Estudio de la inhomogeneidad elástica en vidrios metalicos en la mesoescala

Metallic glasses are amorphous solids produced by rapid cooling, with disordered atomic structure and lacking long-range order. This structural disorder makes them to show mechanical properties different from those observed in a crystalline solid. Metallic glasses are ideally isotropic, but they can become anisotropic during the manufacturing process or as a result of non-homogeneous plastic deformation, creep, etc. Experimental studies showed remnant anisotropy in amorphous PdSiCuP under a homogeneous deformation regime at temperatures close to the glass transition (Tg). In this thesis we studied the remnant anisotropy induced by shear in two amorphous systems by using molecular dynamics simulation. The Cu13Ni34Pd53 system was chosen to approach the PdCuSiP compositions, while the Zr46Cu46Al8 system is an excellent metallic glass former. Amorphous systems were obtained by fast cooling from the liquid and subsequent thermal annealing. Both systems were then sheared in the [100] direction at a deformation speed of 10^10 s^(-1), and returned to its original form at the same speed. Shearing simulations were performed in isothermal-isobaric conditions at different temperatures. The resulting states were examined using the directional pair distribution function (d-PDF), calculated from the distribution function of interatomic distances in planes perpendicular to the selected axis. Remnant anisotropy was detected in both systems after a deformation-recovery cycle. Cu13Ni34Pd53 displays remnant anisotropy below the glass transition at 0 and 300 K after the shear process, and again at 700 K after the full deformation-recovery cycle. The intensity of anisotropy in the d-PDF of Zr46Cu46Al8 is lower than in Cu13Ni34Pd53, possibly due to the different atomic radii. However, it is found in all the studied temperature range, with decreasing intensity with temperature. Anisotropy is concentrated in the [110] planes and [1(-1)0], corresponding to the planes of maximum and minimum shear respectively. This result indicates that remnant anisotropy is highly directional and can go unnoticed if not searched for. It also states that the shear process is essentially symmetrical with respect to the plane [110]. The shear and recovery process induces the creation of free volume, falling into the category of rejuvenation processes discussed in the literature. Counterintuitively, the process of free volume creation is accompanied by a reduction of the distance of the first maximum of the pair distribution function g (r), indicating a decrease of the most likely distance (mode) between first neighbors. However, this decrease in mode is accompanied by an increase of the width of the first peak, increasing the standard deviation of the distribution of distances between first neighbors. This explains the apparent contradiction between the increase in the volume and reduction of the most probable distance between first neighbors. Simultaneously, the second coordination sphere is more homogenous after the deformation and recovery process. As a result, medium range order is increased. The discrepancy between the results obtained between Cu13Ni34Pd53 and Zr46Cu46Al8 may be due to the fact that the potential used in the simulations of Zr46Cu46Al8 is more representative of the behavior of metallic glasses. As a result, we hypothesize that the presence of remnant anisotropy after mechanical deformation could be a general feature in metallic glasses. The computational cost of this study was very high, since it was necessary to simulate million-atom systems to avoid that results were dependent on the size of the simulation box.Los vidrios metálicos son sólidos amorfos producidos por enfriamiento rápido, con estructura atómica