Modelización geoquímica de los procesos de fusión parcial

18 páginas, 6 figuras, 1 apendice.[ES] Durante la fusión, los elementos traza y los isótopos estables sufren fraccionación mientras que los isótopos radiogénicos no varían. Como la distribución de los primeros entre las fases que intervienen sigue las leyes de las soluciones diluidas, se pueden establecer ecuaciones relativamente sencillas, que posibilitan la modelización del proceso. A su vez, el comportamiento de los isótopos radiogénicos hace que los magmas hereden la signatura del sólido del que derivar, lo que facilita la identificación del mismo. Las ecuaciones propuestas para los diferentes tipos de fusión indican que en la fusión en equilibrio la abundancia en el fundido de elementos traza altamente incompatibles alcanza valores muy elevados al comienzo del proceso y disminuye progresivamente al aumentar el grado de fusión, mientras que la concentración de los elementos compatibles crece lentamente al aumentar el porcentaje de fusión y bruscamente cuando éste alcanza valores muy altos. En la fusión fraccionada el primero de los líquidos que se genera removiliza casi completamente a todos los elementos altamente incompatibles del sistema, y los sucesivos líquidos producidos tienen muy baja concentración en dichos elementos. En la fusión incongruente se generan líquidos ricos en aquellos elementos traza que tienen altos coeficientes de reparto para las fases que funden y bajos para las de nueva formación, mientras que están empobrecidos en los elementos que entran en estas últimas fases. Si la fusión tiene lugar en presencia de una fase fluida el líquido está empobrecido, en relación al generado cuando dicha fase está ausente, en aquellos elementos que tienen coeficientes de reparto líquido-fluido aproximadamente iguales a la unidad, ya que una parte de los mismos se concentra en el fluido. Finalmente, en la fusión en desequilibrio o no difusión a la primera fracción de líquido que aparece tiene una concentración en elementos incompatibles superior y en elementos compatibles inferior a la del sólido del que deriva, con lo que la interfase sólido-líquido se empobrece y se enriquece, respectivamente. Sin embargo, al final del proceso la concentración de los elementos en el líquido se iguala a la que tenía la parte de sólido que ha fundido. Para modelizar la fusión parcid en equilibrio se pueden seguir dos vías diferentes, según se disponga o no de los coefcientes de reparto mineral-líquido y se conozcan o no los porcentajes en los que intervienen dichas fases. Si se dispone de dichos parámetros, se puede intentar duplicar las concentraciones elementales observadas en los líquidos primarios, previa selección de unas constantes razonables. Por el contrario, si no se conocen aquellos parámetros la mJdelización se puede llevar a cabo de forma distinta, según se disponga de la composición de los líquidos generados o del residuo. Si se conoce la composición de los líquidos generados, se utilizan las variaciones en las concentraciones elementales que presentan las rocas, mediante un ajuste simultáneo de todas ellas por resolución de un sistema de ecuaciones formado por las expresiones que describen el proceso, para un número suficiente de elementos, o bien independientemente para cada parámetro y elemento. A su vez, si se conoce la composición química de los residuos hay que suponer la composición del protolito y a partir del elemento más residual fijar los dos parámetros que quedan por conocer: el coeficiente de partición global residuofundido para los distintos elementos y el grado de fusión que ha sufrido cada restita, asumiendo, según proceda, el grado de fusión, el coeficiente de reparto global de uno de los elementos o la concentración del mismo.[EN] During melting processes both stable isotopes and trace elements fractionate, whereas radiogenic isotopes do not change. The distribution of the former between the phases that participate, follows diluted solutions laws in such a way that it is possible to establish relatively simple equations to model these processes. Additionally, the radiogenic isotopes behaviour implies that the magmas retain the source signature thus allowing its identification. In the case of equilibrium melting, the highly incompatible elements abundance is very high in the liquid at the beginning of the process and decreases progressively as the melting degree increases. On the contrary, the concentration in compatible elements grows very slowly during the first steps to increase sharply for the highest F values. During fractional melting, the first liquid generated removes almost all the incompatible elements thus producing a relative depletion in those elements in the successive liquids. In the case of incongruent melting, the magmas are enriched in the trace elements with high distribution coefficients for the phases that melt and low for the newly generated phases, and are impoverished in the elements that constitute the new phases. If melting is produced in the presence of a fluid phase, the liquid will be depleted in those elements with fluid/liquid distribution coefficients close to 1, rdative to the same liquid generated without a fluid phase. Finally, during disequilibrium or nondiffusive melting, the first liquid fraction has a concentration in incompatible dements higher and in compatible elements lower than that in the source, so the solid-liquid interface is depleted and enriched, respectively. However, at the end of the process the concentration of elements in the liquid is equated to the abundance in the solid that melted. To model equilibrium me1ting two diferent approaches can be followed, depending on the availability of the mineral-liquid distribution coefficients and the percentages in which the mineral phases have participated. When these parameters are known, it is possible to duplicate the concentrations observed in the primary liquids by selecting reasonable constants. On the contrary, when these parameters are unknown the approach to follow will depend on the knowledge of the cbmposition of the liquids or that of the residue. In the first case, the element concentrations of tbe rocks are used to obtain a simultaneous best-fit solution of a system constituted by tile equations that describe the process, either for a number of elements, or individually for each parameter and element. If the composition of the residue is known, it is necessary to guess the composition of the protolith. Then, from the most residual element the two remaining parameters (the residue- melt bulk distribution coefficient and the degree of melting of each restite) are defined, either assuming the degree of melting, the elements bulk distribution coefficient, or their concentration.Este trabajo se ha realizado dentro del Proyecto de Investigación PB92-lOS «Magmatismo intraplaca relacionado con puntos calientes en la Península Ibérica», financiado por la Dirección General de Investigación Científica y Técnica.Peer reviewe

