Local Electrochemical Investigation of Single Grains of Polycrystalline Cu-16%Zn-8%Al Alloy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mechanical characterization of GdBCO/Ag and YBCO single grains fabricated by top-seeded melt growth at 77 and 300 K

YBaCuO and GdBaCuO + 15 wt% Ag large, single-grain, bulk superconductors have been fabricated via the top-seeded, melt-growth (TSMG) process using a generic NdBCO seed. The mechanical behavior of both materials has been investigated by means of three-point bending (TPB) and transversal tensile tests at 77 and 300 K. The strength, fracture toughness and hardness of the samples were studied for two directions of applied load to obtain comprehensive information about the effect of microstructural anisotropy on the macroscopic and microscopic mechanical properties of these technologically important materials. Splitting (Brazilian) tests were carried out on as-melt-processed cylindrical samples following a standard oxygenation process and with the load applied parallel to the growth-facet lines characteristic of the TSMG process. In addition, the elastic modulus of each material was measured by three different techniques and related to the microstructure of each sample using optical microscopy. The results show that both the mechanical properties and the elastic modulus of both YBCO and GdBCP/Ag are improved at 77 K. However, the GdBCO/Ag samples are less anisotropic and exhibit better mechanical behavior due to the presence of silver particles in the bulk, superconducting matrix. The splitting tensile strength was determined at 77 K and both materials were found to exhibit similar behavior, independently of their differences in microstructure.

Thermal history versus sedimentary history: OSL sensitivity of quartz grains extracted from rocks and sediments

The optically stimulated luminescence (OSL) sensitivity of quartz has a significant influence on luminescence dating procedures. Furthermore, identifying the natural controls of quartz OSL sensitivity is an important step towards new applications of OSL in geology such as provenance tracing. We evaluate the OSL sensitivity (total and the proportion of the informally assigned fast, medium and slow components) of single grains of quartz extracted from 10 different igneous and metamorphic rocks with known formation conditions; and from fluvial and coastal sediments with different sedimentary histories and known source rocks. This sample suite allows assessment of the variability of the OSL sensitivity of single quartz grains with respect to their primary origin and sedimentary history. We observed significant variability in the OSL sensitivity of grains within all studied rock and sediment samples, with the brightest grains of each sample being those dominated by the fast component. Quartz from rocks formed under high temperature (> 500 degrees C) conditions, such as rhyolites and metamorphic rocks from the amphibolite facies, display higher OSL sensitivity. The OSL sensitivity of fluvial sediments which have experienced only a short transport distance is relatively low. These sediments show a small increase in OSL sensitivity downstream, mainly due to a decreasing fraction of ""dim"" grains. The quartz grains from coastal sands present very high sensitivity and variability, which is consistent with their long sedimentary history. The high variability of the OSL sensitivity of quartz from coastal sands is attributed more to the mixture of grains with distinct sedimentary histories than to the provenance from many types of source rocks. The temperature of crystallization and the number of cycles of burial and solar exposure are suggested as the main natural factors controlling the OSL sensitivity of quartz grains. The increase in OSL sensitivity due to cycles of erosion and deposition surpasses the sensitivity inherited from the source rock, with this increase being mainly related to the sensitization of fast OSL components. The discrimination of grains with different sedimentary histories through their OSL sensitivities can allow the development of quantitative provenance methods based on quartz. (C) 2010 Elsevier B.V. All rights reserved.

Small aliquot and single grain IRSL and post-IR IRSL dating of fluvial and alluvial sediments from the Pativilca valley, Peru