desordenada y sin orden de largo alcance. Este desorden estructural les proporciona propiedades mecánicas diferentes de las observadas en un sólido cristalino. Idealmente los vidrios metálicos son isotrópicos pero pueden convertirse en anisotrópicos durante el proceso de fabricación o como consecuencia de una deformación plástica no homogénea, fluencia, etc. Estudios experimentales mostraron anisotropía remanente en PdSiCuP amorfo bajo un régimen de deformación homogéneo a temperaturas cercanas a la transición vítrea (Tg). En esta tesis estudiamos la anisotropía remanente inducida por cizalla en dos sistemas amorfos mediante simulación por dinámica molecular. El sistema Cu13Ni34Pd53 se eligió intentando aproximarse a las composiciones PdCuSiP. Por otra parte, el sistema Zr46Cu46Al8 es un excelente formador de vidrios metálicos. Tras la obtención del sistema amorfo por enfriamiento rápido y equilibrado térmico ambos modelos fueron sometidos a deformación por cizalladura en la dirección [100], a una velocidad de deformación de 10^10 s^(-1), y retornados a su forma original con la misma velocidad, en condiciones isotérmicas-isobáricas a diferentes temperaturas. Los estados obtenidos fueron examinados utilizando la función de distribución par direccional (dPDF), calculada a partir de la distribución de distancias interatómicas en los planos perpendiculares al eje escogido. En ambos sistemas se detectó anisotropía remanente después de un ciclo deformación- recuperación. En Cu13Ni34Pd53 se observa anisotropía remanente por debajo de la transición vítrea en 0 y 300 K al final del proceso de cizalla, y nuevamente en el estado deformado a 700 K. En Zr46Cu46Al8, la intensidad de la anisotropía determinada en las d-PDF es menor que en Cu13Ni34Pd53, posiblemente debido a los radios atómicos, pero se observa en todo el rango de temperaturas estudiadas con intensidad decreciente con la temperatura. La anisotropía se concentra en los planos [110] y [1(-1)0], correspondientes a los planos de máxima y mínima cizalla respectivamente. Este resultado indica que la anisotropía remanente es altamente direccional y puede pasar desapercibida si no se busca específicamente. Asimismo, se observa que el proceso de cizalla es esencialmente simétrico con respecto al plano [1(-1)0]. El proceso de cizalla y recuperación induce la creación de volumen libre, entrando dentro de la categoría de los procesos de rejuvenecimiento analizados en la literatura. Contraintuitivamente, el proceso de creación de volumen libre va acompañando de una reducción de la distancia del primer máximo de la función de distribución de pares g(r), indicando una disminución de la distancia más probable (moda) entre primeros vecinos. Sin embargo, esta disminución de la moda va acompañada de un aumento de la anchura del primer pico, aumentando la desviación estándard de la distribución de distancias entre primeros vecinos. Esto explica la aparente contradicción entre el aumento del volumen y la reducción de la distancia más probable entre primeros vecinos. Simultáneamente, la segunda esfera de coordinación es más homogénea después del proceso de deformación y recuperación. En consecuencia, se produce un aumento del orden a media distancia. La discrepancia entre los resultados obtenidos entre Cu13Ni34Pd53 y Zr46Cu46Al8 puede deberse a que el potencial en Zr46Cu46Al8 es más representativo del comportamiento de los vidrios metálicos. Consecuentemente, la presencia de anisotropía remanente después de deformación mecánica podría ser una característica general en los vidrios metálicos. El coste computacional de este estudio ha sido muy alto, puesto que ha sido necesario simular sistemas con muchos átomos para evitar que los resultados obtenidos fuesen dependientes del tamaño de la caja de simulación utilizadasPostprint (published version