Structural analysis and sintering aids effects in La2Ce2O7 proton conductors

Global warming is an important problem that has to be solved without delay. The development of environmental-friendly energy technology is needed to deal with this issue. Solid Oxide Fuel Cells (SOFC) technology has been proposed as a real alternative to fossil fuel combustion. Proton conductors like La2Ce2O7 (LDC), has several advantages in comparison with BaCeO3 due to its high stability in H2O or CO2 conditions [1]. Furthermore, for industry application is necessary to low the high sintering temperature of typical electrolyte materials. La2Ce2O7 was synthesized by the freeze-drying precursor method and calcination conditions have been optimized to obtain single phase with high compaction at 1400 ºC for 1h. A fully characterization has been carried out using X-ray powder diffraction and scanning electron microscopy. The total conductivity was determined by complex impedance spectroscopy in dry and wet air. Transmission Electron Microscopy (TEM) was used to clarify certainly the structure of La2Ce2O7 due to its still unknown. SAEDs patterns revealed a disordered fluorite, not appearing secondary reflections typical of pyrochlore superstructure, finishing the controversy around the correct structure in this material [2,3]. Moreover, an exhaustive study about lowering the sintering temperature with Co and Zn as sintering aids has been investigated obtaining electrolytes that can be used for SOFC. The sintering aids were impregnated using cobalt and zinc nitrates in ethanol media. Both sintering aids allow for obtain high dense pellets lowering the sintering temperature 300 ºC and 400 ºC for samples with cobalt and zinc, respectively, without compromising the electrical and microstructural properties (Fig 1).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Birth, death and diffusion of interacting particles

Individual-based models of chemical or biological dynamics usually consider individual entities diffusing in space and performing a birth-death type dynamics. In this work we study the properties of a model in this class where the birth dynamics is mediated by the local, within a given distance, density of particles. Groups of individuals are formed in the system and in this paper we concentrate on the study of the properties of these clusters (lifetime, size, and collective diffusion). In particular, in the limit of the interaction distance approaching the system size, a unique cluster appears which helps to understand and characterize the clustering dynamics of the model.Comment: 15 pages, 6 figures, Iop style. To appear in Journal of Physics A: Condensed matte