Infrared stimulated luminescence (IRSL) and post-IR IRSL are applied to small aliquots and single grains to determine the equivalent dose (De) of eleven alluvial and fluvial sediment samples collected in the Pativilca valley, Central Peru at ca. 10°S latitude. Small aliquot De distributions are rather symmetric and display over-dispersion values between 15 and 46%. Small aliquot g-values range between 4 and 8% per decade for the IRSL and 1 and 2% per decade for the post-IR IRSL signal. The single grain De distributions are highly over-dispersed with some of them skewed to higher doses, implying partial bleaching; this is especially true for the post-IR IRSL. Measurements of a modern analog reveal that residuals due to partial bleaching are present in both the IRSL as well as the post-IR IRSL signal. The g-values of individual grains exhibit a wide range with high individual uncertainties and might contribute significantly to the spread of the single grain De values, at least for the IRSL data. Electron Microprobe Analysis performed on single grains reveal that a varying K-content can be excluded as the origin of over-dispersion. Final ages for the different approaches are calculated using the Central Age Model and the Minimum Age Model (MAM). The samples are grouped into well-beached, potentially well-bleached and partially bleached according to the evaluation of the single grain distributions and the agreement of age estimates between methods. The application of the MAM to the single grain data resulted in consistent age estimates for both the fading corrected IRSL and the post-IR IRSL ages, and suggests that both approaches are suitable for dating these samples. Keywords

How Old Is Luzia? Luminescence Dating and Stratigraphic Integrity at Lapa Vermelha, Lagoa Santa, Brazil

During an excavation in the 1970s, a disarticulated female human skeleton, later nicknamed Luzia, was discovered at 12m depth at Lapa Vermelha rockshelter in central Brazil. Radiocarbon dating of associated charcoal suggested an age of 11.4-16.4 ka for the skeleton. The scattering of the skeletal parts, some uncertainty about the exact provenience of the skeleton, and evidence of pervasive insect turbation in the archaeological layers have raised doubts about the accuracy of the age. Luminescence dates for the depositional ages of the sediments at Lapa Vermelha are reported here. Single-grain optically stimulated luminescence (OSL) of quartz along with grain-size, chemical and micro-morphological analyses of the sediments were employed to assess stratigraphic integrity, particularly the degree of sediment mixing. These various lines of evidence point to high stratigraphic integrity with little mixing at Lapa Vermelha. Sediments closest to where Luzia was recovered give OSL ages ranging from 12.7 to 16.0 ka, thus not refuting the original dates. (C) 2010 Wiley Periodicals, Inc.

Chemical analysis and argon geochronology from dive SAR_1 on Cornacya seamount of the Sardinia Channel

Sarcya 1 dive explored a previously unknown 12 My old submerged volcano, labelled Cornacya. A well developed fracturation is characterised by the following directions: N 170 to N-S, N 20 to N 40, N 90 to N 120, N 50 to N 70, which corresponds to the fracturation pattern of the Sardinian margin. The sampled lavas exhibit features of shoshonitic suites of intermediate composition and include amphibole-and mica-bearing lamprophyric xenoliths which are geochemically similar to Ti-poor lamproites. Mica compositions reflect chemical exchanges between the lamprophyre and its shoshonitic host rock suggesting their simultaneous emplacement. Nd compositions of the Cornacya K-rich suite indicate that continental crust was largely involved in the genesis of these rocks. The spatial association of the lamprophyre with the shoshonitic rocks is geochemically similar to K-rich and TiO2-poor igneous suites, emplaced in post-collisional settings. Among shoshonitic rocks, sample SAR 1-01 has been dated at 12.6±0.3 My using the 40Ar/39Ar method with a laser microprobe on single grains. The age of the Cornacya shoshonitic suite is similar to that of the Sisco lamprophyre from Corsica, which similarly is located on the western margin of the Tyrrhenian Sea. Thus, the Cornacya shoshonitic rocks and their lamprophyric xenolith and the Sisco lamprophyre could represent post-collisional suites emplaced during the lithospheric extension of the Corsica-Sardinia block, just after its rotation and before the Tyrrhenian sea opening. Drilling on the Sardinia margin (ODP Leg 107) shows that the upper levels of the present day margin (Hole 654) suffered tectonic subsidence before the lower part (Hole 652). The structure of this lower part is interpreted as the result of an eastward migration of the extension during Late Miocene and Early Pliocene times. Data of Cornacya volcano are in good agreement with this model and provide good chronological constraints for the beginning of the phenomenon.

