Self-Absorption and Luminescence Quantum Yields of Dye-Zeolite L Composites

Electronic absorption and fluorescence spectra based on transmission measurements of thin layers obtained from new perylene−zeolite L composites and new dye1,dye2−zeolite L sandwich composites, the latter acting as antenna systems, have been investigated and analyzed. The influence of extra- and intraparticle self-absorption on the spectral shape and fluorescence quantum yield is discussed in detail. Due to its intraparticle origin, self-absorption and re-emission can often not be avoided in organized systems such as dye−zeolite L composites where a high density of chromophores is a prerequisite for obtaining the desired photophysical properties. We show, however, that it can be avoided or at least minimized by preparing dye1,dye2−zeolite L sandwich composites where donors are present in a much larger amount than the acceptors because they act as antenna systems.

Measuring the bending of asymmetric planar EAP structures

The geometric characterization of low-voltage dielectric electro-active polymer (EAP) structures, comprised of nanometer thickness but areas of square centimeters, for applications such as artificial sphincters requires methods with nanometer precision. Direct optical detection is usually restricted to sub-micrometer resolution because of the wavelength of the light applied. Therefore, we propose to take advantage of the cantilever bending system with optical readout revealing a sub-micrometer resolution at the deflection of the free end. It is demonstrated that this approach allows us to detect bending of rather conventional planar asymmetric, dielectric EAP-structures applying voltages well below 10 V. For this purpose, we built 100 μm-thin silicone films between 50 nm-thin silver layers on a 25 μm-thin polyetheretherketone (PEEK) substrate. The increase of the applied voltage in steps of 50 V until 1 kV resulted in a cantilever bending that exhibits only in restricted ranges the expected square dependence. The mean laser beam displacement on the detector corresponded to 6 nm per volt. The apparatus will therefore become a powerful mean to analyze and thereby improve low-voltage dielectric EAP-structures to realize nanometer-thin layers for stack actuators to be incorporated into artificial sphincter systems for treating severe urinary and fecal incontinence.

Stratigraphic Continuity in 400 Mhz Short-Pulse Radar Profiles of Firn in West Antarctica

We track dated firn horizons within 400 MHz short-pulse radar profiles to find the continuous extent over which they can be used as historical benchmarks to study past accumulation rates in West Antarctica. The 30-40 cm pulse resolution compares with the accumulation rates of most areas. We tracked a particular set that varied from 30 to 90 m in depth over a distance of 600 km. The main limitations to continuity are fading at depth, pinching associated with accumulation rate differences within hills and valleys, and artificial fading caused by stacking along dips. The latter two may be overcome through multi-kilometer distances by matching the relative amplitude and spacing of several close horizons, along with their pulse forms and phases. Modeling of reflections from thin layers suggests that the - 37 to - 50 dB range of reflectivity and the pulse waveforms we observed are caused by the numerous thin ice layers observed in core stratigraphy. Constructive interference between reflections from these close, high-density layers can explain the maintenance of reflective strength throughout the depth of the firn despite the effects of compaction. The continuity suggests that these layers formed throughout West Antarctica and possibly into East Antarctica as well.

Ash layer characteristics and major element oxide content of glasses from ODP Sites 162-982 and 162-985

The Cenozoic volcanic activity on Iceland has been recorded in North Atlantic sediments drilled during several Ocean Drilling Program (ODP)/Deep Sea Drilling Project legs (Legs 104, 151, 152, 162, and 163). Leg 162 (North Atlantic-Arctic Gateways II) recovered ash layers at Sites 982, 985, and 907 (Jansen, Raymo, Blum, et al., 1996, doi:10.2973/odp.proc.ir.162.1996). The revisited Site 907 was first drilled during Leg 151, and the ash from this site has been described in detail by Lacasse et al. (1996, doi:10.2973/odp.proc.sr.151.122.1996) and Werner et al. (1996, doi:10.2973/odp.proc.sr.151.123.1996). Site 982 is located within the Hatton-Rockall Basin on the Rockall Plateau, which is situated west of the British Isles. Site 985 is located northeast of Iceland at the foot of the eastern slope of the Iceland Plateau, adjacent to the Norwegian Basin. Here we report chemical analyses of Neogene tephra layers from Holes 982A, 983B, 982C, 985A, and 985B. The sedimentary sequence at Site 982 spans the lower Miocene-Holocene; Site 985 recovered sediments spanning the upper Oligocene-Holocene. Twenty-two distinct ash layers and ash-bearing sediments were sampled in Holes 982A-982C (Cores 162-982A-16H through 24H, 162-982B-14H through 56X, and 162-982C-15H through 27H), and 59 ash layers were sampled in Holes 985A and 985B (Cores 162-985A-11H through 59X, and 162-985B-11H through 14H). Almost 50% of the sampled ash is strongly altered (predominantly from Site 985). A cluster of altered thin layers in the lower Pliocene of Site 985 (top of Unit III) is remarkable.

