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.

PMMA with Long-Persistent Phosphors and Its Behavior of Luminescence

A new kind of rare earth material with high efficient long-persistent phosphors, such as SrAl2O4: Eu, Dy, has been developed in recent years. The PMMA with long-persistent phosphors is typical one of applications for the phosphors. In this work, we try to probe into the affection of the manufacture process on the PMMA with long-persistent phosphors, to analyze its performance, and its luminescence behavior, especially to study the self-excitation of the PMMA with long-persistent phosphors.

Yellow luminescence mechanism and persistent photoconductivity in n-GaN single crystal films grown on alpha-Al2O3(0001) substrates by LP-MOCVD

Unintentionally doped and Si-doped single crystal n-GaN films have been grown on alpha-Al2O3 (0001) substrates by LP-MOCVD. Room temperature photoluminescence measurement showed that besides the bandedges, the spectrum of an undoped sample was a broad deep-level emission band peaking from 2.19 to 2.30eV, whereas the spectrum for a Si-doped sample was composed of a dominant peak of 2.19eV and a shoulder of 2.32eV. At different temperatures, photoconductance buildup and its decay were also observed for both samples.. The likely origins of persistent photoconductivity and yellow luminescence, which might be associated with deep defects inclusive of either Ga vacancy(V-Ga)/Ga vacancy complex induced by impurities or N antisite (N-Ga), will be proposed.

Competition between band gap and yellow luminescence in undoped GaN grown by MOVPE on sapphire substrate

Undoped GaN epilayer on c-face (0 0 0 1) sapphire substrate has been grown by metalorganic vapor-phase epitaxy (MOVPE) in a horizontal-type low-pressure two-channel reactor. Photoluminescence (PL) as a function of temperature and excitation intensity have been systematically studied, and the competition between near band gap ultraviolet (UV) and defect-related yellow luminescence (YL) has been extensively investigated, It is revealed that the ratio of the UV-to-YL peak intensities depends strongly on the excitation intensity and the measurement temperature. The obtained results have been analyzed in comparison with the theoretical predications based on a bimolecular model. (C) 2001 Elsevier Science B.V. All rights reserved.

Persistent chlamydial infections : role in inflammation and challenges for vaccine development.

The development of chlamydial vaccines continues to be a major challenge for researchers. While acute infections are the main target of vaccine development groups, Chlamydia is well known for its ability to establish chronic or persistent infections in its host. To date, little effort has focussed specifically on the challenges of vaccines to successfully combat the chronic or persistent phase of the disease and yet this will be a necessary aspect of any fully successful chlamydial vaccine. This short review specifically examines the phenomenon of chlamydial persistence and the unique challenges that this brings to vaccine development.

A political economy perspective on persistent inequality, inflation, and redistribution

In this paper we examine the dynamics of the link between inequality and inflation from a political economy perspective. We consider a simple dynamic general equilibrium model in which agents vote over the desired inflation rate in each period, and inequality is persistent. Inflation in our model is a mechanism of redistribution, and we find that the link between inequality and inflation within any period or over time depends on institutional and preference related parameters. Furthermore, we find that differences in the initial distributions of wealth can yield a diverse set of patterns for the evolution of the inflation and inequality link. Relative to existing literature, our model leads to more precise predictions about the inflation-inequality correlation. To that end, results in the extant empirical literature on the inflation and inequality link need to be interpreted with caution.

Persistent navigation and mapping using a biologically inspired SLAM system

The challenge of persistent navigation and mapping is to develop an autonomous robot system that can simultaneously localize, map and navigate over the lifetime of the robot with little or no human intervention. Most solutions to the simultaneous localization and mapping (SLAM) problem aim to produce highly accurate maps of areas that are assumed to be static. In contrast, solutions for persistent navigation and mapping must produce reliable goal-directed navigation outcomes in an environment that is assumed to be in constant flux. We investigate the persistent navigation and mapping problem in the context of an autonomous robot that performs mock deliveries in a working office environment over a two-week period. The solution was based on the biologically inspired visual SLAM system, RatSLAM. RatSLAM performed SLAM continuously while interacting with global and local navigation systems, and a task selection module that selected between exploration, delivery, and recharging modes. The robot performed 1,143 delivery tasks to 11 different locations with only one delivery failure (from which it recovered), traveled a total distance of more than 40 km over 37 hours of active operation, and recharged autonomously a total of 23 times.