Accurate Estimation of Chlorophyll-a Concentration in the Coastal Areas of the Ebro Delta (NW Mediterranean) Using Sentinel-2 and Its Application in the Selection of Areas for Mussel Aquaculture

Multispectral satellite remote sensing imagery, together with appropriate modeling, have been proven to provide chlorophyll-a maps that are useful to evaluate the suitability of coastal areas for carrying out shellfish aquaculture. However, current approaches used for chlorophyll-a estimation in very shallow coastal areas often fail in their accuracy. To overcome this limitation, an algorithm that provides an accurate estimation of chlorophyll-a concentration in the coastal areas of the Ebro delta (North Western Mediterranean) using atmospherically corrected Sentinel 2 (S2) remote sensing reflectances (Rrs) has been calibrated and validated. The derived chlorophyll-a maps created have been used in a dynamic carrying capacity model that covers areas from very rich waters inside the embayment to the more oligotrophic waters in the open sea. The use of carrying capacity models is recommended to evaluate the potential of marine coastal areas for bivalve mollusk aquaculture. In this context, the depletion of chlorophyll-a is an indicator of negative environmental impact and thus a continuous monitoring of chlorophyll-a is key. The proposed methodology allows estimation of chlorophyll-a concentration from Sentinel-2 with an accuracy higher than 70% in most cases. The carrying capacity and the suitability of the external areas of the Ebro delta have been determined. The results show that these areas can hold a significant mussel production. The methodology presented in this study aims to provide a tool to the shellfish aquaculture industry.info:eu-repo/semantics/publishedVersio