Chemistry of siliciclastic and volcanoclastic sediments of DSDP Site 47-397

The Lower Cretaceous and Miocene sequences of the NW African passive continental margin consist of siliciclastic, volcaniclastic and hybrid sediments. These sediments contain a variety of diagenetic carbonates associated with zeolites, smectite clays and pyrite, reflecting the detrital mineralogical composition and conditions which prevailed during opening of the North Atlantic. In the Lower Cretaceous siliciclastic sediments, siderite (-6 per mil to +0.7per mil d18O PDB, -19.6 per mil to +0.6 per mil d13C PDB) was precipitated as thin layers and nodules from modified marine porewaters with input of dissolved carbon from the alteration of organic matter. Microcrystalline dolomite layers, lenses, nodules and disseminated crystals (-3.0 per mil to +2.5 per mil d18O PDB, -7.2 per mil to +4.9 per mil d13C PDB) predominate in slump and debris-flow deposits within the Lower Miocene sequence. During the opening of the Atlantic, volcanic activity in the Canary Islands area resulted in input of volcaniclastic sediments to the Middle and Upper Miocene sequences. Calcite is the dominant diagenetic carbonate in the siliciclastic-bioclastic-volcaniclastic hybrid and in the volcaniclastic sediments, which commonly contain pore-rimming smectite. Diagenetic calcite (-22 per mil to +1.6 per mil d18O PDB, -35.7 per mil to +0.8 per mil d13C PDB) was precipitated due to the interaction of volcaniclastic and bioclastic grains with marine porewaters. Phillipsite is confined to the alteration of volcaniclastic sediments, whereas clinoptilolite is widely disseminated, occurring essentially within foraminiferal chambers, and formed due to the dissolution of biogenic silica.

Isotopic survey of diagenetic carbonates, at DSDP Leg 63 Holes

Authigenic carbonates, principally calcium-rich dolomites, with extremely variable isotopic compositions were recovered in organic-rich marine sediments during Leg 63 drilling off southern California and Baja California. These carbonates occur as thin layers in fine-grained, diatomaceous sediments and siliceous rocks, mostly deposited during the Neogene. A combination of textural, geochemical, and isotopic evidence indicates these dolomites formed as cements and precipitates in shallow subsurface zones of high alkalinity spawned by abundant CO2 and methane production during progressive microbial decay of organic matter. Depths and approximate temperatures of formation estimated from oxygen isotopes are 87 to 658 meters and 10°C to 50°C, respectively. Within any sedimentary section, dolomites may form simultaneously at several depths or at different times within the same interval. Highly variable carbon isotopes (-30 to +16 per mil) reflect the isotopic reservoir in which the carbonates formed. Oxidation of organic matter through microbial reduction of sulfate at shallow depths favors light-carbon carbonates such as those at Sites 468 and 471; heavy-carbon carbonates at Site 467 most likely formed below this zone where HC**12O3**- is preferentially removed by reduction of CO2 to methane during methanogenesis. An important controlling factor is the sedimentation rate, which dictates both the preservation of organic matter on the sea floor and depth distribution of subsurface zones of organic-matter decay.

Chemical and isotope composition of poor fluid from gas-hydrate samples of ODP Site 146-892

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2-19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ~17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperatures of the recovered core ranged from 2 to -1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (delta34S, +27.4?) were released. The delta13C values of the CH4 in the gas hydrate, -64.5 to -67.5? (PDB), together with deltaD values of -197 to -199? (SMOW) indicate a primarily microbial source for the CH4. The delta18O value of the hydrate H2O is +2.9? (SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a >=99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.