Lead isotopes of feldspar in North Atlantic Ocean sediments

The provenance of ice-rafted debris (IRD) deposited in the North Atlantic before, during, and after Heinrich event 2 has been determined through measuring the lead isotopic composition of single feldspar grains and multiple-grain composites from the larger than 150-µm size fraction, from cores from the eastern and western North Atlantic and from the Labrador Sea. Single-grain analyses are used to identify the specific continental sources of the IRD, whereas composite samples are used to assess the relative IRD contributions from different sources. All single grains from Heinrich layer 2 (H 2) as well as H 2 composites plot along a correlation line on a 207Pb/204Pb versus 206Pb/204Pb diagram characteristic of the Churchill province of the Canadian shield. This is yet another strong piece of evidence that this Heinrich event was dominated by a massive iceberg discharge of the Laurentide ice sheet lobe located over Hudson Bay. In contrast, single grains from the ambient glacial sediment (above and below H 2) have multiple sources: many of them also lie along the correlation line with H 2 grains, but many others have Pb signatures consistent with derivation from the Grenville province and the Appalachian range in North America and possibly from Scandinavia and Greenland. Composites from the ambient sediment generally lie well to the right of the H 2 reference line in agreement with the results of the single-grain analyses. The evidence provided by lead isotopes regarding the dominant role played by the Hudson Bay lobe of the Laurentide ice sheet in the development of the Heinrich events lends support to the binge/purge model advanced by MacAyeal [1993a, b] that invokes trapping of geothermal heat by the base of the icecap and subsequent basal melting as the mechanism that triggered the Heinrich events.

Composition of bottom sediments and rocks from the Philippine Trough

New data on bottom sediments and igneous rocks of the Philippine Trench are under consideration. They show differences in geological structures of the island slope and the ocean slope of the trench. The island slope is comparable to the accretionary prism formations on the Philippines; there processes of gravitational re-deposition of sediments occur. The ocean slope is an edge of the Philippine Plate sinking into the trough, where basalts of the oceanic crust are exposed.

Chemical and mineral compositions of recent and ancient sediments and sedimentary rocks from the Mariana Trench

On the bed and on the ocean slope of the southern latitudinal part of the Mariana Trench ancient sediments, as well as sedimentary and igneous rocks are exposed. In the lower part of the sampled part of the studied section Late Oligocene to Early Miocene chalk-like limestones and marls occur. Upward marly tuffites and tuffs (apparently alternating with carbonate rocks) occur. These rocks are overlain by Early Miocene tuffaceous clays and siliceous-clayey muds. In the upper part of the section there are Pleistocene pelagic clays and ethmodiscus oozes.

Pore depth evolution of a pyrochlore pellet

The long-term stability of ceramic materials that are considered as potential nuclear waste forms is governed by heterogeneous surface reactivity. Thus, instead of a mean rate, the identification of one or more dominant contributors to the overall dissolution rate is the key to predict the stability of waste forms quantitatively. Direct surface measurements by vertical scanning interferometry (VSI) and their analysis via material flux maps and resulting dissolution rate spectra provide data about dominant rate contributors and their variability over time. Using pyrochlore (Nd2Zr2O7) pellet dissolution under acidic conditions as an example, we demonstrate the identification and quantification of dissolution rate contributors, based on VSI data and rate spectrum analysis. Heterogeneous surface alteration of pyrochlore varies by a factor of about 5 and additional material loss by chemo-mechanical grain pull-out within the uppermost grain layer. We identified four different rate contributors that are responsible for the observed dissolution rate range of single grains. Our new concept offers the opportunity to increase our mechanistic understanding and to predict quantitatively the alteration of ceramic waste forms.