Estudio de la inhomogeneidad elástica en vidrios metalicos en la mesoescala

Metallic glasses are amorphous solids produced by rapid cooling, with disordered atomic structure and lacking long-range order. This structural disorder makes them to show mechanical properties different from those observed in a crystalline solid. Metallic glasses are ideally isotropic, but they can become anisotropic during the manufacturing process or as a result of non-homogeneous plastic deformation, creep, etc. Experimental studies showed remnant anisotropy in amorphous PdSiCuP under a homogeneous deformation regime at temperatures close to the glass transition (Tg). In this thesis we studied the remnant anisotropy induced by shear in two amorphous systems by using molecular dynamics simulation. The Cu13Ni34Pd53 system was chosen to approach the PdCuSiP compositions, while the Zr46Cu46Al8 system is an excellent metallic glass former. Amorphous systems were obtained by fast cooling from the liquid and subsequent thermal annealing. Both systems were then sheared in the [100] direction at a deformation speed of 10^10 s^(-1), and returned to its original form at the same speed. Shearing simulations were performed in isothermal-isobaric conditions at different temperatures. The resulting states were examined using the directional pair distribution function (d-PDF), calculated from the distribution function of interatomic distances in planes perpendicular to the selected axis. Remnant anisotropy was detected in both systems after a deformation-recovery cycle. Cu13Ni34Pd53 displays remnant anisotropy below the glass transition at 0 and 300 K after the shear process, and again at 700 K after the full deformation-recovery cycle. The intensity of anisotropy in the d-PDF of Zr46Cu46Al8 is lower than in Cu13Ni34Pd53, possibly due to the different atomic radii. However, it is found in all the studied temperature range, with decreasing intensity with temperature. Anisotropy is concentrated in the [110] planes and [1(-1)0], corresponding to the planes of maximum and minimum shear respectively. This result indicates that remnant anisotropy is highly directional and can go unnoticed if not searched for. It also states that the shear process is essentially symmetrical with respect to the plane [110]. The shear and recovery process induces the creation of free volume, falling into the category of rejuvenation processes discussed in the literature. Counterintuitively, the process of free volume creation is accompanied by a reduction of the distance of the first maximum of the pair distribution function g (r), indicating a decrease of the most likely distance (mode) between first neighbors. However, this decrease in mode is accompanied by an increase of the width of the first peak, increasing the standard deviation of the distribution of distances between first neighbors. This explains the apparent contradiction between the increase in the volume and reduction of the most probable distance between first neighbors. Simultaneously, the second coordination sphere is more homogenous after the deformation and recovery process. As a result, medium range order is increased. The discrepancy between the results obtained between Cu13Ni34Pd53 and Zr46Cu46Al8 may be due to the fact that the potential used in the simulations of Zr46Cu46Al8 is more representative of the behavior of metallic glasses. As a result, we hypothesize that the presence of remnant anisotropy after mechanical deformation could be a general feature in metallic glasses. The computational cost of this study was very high, since it was necessary to simulate million-atom systems to avoid that results were dependent on the size of the simulation box.Los vidrios metálicos son sólidos amorfos producidos por enfriamiento rápido, con estructura atómica desordenada y sin orden de largo alcance. Este desorden estructural les proporciona propiedades mecánicas diferentes de las observadas en un sólido cristalino. Idealmente los vidrios metálicos son isotrópicos pero pueden convertirse en anisotrópicos durante el proceso de fabricación o como consecuencia de una deformación plástica no homogénea, fluencia, etc. Estudios experimentales mostraron anisotropía remanente en PdSiCuP amorfo bajo un régimen de deformación homogéneo a temperaturas cercanas a la transición vítrea (Tg). En esta tesis estudiamos la anisotropía remanente inducida por cizalla en dos sistemas amorfos mediante simulación por dinámica molecular. El sistema Cu13Ni34Pd53 se eligió intentando aproximarse a las composiciones PdCuSiP. Por otra parte, el sistema Zr46Cu46Al8 es un excelente formador de vidrios metálicos. Tras la obtención del sistema amorfo por enfriamiento rápido y equilibrado térmico ambos modelos fueron sometidos a deformación por cizalladura en la dirección [100], a una velocidad de deformación de 10^10 s^(-1), y retornados a su forma original con la misma velocidad, en condiciones isotérmicas-isobáricas a diferentes temperaturas. Los estados obtenidos fueron examinados utilizando la función de distribución par direccional (dPDF), calculada a partir de la distribución de distancias interatómicas en los planos perpendiculares al eje escogido. En ambos sistemas se detectó anisotropía remanente después de un ciclo deformación- recuperación. En Cu13Ni34Pd53 se observa anisotropía remanente por debajo de la transición vítrea en 0 y 300 K al final del proceso de cizalla, y nuevamente en el estado deformado a 700 K. En Zr46Cu46Al8, la intensidad de la anisotropía determinada en las d-PDF es menor que en Cu13Ni34Pd53, posiblemente debido a los radios atómicos, pero se observa en todo el rango de temperaturas estudiadas con intensidad decreciente con la temperatura. La anisotropía se concentra en los planos [110] y [1(-1)0], correspondientes a los planos de máxima y mínima cizalla respectivamente. Este resultado indica que la anisotropía remanente es altamente direccional y puede pasar desapercibida si no se busca específicamente. Asimismo, se observa que el proceso de cizalla es esencialmente simétrico con respecto al plano [1(-1)0]. El proceso de cizalla y recuperación induce la creación de volumen libre, entrando dentro de la categoría de los procesos de rejuvenecimiento analizados en la literatura. Contraintuitivamente, el proceso de creación de volumen libre va acompañando de una reducción de la distancia del primer máximo de la función de distribución de pares g(r), indicando una disminución de la distancia más probable (moda) entre primeros vecinos. Sin embargo, esta disminución de la moda va acompañada de un aumento de la anchura del primer pico, aumentando la desviación estándard de la distribución de distancias entre primeros vecinos. Esto explica la aparente contradicción entre el aumento del volumen y la reducción de la distancia más probable entre primeros vecinos. Simultáneamente, la segunda esfera de coordinación es más homogénea después del proceso de deformación y recuperación. En consecuencia, se produce un aumento del orden a media distancia. La discrepancia entre los resultados obtenidos entre Cu13Ni34Pd53 y Zr46Cu46Al8 puede deberse a que el potencial en Zr46Cu46Al8 es más representativo del comportamiento de los vidrios metálicos. Consecuentemente, la presencia de anisotropía remanente después de deformación mecánica podría ser una característica general en los vidrios metálicos. El coste computacional de este estudio ha sido muy alto, puesto que ha sido necesario simular sistemas con muchos átomos para evitar que los resultados obtenidos fuesen dependientes del tamaño de la caja de simulación utilizada