Investigation on the structural and magnetic properties of sputtered TbFe2/Fe3Ga heterostructures

We have analyzed the structural and magnetic properties of as-grown and annealed [TbFe2/Fe3Ga]n heterostructures grown by sputtering. Evidence of the bcc structure in the Fe3Ga layers has been found. The diffraction peak related to this structure shifts to high angles with the annealing temperature. Also, we have observed a change in the microstructure of the Tb-Fe layers when the thickness layer is reduced in the as-grown heterostructures. Moreover, the Tb content is lower than 33% of the TbFe2 Laves phase and it depends on the layer thickness. The thermal treatments promote the increase of the Tb content, but only in the heterostructures with thick layers. The strong lattice mismatch between the Tb-Fe and Fe-Ga layers seems to prevent a complete Tb diffusion upon the annealing process. Thus, the crystallization of the TbFe2 Laves phase is inhibited in the heterostructures with thin layers, although our experimental results indicate the presence of potential magnetostrictive TbFeGa alloys

Confined crystallization of nanolayered poly(ethylene terephthalate) using X-ray diffraction methods

The development of crystalline lamellae in ultra-thin layers of poly(ethylene terephthalate) PET confined between polycarbonate (PC) layers in an alternating assembly is investigated as a function of layer thickness by means of X-ray diffraction methods. Isothermal crystallization from the glassy state is in-situ followed by means of small-angle X-ray diffraction. It is found that the reduced size of the PET layers influences the lamellar nanostructure and induces a preferential lamellar orientation. Two lamellar populations, flat-on and edge-on, are found to coexist in a wide range of crystallization temperatures (Tc = 117–150 °C) and within layer thicknesses down to 35 nm. Flat-on lamellae appear at a reduced crystallization rate with respect to bulk PET giving rise to crystals of similar dimensions separated by larger amorphous regions. In addition, a narrower distribution of lamellar orientations develops when the layer thickness is reduced or the crystallization temperature is raised. In case of edge-on lamellae, crystallization conditions also influence the development of lamellar orientation; however, the latter is little affected by the reduced size of the layers. Results suggest that flat-on lamellae arise as a consequence of spatial confinement and edge-on lamellae could be generated due to the interactions with the PC interface. En este trabajo se investiga mediante difracción de rayos X a ángulos bajos (SAXS) y a ángulos altos (WAXS), la cristalización de láminas delgadas de Polietilén tereftalato (PET) confinadas entre láminas de Policarbonato (PC), tomando como referencia PET sin confinar. El espesor de las capas de PET varía entre 35nm y 115 nm. Se realizaron medidas de difracción a tres temperaturas de cristalización (117ºC, 132ºC y 150ºC) encontrándose que el reducido espesor de las capas de PET influye en la estructura lamelar que se desarrolla, induciendo una orientación preferente de las láminas. Se integró la intensidad difractada alrededor del máximo en SAXS para obtener una representación de la intensidad en función del ángulo acimutal. Mediante análisis de mínimos cuadrados se separó la curva experimental obtenida en tres contribuciones diferentes: una función Gausiana que describe la distribución de las orientaciones de las lamelas, una función lorenziana asociada a los máximos meridionales (asociados a las interfases PET-PC) y un background constante. Por otra parte la cantidad de material cristalizado se estimó asumiendo que la intensidad del background en el barrido acimutal, una vez restado el background del primer difractograma (sin máximos en SAXS) se asocia con la contribución del material isotrópico que resta en la muestra cristalizada. Se observa la coexistencia de dos poblaciones de lamelas: flat-on y edge-on. A medida que el espesor de las láminas de PET disminuye la población de las lamelas flat-on experimenta los siguientes cambios: 1) la distribución de orientación se estrecha, 2) la fracción de material cristalizado orientado aumenta, 3) la cinética de cristalización se ralentiza y 4) el largo espaciado aumenta es decir las regiones amorfas entre lamelas aumentan su tamaño. Parece demostrarse que es en las primeras etapas del crecimiento lamelar cuando la restricción espacial fuerza a las lamelas a esta orientación tipo flat-on frente a la orientación edge-on.

Interconexión monolítica de dispositivos fotovoltaicos basados en a-Si mediante ablación directa con fuentes láser ultravioleta