Mechanical behavior of 2G REBCO HTS at 77 and 300 K

El gran esfuerzo realizado durante la última década con el fin de integrar los diferentes materiales superconductores en el campo de los sistemas eléctricos y en otras aplicaciones tecnológicas ha dado lugar a un campo de investigación amplio y prometedor. El comportamiento eléctrico de los Superconductores de Alta Temperatura (SAT) crítica (masivo y cintas) depende de diferentes parámetros desde su fabricación hasta la aplicación final con imanes o cables. Sin embargo, las aplicaciones prácticas de estos materiales están fuertemente vinculadas con su comportamiento mecánico tanto a temperatura ambiente (manipulación durante fabricación o instalación) como a temperaturas criogénicas (condiciones de servicio). En esta tesis se ha estudiado el comportamiento mecánico de materiales masivos y cintas de alta temperatura crítica a 300 y 77 K (utilizando nitrógeno líquido). Se han obtenido la resistencia en flexión, la tenacidad de fractura y la resistencia a tracción a la temperatura de servicio y a 300 K. Adicionalmente, se ha medido la dureza mediante el ensayo Vickers y nanoindentación. El módulo Young se midió mediante tres métodos diferentes: 1) nanoindentación, 2) ensayos de flexión en tres puntos y 3) resonancia vibracional mediante grindosonic. Para cada condición de ensayo, se han analizado detalladamente las superficies de fractura y los micromecanismos de fallo. Las propiedades mecánicas de los materiales se han comparado con el fin de entender la influencia de las técnicas de procesado y de las características microestructurales de los monocristales en su comportamiento mecánico. Se ha estudiado el comportamiento electromecánico de cintas comerciales superconductoras de YBCO mediante ensayos de tracción y fatiga a 77 y 300 K. El campo completo de deformaciones en la superficie del material se ha obtenido utilizando Correlación Digital de Imágenes (DIC, por sus siglas en inglés) a 300 K. Además, se realizaron ensayos de fragmentación in situ dentro de un microscopio electrónico con el fin de estudiar la fractura de la capa superconductora y determinar la resistencia a cortante de la intercara entre el substrato y la capa cerámica. Se ha conseguido ver el proceso de la fragmentación aplicando tensión axial y finalmente, se han implementado simulaciones mediante elementos finitos para reproducir la delaminación y el fenómeno de la fragmentación. Por último, se han preparado uniones soldadas entre las capas de cobre de dos cintas superconductoras. Se ha medido la resistencia eléctrica de las uniones con el fin de evaluar el metal de soldadura y el proceso. Asimismo, se ha llevado a cabo la caracterización mecánica de las uniones mediante ensayos "single lap shear" a 300 y 77 K. El efecto del campo magnético se ha estudiado aplicando campo externo hasta 1 T perpendicular o paralelo a la cinta-unión a la temperatura de servicio (77 K). Finalmente, la distribución de tensiones en cada una de las capas de la cinta se estudió mediante simulaciones de elementos finitos, teniendo en cuenta las capas de la cinta mecánicamente más representativas (Cu-Hastelloy-Cu) que influyen en su comportamiento mecánico. The strong effort that has been made in the last years to integrate the different superconducting materials in the field of electrical power systems and other technological applications led to a wide and promising research field. The electrical behavior of High Temperature Superconducting (HTS) materials (bulk and coated conductors) depends on different parameters since their processing until their final application as magnets or cables. However, practical applications of such materials are strongly related with their mechanical performance at room temperature (handling) as well as at cryogenic temperatures (service conditions). In this thesis, the mechanical behavior of HTS bulk and coated conductors was investigated at 300 and 77 K (by immersion in liquid nitrogen). The flexural strength, the fracture toughness and the tensile strength were obtained at service temperature as well as at 300 K. Furthermore, their hardness was determined by Vickers measurements and nanoindentation and the Young's modulus was measured by three different techniques: 1) nanoindentation, 2) three-point bending tests and 3) vibrational resonance with a grindosonic device. The fracture and deformation micromechanics have been also carefully analyzed for each testing condition. The comparison between the studied materials has been performed in order to understand the influence of the main sintering methods and the microstructural characteristics of the single grains on the macroscopic mechanical behavior. The electromechanical behavior of commercial YBCO coated conductors was studied. The mechanical behavior of the tapes was studied under tensile and fatigue tests at 77 and 300 K. The complete strain field on the surface of the sample was obtained by applying Digital Image Correlation (DIC) at 300 K. Addionally, in situ fragmentation tests inside a Scanning Electron Microscope (SEM) were carried out in order to study the fragmentation of the superconducting layer and determine the interfacial shear strength between substrate and ceramic layer. The fragmentation process upon loading of the YBCO layer has been observed and finally, Finite Element Simulations were employed to reproduce delamination and fragmentation phenomena. Finally, joints between the stabilizing Cu sides of two coated conductors have been prepared. The electrical resistivity of the joints was measured for the purpose of qualifying the soldering material and evaluating the soldering process. Additionally, mechanical characterization under single lap shear tests at 300 and 77 K has been carried out. The effect of the applied magnetic field has been studied by applying external magnetic field up to 1 T perpendicular and parallel to the tape-joint at service temperature (77 K). Finally, finite element simulations were employed to study the distribution of the stresses in earch layer, taking into account the three mechanically relevant layers of the coated conductor (Cu-Hastelloy-Cu) that affect its mechanical behavior