Plastic deformation induced anisotropy in metallic glasses: A molecular dynamics study

The atomic structure of a Cu13Ni34Pd53 metallic glass was studied by molecular dynamics simulation at different temperatures along a shear deformation cycle. A simulation box of 1 million atoms was deformed in the x axis and then the original orthogonal shape was recovered. Directional pair distribution functions were computed in the coordinate planes and some significant directions along the shear deformation cycle. No anisotropy was found in the initial state, while post-deformation anisotropy was revealed by significant differences of the partial pair distribution functions. The analysis of atomic environments concluded that the remnant anisotropy remains constrained into the shear plane. Low temperature samples showed remnant anisotropy after the full shear sample, while close to the glass transition the anisotropy induced by the initial shear process is removed by the subsequent recovery process.Peer ReviewedPostprint (published version

Study of medium range reordering by plastic deformation in Cu46Zr46Al8

The influence of shear in the atomic structure of ternary Cu46Zr46Al8 metallic glass was studied at different temperatures by molecular dynamics (MD) simulation. At temperatures above and below the glass transition temperature the system was subjected to a shear deformation cycle; the shear deformation was carried in the [100] direction and then the original geometry was recovered. The system was analyzed in three states: initial state (before deformation), deformed state (sheared) and final state (recovery). The different states obtained by the atomistic simulations were examined by computing the directional pair distribution functions (dPDF) in the coordinate planes. The results showed by dPDFs of the planes perpendicular to the coordinate axis are apparently isotropic. However, the dPDF disengage when computed perpendicular to rotated axis. This reveals that the anisotropy introduced during the deformation cycles appears in directions [110] and [1?0], tilted 45° with respect to the direction of the applied shear. To analyze the subtle structural change we systematically computed the positions and widths of the dPDF peaks on the rotated directions, thence allowing us to describe in detail the different signatures of anisotropy induced by deformation in the metallic glasses.Peer ReviewedPostprint (published version

Influencia en el medio ambiente de los vertidos intencionales de boratos a orillas de la Ruta Nacional 51-Salta

La ruta nacional 51, que forma parte del corredor bioceánico que conecta Salta con Chile, es utilizada para el transporte de mercaderías y minerales (boratos) de la puna. A orillas de esta ruta se observa la presencia de numerosos montículos de boratos por vertidos intencionales. Dichos vertidos, según información de los pobladores del lugar, son debidos a descarga del sobrepeso de los camiones que transportan el mineral cuando se tiene conocimiento que se realizan controles de carga. En este trabajo se analiza la influencia en el medio ambiente de dichos vertidos intencionales, realizando la identificación de los puntos de vertido y muestreo, caracterización física y química (B soluble, B2O3, Cl⁻, SO4⁼, OCa, ONa2), volumen de vertido y evaluación de los resultados para determinar su potencial de riesgo. La realización de este trabajo determina resultados importantes concluyendo con recomendaciones y sugerencias para la comunidad que habita a orillas de la mencionada ruta.The national route 51, which is part of the bioceanic corridor that joins Salta with Chile, is used for the transport of merchandises and minerals (borates) from La Puna. On its banks numerous mounds of borates can be observed as the result of intentional spills. These spills accordind to the settlers' information of the place, are the unloadings of the overweight of the trucks that transport this mineral when the knowledge is had that loads controls are made. In this work the influence in the environment of these spills are analyzed carrying out the identification of the dumping places, sampling, physical and chemical characterization (soluble boron, B2O3, Cl⁻, SO4⁼, OCa, ONa2), volume of the spills and the evaluation of the results to settle its potential of risk. The accomplishment of this work determines important results concluding with recommendations and suggestions for the community that inhabits near the mentioned route.Asociación Argentina de Energías Renovables y Medio Ambiente (ASADES

Influencia en el medio ambiente de los vertidos intencionales de boratos a orillas de la Ruta Nacional 51-Salta

La ruta nacional 51, que forma parte del corredor bioceánico que conecta Salta con Chile, es utilizada para el transporte de mercaderías y minerales (boratos) de la puna. A orillas de esta ruta se observa la presencia de numerosos montículos de boratos por vertidos intencionales. Dichos vertidos, según información de los pobladores del lugar, son debidos a descarga del sobrepeso de los camiones que transportan el mineral cuando se tiene conocimiento que se realizan controles de carga. En este trabajo se analiza la influencia en el medio ambiente de dichos vertidos intencionales, realizando la identificación de los puntos de vertido y muestreo, caracterización física y química (B soluble, B2O3, Cl⁻, SO4⁼, OCa, ONa2), volumen de vertido y evaluación de los resultados para determinar su potencial de riesgo. La realización de este trabajo determina resultados importantes concluyendo con recomendaciones y sugerencias para la comunidad que habita a orillas de la mencionada ruta.The national route 51, which is part of the bioceanic corridor that joins Salta with Chile, is used for the transport of merchandises and minerals (borates) from La Puna. On its banks numerous mounds of borates can be observed as the result of intentional spills. These spills accordind to the settlers' information of the place, are the unloadings of the overweight of the trucks that transport this mineral when the knowledge is had that loads controls are made. In this work the influence in the environment of these spills are analyzed carrying out the identification of the dumping places, sampling, physical and chemical characterization (soluble boron, B2O3, Cl⁻, SO4⁼, OCa, ONa2), volume of the spills and the evaluation of the results to settle its potential of risk. The accomplishment of this work determines important results concluding with recommendations and suggestions for the community that inhabits near the mentioned route.Asociación Argentina de Energías Renovables y Medio Ambiente (ASADES