Resumen En la última década la tecnología láser se ha convertido en una herramienta imprescindible en la fabricación de dispositivos fotovoltaicos, muy especial¬mente en aquellos basados en tecnología de lámina delgada. Independiente¬mente de crisis coyunturales en el sector, la evolución en los próximos años de estas tecnologías seguirá aprovechándose de la flexibilidad y calidad de proceso de la herramienta láser para la consecución de los dos objetivos básicos que harán de la fotovoltaica una opción energética económicamente viable: la reducción de costes de fabricación y el aumento de eficiencia de los dispositivos. Dentro de las tecnologías fotovoltaicas de lámina delgada, la tecnología de dispositivos basados en silicio amorfo ha tenido un gran desarrollo en sistemas estándar en configuración de superestrato, pero su limitada efi¬ciencia hace que su supervivencia futura pase por el desarrollo de formatos en configuración de substrato sobre materiales flexibles de bajo coste. En esta aproximación, las soluciones industriales basadas en láser actualmente disponibles para la interconexión monolítica de dispositivos no son aplica¬bles, y desde hace años se viene investigando en la búsqueda de soluciones apropiadas para el desarrollo de dichos procesos de interconexión de forma que sean transferibles a la industria. En este contexto, esta Tesis propone una aproximación completamente orig¬inal, demostrando la posibilidad de ejecutar una interconexión completa de estos dispositivos irradiando por el lado de la lámina (es decir de forma com¬patible con la opción de configuración de substrato y, valga la redundancia, con el substrato del dispositivo opaco), y con fuentes láser emitiendo en UV. Este resultado, obtenido por primera vez a nivel internacional con este trabajo, aporta un conocimiento revelador del verdadero potencial de estas fuentes en el desarrollo industrial futuro de estas tecnologías. Si bien muy posiblemente la solución industrial final requiera de una solución mixta con el empleo de fuentes en UV y, posiblemente, en otras longitudes de onda, esta Tesis y su planteamiento novedoso aportan un conocimiento de gran valor a la comunidad internacional por la originalidad del planteamiento seguido, los resultados parciales encontrados en su desarrollo (un número importante de los cuales han aparecido en revistas del JCR que recogen en la actualidad un número muy significativo de citas) y porque saca además a la luz, con las consideraciones físicas pertinentes, las limitaciones intrínsecas que el desarrollo de procesos de ablación directa selectiva con láseres UV en parte de los materiales utilizados presenta en el rango temporal de in¬teracción de ns y ps. En este trabajo se han desarrollado y optimizado los tres pasos estándar de interconexión (los habitualmente denominados Pl, P2 y P3 en la industria fotovoltaica) demostrando las ventajas y limitaciones del uso de fuentes en UV tanto con ancho temporal de ns como de ps. En particular destaca, por el éxito en los resultados obtenidos, el estudio de procesos de ablación selectiva de óxidos conductores transparentes (en este trabajo utilizados tanto como contacto frontal así como posterior en los módulos) que ha generado resultados, de excelente acogida científica a nivel internacional, cuya aplicación trasciende el ámbito de las tecnologías de silicio amorfo en lámina delgada. Además en este trabajo de Tesis, en el desarrollo del objetivo citado, se han puesto a punto técnicas de análisis de los procesos láser, basadas en métodos avanzados de caracterización de materiales (como el uso combi¬nado de la espectroscopia dispersiva de rayos X y la microscopía confocal de barrido) que se presentan como auténticos avances en el desarrollo de técnicas específicas de caracterización para el estudio de los procesos con láser de ablación selectiva de materiales en lámina delgada, procesos que no solo tienen impacto en el ámbito de la fotovoltaica, sino también en la microelectrónica, la biotecnología, la microfabricación, etc. Como resultado adicional, parte de los resultados de este trabajo, han sido aplicados exi¬tosamente por el grupo de investigaci´on en la que la autora desarrolla su labor para conseguir desarrollar procesos de enorme inter´es en otras tec-nolog´ıas fotovoltaicas, como las tecnolog´ıas est´andar de silicio amorfo sobre vidrio en configuraci´on de superestrato o el procesado de capas delgadas en tecnolog´ıas convencionales de silicio cristalino. Por u´ltimo decir que este trabajo ha sido posible por una colaboraci´on muy estrecha entre el Centro L´aser de la UPM, en el que la autora de¬sarrolla su labor, y el Grupo de Silicio Depositado del Centro de Inves¬tigaciones Energ´eticas, Medioambientales y Tecnol´ogicas, CIEMAT, que, junto al Grupo de Energ´ıa Fotovoltaica de la Universidad de Barcelona, han preparado la mayor parte de las muestras utilizadas en este estudio. Dichas colaboraciones se han desarrollado en el marco de varios proyectos de investigaci´on aplicada con subvenci´on pu´blica, tales como el proyecto singular estrat´egico PSE-MICROSIL08 (PSE-120000-2006-6), el proyecto INNDISOL (IPT-420000-2010-6), ambos financiados porel Fondo Europeo de Desarrollo Regional FEDER (UE) ”Una manera de hacer