Hybrid robot control and SLAM for persistent navigation and mapping

For a mobile robot to operate autonomously in real-world environments, it must have an effective control system and a navigation system capable of providing robust localization, path planning and path execution. In this paper we describe the work investigating synergies between mapping and control systems. We have integrated development of a control system for navigating mobile robots and a robot SLAM system. The control system is hybrid in nature and tightly coupled with the SLAM system; it uses a combination of high and low level deliberative and reactive control processes to perform obstacle avoidance, exploration, global navigation and recharging, and draws upon the map learning and localization capabilities of the SLAM system. The effectiveness of this hybrid, multi-level approach was evaluated in the context of a delivery robot scenario. Over a period of two weeks the robot performed 1143 delivery tasks to 11 different locations with only one delivery failure (from which it recovered), travelled a total distance of more than 40km, and recharged autonomously a total of 23 times. In this paper we describe the combined control and SLAM system and discuss insights gained from its successful application in a real-world context.

Persistent ocean monitoring with underwater gliders : towards accurate reconstruction of dynamic ocean processes

Ocean processes are dynamic and complex events that occur on multiple different spatial and temporal scales. To obtain a synoptic view of such events, ocean scientists focus on the collection of long-term time series data sets. Generally, these time series measurements are continually provided in real or near-real time by fixed sensors, e.g., buoys and moorings. In recent years, an increase in the utilization of mobile sensor platforms, e.g., Autonomous Underwater Vehicles, has been seen to enable dynamic acquisition of time series data sets. However, these mobile assets are not utilized to their full capabilities, generally only performing repeated transects or user-defined patrolling loops. Here, we provide an extension to repeated patrolling of a designated area. Our algorithms provide the ability to adapt a standard mission to increase information gain in areas of greater scientific interest. By implementing a velocity control optimization along the predefined path, we are able to increase or decrease spatiotemporal sampling resolution to satisfy the sampling requirements necessary to properly resolve an oceanic phenomenon. We present a path planning algorithm that defines a sampling path, which is optimized for repeatability. This is followed by the derivation of a velocity controller that defines how the vehicle traverses the given path. The application of these tools is motivated by an ongoing research effort to understand the oceanic region off the coast of Los Angeles, California. The computed paths are implemented with the computed velocities onto autonomous vehicles for data collection during sea trials. Results from this data collection are presented and compared for analysis of the proposed technique.

Persistent ocean monitoring with underwater gliders : adapting sampling resolution

Ocean processes are dynamic, complex, and occur on multiple spatial and temporal scales. To obtain a synoptic view of such processes, ocean scientists collect data over long time periods. Historically, measurements were continually provided by fixed sensors, e.g., moorings, or gathered from ships. Recently, an increase in the utilization of autonomous underwater vehicles has enabled a more dynamic data acquisition approach. However, we still do not utilize the full capabilities of these vehicles. Here we present algorithms that produce persistent monitoring missions for underwater vehicles by balancing path following accuracy and sampling resolution for a given region of interest, which addresses a pressing need among ocean scientists to efficiently and effectively collect high-value data. More specifically, this paper proposes a path planning algorithm and a speed control algorithm for underwater gliders, which together give informative trajectories for the glider to persistently monitor a patch of ocean. We optimize a cost function that blends two competing factors: maximize the information value along the path, while minimizing deviation from the planned path due to ocean currents. Speed is controlled along the planned path by adjusting the pitch angle of the underwater glider, so that higher resolution samples are collected in areas of higher information value. The resulting paths are closed circuits that can be repeatedly traversed to collect long-term ocean data in dynamic environments. The algorithms were tested during sea trials on an underwater glider operating off the coast of southern California, as well as in Monterey Bay, California. The experimental results show significant improvements in data resolution and path reliability compared to previously executed sampling paths used in the respective regions.

Mortality, fertility, and persistent income inequality

Many developing countries are plagued by persistent inequality in income distribution. While a growing body of economic-demographic literature emphasizes differential fertility channel, this paper investigates differential child mortality--differences in child mortality across income groups--as a critical link through which income inequality persists. Using an overlapping generations model in which both child mortality and fertility are endogenously determined by parental choice, this paper demonstrates that differential child mortality and its interaction with differential fertility may generate an "income inequality trap." The trap is characterized by higher child mortality and lower degree of skill formation among the poorer households. The model can also explain the behavior of aggregate fertility and mortality rates for countries at various stages of development, consonant with patterns of demographic transition. The results indicate that provision of public health that raises the productivity of private health spending may be an effective way to reduce income inequality

A two week persistent navigation and mapping experiment using RatSLAM : insights and current developments

One of the major challenges in achieving long term robot autonomy is the need for a SLAM algorithm that can perform SLAM over the operational lifetime of the robot, preferably without human intervention or supervision. In this paper we present insights gained from a two week long persistent SLAM experiment, in which a Pioneer robot performed mock deliveries in a busy office environment. We used the biologically inspired visual SLAM system, RatSLAM, combined with a hybrid control architecture that selected between exploring the environment, performing deliveries, and recharging. The robot performed more than a thousand successful deliveries with only one failure (from which it recovered), travelled more than 40 km over 37 hours of active operation, and recharged autonomously 23 times. We discuss several issues arising from the success (and limitations) of this experiment and two subsequent avenues of work.