Adaptive threshold PCA for fault detection and isolation

Fault diagnosis is an important issue in industrial processes to avoid economic losses, process damage, and to guarantee safe working conditions for the operators. For high scale industrial processes the data-driven based methods are the best solution for process monitoring and fault diagnosis. Thus, in this paper, the principal component analysis is shown to detect and isolate faults. Also, a dynamic threshold is implemented to avoid false alarms because incipient faults are difficult to be detected. As a case of study, the Tennessee Eastman (TE) process is used to apply this strategy because the interaction among five units with internal control loops makes difficult to have an approached model. As results are shown the detection times, for cases where were analyzed incipient faults, the time required for fault detection must be improved, in this work, an adaptive threshold was used to reduce the false alarms but it also increases the detection times. It was concluded that the Q chart gave a better result for fault detection; the isolation times were similar to the detection ones. Two incipient faults could not be detected, the fault detection rate was similar to the shown in literature, but the detection times were better in 35% of the cases, unfortunately for four faults the detection times were bigger than the reported in other papers. It is proposed to help this method with independent component analysis due it is not guaranteed to have a Gaussian distribution in the samples

Evaluation of different methodologies for primary human dermal fibroblast spheroid formation: automation through 3D bioprinting technology

Cell spheroids have recently emerged as an effective tool to recapitulate native microenvironments of living organisms in an in vitro scenario, increasing the reliability of the results obtained and broadening their applications in regenerative medicine, cancer research, disease modeling and drug screening. In this study the generation of spheroids containing primary human dermal fibroblasts was approached using the two-widely employed methods: hanging-drop and U-shape low adhesion plate (LA-plate). Moreover, extrusion-based three-dimensional (3D) bioprinting was introduced to achieve a standardized and scalable production of cell spheroids, decreasing considerably the possibilities of human error. This was ensured when U-shape LA-plates were used, showing an 85% formation efficiency, increasing up to a 98% when it was automatized using the 3D bioprinting technologies. However, sedimentation effect within the cartridge led to a reduction of 20% in size of the spheroid during the printing process. Hyaluronic acid (HA) was chosen as viscosity enhancer to supplement the bioink and overcome cell sedimentation within the cartridge due to the high viability values exhibited by the cells -around 80%- at the used conditions. Finally, (ANCOVA) of spheroid size over time for different printing conditions stand out HA 0.4% (w/v) 60 kDa as the viscosity-improved bioink that exhibit the highest cell viability and spheroid formation percentages. Besides, not only did it ensure cell spheroid homogeneity over time, reducing cell sedimentation effects, but also wider spheroid diameters over time with less variability, outperforming significantly manual loading.We kindly thank Daniel García for their guidance with the rheological experiments. This work was supported by Programa de Actividades de I + D entre Grupos de Investigación de la Comunidad de Madrid, S2018/ BAA-4480, Biopieltec-CM, Programa Estatal de I + D + i Orientada a los Retos de la Sociedad, RTI2018-101627-B-I00 and Cátedra Fundación Ramón Areces. The experimental techniques used during this study were performed in the CleanRooms of Bioengineering, Universidad Carlos III de Madrid, Madrid, Spain

Fundamental group of plane curves and related invariants

The article under review contains a study of the topology of a pair (P2,C), where C is an algebraic curve in the complex projective plane. The basic problem is to find invariants which are sensitive enough to distinguish many pairs, and for which there is an algorithm for checking this. The homology of the complement is certainly computable in this sense, but it is too coarse to be really useful. The fundamental group of the complement, by contrast, is very sensitive. The article reviews the Zariski-van Kampen method for finding a presentation for it. However, it is not clear whether the isomorphism problem for this class of groups is solvable. The article surveys many other invariants, such as the Alexander polynomial and characteristic varieties, which are more computable. This last set of invariants was introduced, in this context, by A. S. Libgober [in Applications of algebraic geometry to coding theory, physics and computation (Eilat, 2001), 215–254, Kluwer Acad. Publ., Dordrecht, 200