Europa y el MICINN, y los proyectos de Plan Nacional AMIC (ENE2010-21384-C04-´ 02) y CLASICO (ENE2007-6772-C04-04), cuya financiaci´on ha permitido en gran parte llevar a t´ermino este trabajo Abstract In the last decade, the laser technology has turned into an indispensable tool in the production of photovoltaic devices, especially of those based on thin film technology. Regardless the current crisis in the sector, the evolution of these technologies in the upcoming years will keep taking advantage of the flexibility and process quality of the laser tool for the accomplishment of the two basic goals that will convert the photovoltaic energy into economically viable: the manufacture cost reduction and the increase in the efficiency of the devices. Amongst the thin film laser technologies, the technology of devices based on amorphous silicon has had a great development in standard systems of superstrate configuration, but its limited efficiency makes its survival de¬pendant on the development of formats in substrate configuration with low cost flexible materials. In this approach, the laser industrial solutions cur¬rently available for the monolithic interconnection are not applicable, and in the last few years the investigations have been focused on the search of appropriate solutions for the development of such interconnection processes in a way that the same are transferable to the industry. In this context, this Thesis proposes a totally original approach, proving the possibility of executing a full interconnection of these devices by means of irradiation from the film side, i.e., compatible with the substrate con¬figuration, and with UV laser sources. This result, obtained for the first time at international level in this work, provides a revealing knowledge of the true potential of these sources in the future industrial development of these technologies. Even though very probably the final industrial solution will require a combination of the use of UV sources along with other wave¬lengths, this Thesis and its novel approach contribute with a high value to the international community because of the originality of the approach, the partial results found throughout its development (out of which, a large number has appeared in JCR journals that currently accumulate a signifi¬cant number of citations) and brings to light, with the pertinent scientific considerations, the intrinsic limitations that the selective direct ablation processes with UV laser present in the temporal range of interaction of ns and ps for part of the materials used in this study. More particularly, the three standard steps of interconnection (usually de¬nominated P1, P2 and P3 in the photovoltaic industry) have been developed and optimized, showing the advantages as well as the limitations of the use of UV sources in both the ns and ps pulse-width ranges. It is highly remark¬able, because of the success in the obtained results, the study of selective ablation processes in transparent conductive oxide (in this work used as a front and back contact), that has generated results, of excellent interna¬tional scientific reception, whose applications go beyond the scope of thin film photovoltaic technologies based on amorphous silicon. Moreover, in this Thesis, with the development of the mentioned goal, differ¬ent techniques of analysis of laser processes have been fine-tuned, basing the same in advanced methods for material characterization (like the combined use of EDX Analysis and Confocal Laser Scanning Microscopy) that can be presented as true breakthroughs in the development of specific techniques for characterization in the study of laser processes of selective ablation of materials in thin film technologies, processes that not only have impact in the photovoltaic field, but also in those of microelectronics, biotechnology, micro-fabrication, etc. As an additional outcome, part of the results of this work has been suc¬cessfully applied, by the investigation group to which the author belongs, to the development of processes of enormous interest within other photo¬voltaic technologies, such as the standard technologies on amorphous silicon over glass in superstrate configuration or the processing of thin layers in conventional technologies using crystalline silicon. Lastly, it is important to mention that this work has been possible thanks to the close cooperation between the Centro L´aser of the UPM, in which the author develops her work, and the Grupo de Silicio Depositado of Centro de Investigaciones Energ´eticas, Medioambientales y Tecnol´ogicas, CIEMAT, which, along with the Grupo de Energ´ıa Fotovoltaica of Univer¬sidad de Barcelona, has prepared the largest part of the samples utilized in this study. Such collaborations have been carried out in the context of several projects of applied investigation with public funding, like Proyecto Singular Estrat´egico PSE-MICROSIL08 (PSE-120000-2006-6), Proyecto IN-NDISOL (IPT-420000-2010-6), both funded by the European Regional De¬velopment Fund (ERDF), ”Una manera de hacer Europa” and MICINN, and the projects of Plan Nacional AMIC (ENE2010-21384-C04-02) and ´ CLASICO (ENE2007-6772-C04-04), whose funds have enabled the devel-opment of large part of this work.

