obter dados termodinâmicos das fases presentes nas misturas e compará-los com os resultados experimentais. Além disso, também foram calculados dados de capacidade de sulfeto (Cs), partição de enxofre (Ls) e basicidade ótica () das misturas iniciais. Posteriormente, foram realizados os ensaios experimentais em escala laboratorial para ferro-gusa, ferro fundido e aço, respectivamente nas temperaturas de 1400°C, 1550°C e 1600°C. Nos ensaios de dessulfuração do aço e do ferro-gusa, utilizou-se um rotor de alumina com o objetivo de favorecer a agitação no metal e aumentar a remoção de enxofre. Na etapa de dessulfuração do ferro-gusa, constatou-se que a fase sólida de CaO é a responsável pela remoção de enxofre e que a presença das fases silicato tricálcio e aluminato tricálcio (3CaO.SiO2 e 3CaO.Al2O3) limitam a reação, sendo maiores suas concentrações nas escórias que utilizaram o resíduo de mármore e sodalita, devido a presença de SiO2 e Al2O3 nestas matérias-primas. Já para o aço e o ferro fundido, que foram estudados com escórias à base de CaO e Al2O3, observou-se que o aumento da fase líquida favoreceu a dessulfuração. Verificou-se que a dessulfuração no ferro fundido foi por escória de topo e no aço por um processo misto, onde a fase líquida e fase sólida participaram da dessulfuração.

Sedimentologic and magnetic data of sediment cores on the western slope of the Mid-Atlantic Ridge

The relative paleointensity (RPI) method assumes that the intensity of post depositional remanent magnetization (PDRM) depends exclusively on the magnetic field strength and the concentration of the magnetic carriers. Sedimentary remanence is regarded as an equilibrium state between aligning geomagnetic and randomizing interparticle forces. Just how strong these mechanical and electrostatic forces are, depends on many petrophysical factors related to mineralogy, particle size and shape of the matrix constituents. We therefore test the hypothesis that variations in sediment lithology modulate RPI records. For 90 selected Late Quaternary sediment samples from the subtropical and subantarctic South Atlantic Ocean a combined paleomagnetic and sedimentological dataset was established. Misleading alterations of the magnetic mineral fraction were detected by a routine Fe/kappa test (Funk, J., von Dobeneck, T., Reitz, A., 2004. Integrated rock magnetic and geochemical quantification of redoxomorphic iron mineral diagenesis in Late Quaternary sediments from the Equatorial Atlantic. In: Wefer, G., Mulitza, S., Ratmeyer, V. (Eds.), The South Atlantic in the Late Quaternary: reconstruction of material budgets and current systems. Springer-Verlag, Berlin/Heidelberg/New York/Tokyo, pp. 239-262). Samples with any indication of suboxic magnetite dissolution were excluded from the dataset. The parameters under study include carbonate, opal and terrigenous content, grain size distribution and clay mineral composition. Their bi- and multivariate correlations with the RPI signal were statistically investigated using standard techniques and criteria. While several of the parameters did not yield significant results, clay grain size and chlorite correlate weakly and opal, illite and kaolinite correlate moderately to the NRM/ARM signal used here as a RPI measure. The most influential single sedimentological factor is the kaolinite/illite ratio with a Pearson's coefficient of 0.51 and 99.9% significance. A three-member regression model suggests that matrix effects can make up over 50% of the observed RPI dynamics.

Grain size distribution analysis of prominent beds on Southern Central Chilean seamounts

Gravity cores obtained from isolated seamounts located within, and rising up to 300 m from the sediment-filled Peru-Chile Trench off Southern Central Chile (36°S-39°S) contain numerous turbidite layers which are much coarser than the hemipelagic background sedimentation. The mineralogical composition of some of the beds indicates a mixed origin from various source terrains while the faunal assemblage of benthic foraminifera in one of the turbidite layers shows a mixed origin from upper shelfal to middle-lower bathyal depths which could indicate a multi-source origin and therefore indicate an earthquake triggering of the causing turbidity currents. The bathymetric setting and the grain size distribution of the sampled layers, together with swath echosounder and sediment echosounder data which monitor the distribution of turbidites on the elevated Nazca Plate allow some estimates on the flow direction, flow velocity and height of the causing turbidity currents. We discuss two alternative models of deposition, both of which imply high (175-450 m) turbidity currents and we suggest a channelized transport process as the general mode of turbidite deposition. Whether these turbidites are suspension fallout products of thick turbiditic flows or bedload deposits from sheet-like turbidity currents overwhelming elevated structures cannot be decided upon using our sedimentological data, but the specific morphology of the seamounts rather argues for the first option. Oxygen isotope stratigraphy of one of the cores indicates that the turbiditic sequences were deposited during the last Glacial period and during the following transition period and turbiditic deposition stopped during the Holocene. This climatic coupling seems to be dominant, while the occurrence of megathrust earthquakes provides a trigger mechanism. This seismic triggering takes effect only during times of very high sediment supply to the shelf and slope.