Nonlinear Interaction of Transversal Modes in a CO2 Laser

We show the possibility of achieving experimentally a Takens-Bogdanov bifurcation for the nonlinear interaction of two transverse modes ($l = \pm 1$) in a $CO_2$ laser. The system has a basic O(2) symmetry which is perturbed by some symmetry-breaking effects that still preserve the $Z_2$ symmetry. The pattern dynamics near this codimension two bifurcation under such symmetries is described. This dynamics changes drastically when the laser properties are modified.Comment: 16 pages, 0 figure

Influence of lanthanum doping on the structure and transport properties of CeO2

LaxCe1-xO2-x/2 materials are oxide and/or proton conductors depending on the La-content and they are of interest for numerous electrochemical applications at high temperatures, including membranes for hydrogen separation and fuel cell electrolytes. Samples with low La-content exhibit (x0.4) crystallize with cubic fluorite type structure; while for x>0.4 the structure is still unclear. The crystal structure of these materials is still unknown, some authors reported that the materials exhibit fluorite type structure in the whole compositional range. However, another authors reported a pyrochlore type structure for x0.5. The stabilization of the fluorite or pyrochlore type structure depends mainly on the oxygen sublattice and the vacancy ordering1. In this contribution, LaxCe1-xO2-δ (0<x0.7) materials are prepared by the freeze-drying precursor method and the sintering conditions have been optimized to obtain dense ceramic samples. A complete structural characterization has been carried out by X-ray powder diffraction and scanning electron microscopy. The average structure determined by conventional XRD indicates that the materials are single fluorite compounds for x0.6. However, the local structure determined by combined electron diffraction and HRTEM is more complex. The SAED patterns reveal diffuse scatterings for x0.5 that have been associated with O-vacancy ordering, leading to a superstructure relative to a single fluorite . This finding is further confirmed by the HRTEM images in the same zone axis. Thermogravimetric and Raman analysis confirmed an increase of oxygen vacancy concentration with La-doping. The overall conductivity was determined by complex impedance spectroscopy in different atmospheres. The samples with high La-content exhibit an important proton contribution at low temperature. In addition, all samples are mixed ion-electronic conductors in hydrogen containing atmosphereUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Carbon and oxygen abundances from recombination lines in low-metallicity star-forming galaxies. Implications for chemical evolution

We present deep echelle spectrophotometry of the brightest emission-line knots of the star-forming galaxies He 2-10, Mkn 1271, NGC 3125, NGC 5408, POX 4, SDSS J1253-0312, Tol 1457-262, Tol 1924-416 and the HII region Hubble V in the Local Group dwarf irregular galaxy NGC 6822. The data have been taken with the Very Large Telescope Ultraviolet-Visual Echelle Spectrograph in the 3100-10420 {\AA} range. We determine electron densities and temperatures of the ionized gas from several emission-line intensity ratios for all the objects. We derive the ionic abundances of C$^{2+}$ and/or O$^{2+}$ from faint pure recombination lines (RLs) in several of the objects, permitting to derive their C/H and C/O ratios. We have explored the chemical evolution at low metallicities analysing the C/O vs. O/H, C/O vs. N/O and C/N vs. O/H relations for Galactic and extragalactic HII regions and comparing with results for halo stars and DLAs. We find that HII regions in star-forming dwarf galaxies occupy a different locus in the C/O vs. O/H diagram than those belonging to the inner discs of spiral galaxies, indicating their different chemical evolution histories, and that the bulk of C in the most metal-poor extragalactic HII regions should have the same origin than in halo stars. The comparison between the C/O ratios in HII regions and in stars of the Galactic thick and thin discs seems to give arguments to support the merging scenario for the origin of the Galactic thick disc. Finally, we find an apparent coupling between C and N enrichment at the usual metallicities determined for HII regions and that this coupling breaks in very low-metallicity objects.Comment: 27 pages, 12 figures, Accepted for publication in Monthly Notices of the Royal Astronomical Societ