Low Work-Function Thermionic Emission and Orbital-Motion-Limited Ion Collection at Bare-Tether Cathodic Contact

Una amarra electrodinámica (electrodynamic tether) opera sobre principios electromagnéticos intercambiando momento con la magnetosfera planetaria e interactuando con su ionosfera. Es un subsistema pasivo fiable para desorbitar etapas de cohetes agotadas y satélites al final de su misión, mitigando el crecimiento de la basura espacial. Una amarra sin aislamiento captura electrones del plasma ambiente a lo largo de su segmento polarizado positivamente, el cual puede alcanzar varios kilómetros de longitud, mientras que emite electrones de vuelta al plasma mediante un contactor de plasma activo de baja impedancia en su extremo catódico, tal como un cátodo hueco (hollow cathode). En ausencia de un contactor catódico activo, la corriente que circula por una amarra desnuda en órbita es nula en ambos extremos de la amarra y se dice que ésta está flotando eléctricamente. Para emisión termoiónica despreciable y captura de corriente en condiciones limitadas por movimiento orbital (orbital-motion-limited, OML), el cociente entre las longitudes de los segmentos anódico y catódico es muy pequeño debido a la disparidad de masas entre iones y electrones. Tal modo de operación resulta en una corriente media y fuerza de Lorentz bajas en la amarra, la cual es poco eficiente como dispositivo para desorbitar. El electride C12A7 : e−, que podría presentar una función de trabajo (work function) tan baja como W = 0.6 eV y un comportamiento estable a temperaturas relativamente altas, ha sido propuesto como recubrimiento para amarras desnudas. La emisión termoiónica a lo largo de un segmento así recubierto y bajo el calentamiento de la operación espacial, puede ser más eficiente que la captura iónica. En el modo más simple de fuerza de frenado, podría eliminar la necesidad de un contactor catódico activo y su correspondientes requisitos de alimentación de gas y subsistema de potencia, lo que resultaría en un sistema real de amarra “sin combustible”. Con este recubrimiento de bajo W, cada segmento elemental del segmento catódico de una amarra desnuda de kilómetros de longitud emitiría corriente como si fuese parte de una sonda cilíndrica, caliente y uniformemente polarizada al potencial local de la amarra. La operación es similar a la de una sonda de Langmuir 2D tanto en los segmentos catódico como anódico. Sin embargo, en presencia de emisión, los electrones emitidos resultan en carga espacial (space charge) negativa, la cual reduce el campo eléctrico que los acelera hacia fuera, o incluso puede desacelerarlos y hacerlos volver a la sonda. Se forma una doble vainas (double sheath) estable con electrones emitidos desde la sonda e iones provenientes del plasma ambiente. La densidad de corriente termoiónica, variando a lo largo del segmento catódico, podría seguir dos leyes distintas bajo diferentes condiciones: (i) la ley de corriente limitada por la carga espacial (space-charge-limited, SCL) o (ii) la ley de Richardson-Dushman (RDS). Se presenta un estudio preliminar sobre la corriente SCL frente a una sonda emisora usando la teoría de vainas (sheath) formada por la captura iónica en condiciones OML, y la corriente electrónica SCL entre los electrodos cilíndricos según Langmuir. El modelo, que incluye efectos óhmicos y el efecto de transición de emisión SCL a emisión RDS, proporciona los perfiles de corriente y potencial a lo largo de la longitud completa de la amarra. El análisis muestra que en el modo más simple de fuerza de frenado, bajo condiciones orbitales y de amarras típicas, la emisión termoiónica proporciona un contacto catódico eficiente y resulta en una sección catódica pequeña. En el análisis anterior, tanto la transición de emisión SCL a RD como la propia ley de emisión SCL consiste en un modelo muy simplificado. Por ello, a continuación se ha estudiado con detalle la solución de vaina estacionaria de una sonda con emisión termoiónica polarizada negativamente respecto a un plasma isotrópico, no colisional y sin campo magnético. La existencia de posibles partículas atrapadas ha sido ignorada y el estudio incluye tanto un estudio semi-analítico mediante técnica asintóticas como soluciones numéricas completas del problema. Bajo las tres condiciones (i) alto potencial, (ii) R = Rmax para la validez de la captura iónica OML, y (iii) potencial monotónico, se desarrolla un análisis asintótico auto-consistente para la estructura de plasma compleja que contiene las tres especies de cargas (electrones e iones del plasma, electrones emitidos), y cuatro regiones espaciales distintas, utilizando teorías de movimiento orbital y modelos cinéticos de las especies. Aunque los electrones emitidos presentan carga espacial despreciable muy lejos de la sonda, su efecto no se puede despreciar en el análisis global de la estructura de la vaina y de dos capas finas entre la vaina y la región cuasi-neutra. El análisis proporciona las condiciones paramétricas para que la corriente sea SCL. También muestra que la emisión termoiónica aumenta el radio máximo de la sonda para operar dentro del régimen OML y que la emisión de electrones es mucho más eficiente que la captura iónica para el segmento catódico de la amarra. En el código numérico, los movimientos orbitales de las tres especies son modelados para potenciales tanto monotónico como no-monotónico, y sonda de radio R arbitrario (dentro o más allá del régimen de OML para la captura iónica). Aprovechando la existencia de dos invariante, el sistema de ecuaciones Poisson-Vlasov se escribe como una ecuación integro-diferencial, la cual se discretiza mediante un método de diferencias finitas. El sistema de ecuaciones algebraicas no lineal resultante se ha resuelto de con un método Newton-Raphson paralelizado. Los resultados, comparados satisfactoriamente con el análisis analítico, proporcionan la emisión de corriente y la estructura del plasma y del potencial electrostático. ABSTRACT An electrodynamic tether operates on electromagnetic principles and exchanges momentum through the planetary magnetosphere, by continuously interacting with the ionosphere. It is a reliable passive subsystem to deorbit spent rocket stages and satellites at its end of mission, mitigating the growth of orbital debris. A tether left bare of insulation collects electrons by its own uninsulated and positively biased segment with kilometer range, while electrons are emitted by a low-impedance active device at the cathodic end, such as a hollow cathode, to emit the full electron current. In the absence of an active cathodic device, the current flowing along an orbiting bare tether vanishes at both ends and the tether is said to be electrically floating. For negligible thermionic emission and orbital-motion-limited (OML) collection throughout the entire tether (electron/ion collection at anodic/cathodic segment, respectively), the anodic-to-cathodic length ratio is very small due to ions being much heavier, which results in low average current and Lorentz drag. The electride C12A7 : e−, which might present a possible work function as low as W = 0.6 eV and moderately high temperature stability, has been proposed as coating for floating bare tethers. Thermionic emission along a thus coated cathodic segment, under heating in space operation, can be more efficient than ion collection and, in the simplest drag mode, may eliminate the need for an active cathodic device and its corresponding gas-feed requirements and power subsystem, which would result in a truly “propellant-less” tether system. With this low-W coating, each elemental segment on the cathodic segment of a kilometers-long floating bare-tether would emit current as if it were part of a hot cylindrical probe uniformly polarized at the local tether bias, under 2D probe conditions that are also applied to the anodic-segment analysis. In the presence of emission, emitted electrons result in negative space charge, which decreases the electric field that accelerates them outwards, or even reverses it, decelerating electrons near the emitting probe. A double sheath would be established with electrons being emitted from the probe and ions coming from the ambient plasma. The thermionic current density, varying along the cathodic segment, might follow two distinct laws under different con ditions: i) space-charge-limited (SCL) emission or ii) full Richardson-Dushman (RDS) emission. A preliminary study on the SCL current in front of an emissive probe is presented using the orbital-motion-limited (OML) ion-collection sheath and Langmuir’s SCL electron current between cylindrical electrodes. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects considered and the transition from SCL to full RDS emission is included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission provides efficient cathodic contact and leads to a short cathodic section. In the previous analysis, both the transition between SCL and RDS emission and the current law for SCL condition have used a very simple model. To continue, considering an isotropic, unmagnetized, colissionless plasma and a stationary sheath, the probe-plasma contact is studied in detail for a negatively biased probe with thermionic emission. The possible trapped particles are ignored and this study includes both semianalytical solutions using asymptotic analysis and complete numerical solutions. Under conditions of i) high bias, ii) R = Rmax for ion OML collection validity, and iii) monotonic potential, a self-consistent asymptotic analysis is carried out for the complex plasma structure involving all three charge species (plasma electrons and ions, and emitted electrons) and four distinct spatial regions using orbital motion theories and kinetic modeling of the species. Although emitted electrons present negligible space charge far away from the probe, their effect cannot be neglected in the global analysis for the sheath structure and two thin layers in between the sheath and the quasineutral region. The parametric conditions for the current to be space-chargelimited are obtained. It is found that thermionic emission increases the range of probe radius for OML validity and is greatly more effective than ion collection for cathodic contact of tethers. In the numerical code, the orbital motions of all three species are modeled for both monotonic and non-monotonic potential, and for any probe radius R (within or beyond OML regime for ion collection). Taking advantage of two constants of motion (energy and angular momentum), the Poisson-Vlasov equation is described by an integro differential equation, which is discretized using finite difference method. The non-linear algebraic equations are solved using a parallel implementation of the Newton-Raphson method. The results, which show good agreement with the analytical results, provide the results for thermionic current, the sheath structure, and the electrostatic potential.

Low work-function thermionic emission and orbital-motion-limited ion collection at bare-tether cathodic contact

With a thin coating of low-work-function material, thermionic emission in the cathodic segment of bare tethers might be much greater than orbital-motion-limited (OML) ion collection current. The space charge of the emitted electrons decreases the electric field that accelerates them outwards, and could even reverse it for high enough emission, producing a potential hollow. In this work, at the conditions of high bias and relatively low emission that make the potential monotonic, an asymptotic analysis is carried out, extending the OML ion-collection analysis to investigate the probe response due to electrons emitted by the negatively biased cylindrical probe. At given emission, the space charge effect from emitted electrons increases with decreasing magnitude of negative probe bias. Although emitted electrons present negligible space charge far away from the probe, their effect cannot be neglected in the global analysis for the sheath structure and two thin layers in between sheath and the quasineutral region. The space-charge-limited condition is located. It is found that thermionic emission increases the range of probe radius for OML validity and is greatly more effective than ion collection for cathodic contact of tethers.

Lithology and measurement of largest grains in ODP Hole 152-918D (Table 1)

Shipboard analysis of the 1183-m sedimentary section recovered at Site 918 in the Irminger Basin during Ocean Drilling Program Leg 152 revealed material of glacial origin (diamictons, ice-rafted debris (IRD) and dropstones) as deep as 543 m below sea floor (bsf). The sediment containing the deepest dropstone was biostratigraphically dated shipboard as approximately 7 Ma, pushing back the date for the onset of glaciation on southern Greenland by 5 Ma. Thin layers of fine sand were found as much as 60 m deeper in the core, raising the possibility of an even earlier date for glaciation. To determine the sedimentary history of these deeper sand layers, the surface textures on quartz grains from eleven cores bracketing the interval of interest were analyzed by scanning electron microscope. The results suggest that the grains in the 60-m interval below the deepest dropstone have a glacial history. At that level, an 11 -Ma Sr-isotope date was obtained from planktonic foraminifers. This late Miocene timing is supported biostratigraphically by both nannofossil and foraminifer assemblages, indicating a new minimum age for the onset of glaciation on southern Greenland and in the North Atlantic.

(Table 1) Stratigraphic distribution and abundances of Cretaceous radiolarians from ODP Holes 130-803D and 130-807C

Among the five sites drilled during Ocean Drilling Program Leg 130, two deep holes (8O3D and 807C) penetrated Cretaceous sediments overlying the basaltic pillows, flows, and possibly basement rocks. Abundant, poorly preserved radiolarians with limited diversity were recovered from a few horizons within the sediments proximal to the basalt. At Site 803, three thin layers of radiolarites interbedded with claystone and clayey siltstone yielded radiolarian assemblages of late Albian age. At Site 807, several layers of radiolarian siltstones were recovered proximal to the basalt. Among them the most significant radiolarian assemblage is an Aptian fauna, located approximately 7 m above the basaltic flows. The Aptian radiolarian age for Site 807 is at least in accord with those suggested by planktonic foraminifer and paleomagnetic evidence. These Cretaceous radiolarians are the oldest assemblages recorded from the Ontong Java Plateau region.

Calcium carbonate, organic carbon, sediment description and hydrogen and oxygen index at DSDP Sites 93-603, 93-605, 93-604 and 95-603

The organic matter contents of sediments and rocks sampled during DSDP Leg 93 have been characterized by CHN and Rock-Eval analyses. Most samples from Sites 604 and 605 on the New Jersey continental slope and from Site 603 on the Hatteras outer continental rise contained less than 0.5% organic carbon. Some Neogene samples from the slope contained 1 to 2% organic carbon, and Cretaceous samples from the outer rise were as rich as 13.6% organic carbon by weight. Thin layers of black claystones of Santonian, Cenomanian, and Albian age were found interbedded in organiccarbon- lean, bioturbated, turbiditic claystones. Similar layers of turbiditic black marlstones were interspersed among Neocomian limestones and sandstones. Although the organic matter in many of the samples appeared to be detrital continental material, according to Rock-Eval and C/N values, Cenomanian black shales, in particular, contained substantial proportions of marine-derived organic matter.