(Table 1) Crystal sizes of measured samples from the Bush Hill region in the Gulf of Mexico and from ODP Leg 204 at the Hydrate Ridge offshore Oregon

The grain sizes of gas hydrate crystallites are largely unknown in natural samples. Single grains are hardly detectable with electron or optical microscopy. For the first time, we have used high-energy synchrotron diffraction to determine grain sizes of six natural gas hydrates retrieved from the Bush Hill region in the Gulf of Mexico and from ODP Leg 204 at the Hydrate Ridge offshore Oregon from varying depth between 1 and 101 metres below seafloor. High-energy synchrotron radiation provides high photon fluxes as well as high penetration depth and thus allows for investigation of bulk sediment samples. Gas hydrate grain sizes were measured at the Beam Line BW 5 at the HASYLAB/Hamburg. A 'moving area detector method', originally developed for material science applications, was used to obtain both spatial and orientation information about gas hydrate grains within the sample. The gas hydrate crystal sizes appeared to be (log-)normally distributed in the natural samples. All mean grain sizes lay in the range from 300 to 600 µm with a tendency for bigger grains to occur in greater depth. Laboratory-produced methane hydrate, aged for 3 weeks, showed half a log-normal curve with a mean grain size value of c. 40 µm. The grains appeared to be globular shaped.

Chemical composition of plagioclase from DSDP Legs 45 and 46, Atlantic Ocean

Phyric basalts recovered from DSDP Legs 45 and 46 contain abundant plagioclase phenocrysts which occur as either discrete single grains (megacrysts) or aggregates (glomerocrysts) and which are too abundant and too anorthitic to have crystallized from a liquid with the observed bulk rock composition. Almost all the plagioclase crystals are complexly zoned. In most cases two abrupt and relatively large compositional changes associated with continuous internal morphologic boundaries divide the plagioclase crystals into three parts: core, mantle and rim. The cores exhibit two major types of morphology: tabular, with a euhedral to slightly rounded outline; or a skeletal inner core wrapped by a slightly rounded homogeneous outer core. The mantle region is characterized by a zoning pattern composed of one to several spikes/plateaus superimposed on a gently zoned base line, with one large plateau always at the outside of the mantle, and by, in most cases, a rounded internal morphology. The inner rim is typically oscillatory zoned. The width of the outer rim can be correlated with the position of the individual crystal in the basalt pillow. The presence of a skeletal inner core and the concentration of glass inclusions in low-An zones in the mantle region suggest that the liquid in which these parts of the crystals were growing was undercooled some amount. The resorption features at the outer margins of low-An zones indicate superheating of the liquid with respect to the crystal. It is proposed that the plagioclase cores formed during injection of primitive magma into a previously existing magma chamber, that the mantle formed during mixing of a partially mixed magma and the remaining magma already in the chamber, and that the inner rim formed when the mixed magma was in a sheeted dike system. The large plateau at the outside of the mantle may have formed during the injection of the next batch of primitive magma into the main chamber, which may trigger an eruption. This model is consistent with fluid dynamic calculations and geochemically based magma mixing models, and is suggested to be the major mechanism for generating the disequilibrium conditions in the magma.

Particle positions of numerical experiments 1 to 4

In mixed sediment beds, erosion resistance can change relative to that of beds composed of a uniform sediment because of varying textural and/or other grain-size parameters, with effects on pore water flow that are difficult to quantify by means of analogue techniques. To overcome this difficulty, a three-dimensional numerical model was developed using a finite difference method (FDM) flow model coupled with a distinct element method (DEM) particle model. The main aim was to investigate, at a high spatial resolution, the physical processes occurring during the initiation of motion of single grains at the sediment-water interface and in the shallow subsurface of simplified sediment beds under different flow velocities. Increasing proportions of very fine sand (D50=0.08 mm) were mixed into a coarse sand matrix (D50=0.6 mm) to simulate mixed sediment beds, starting with a pure coarse sand bed in experiment 1 (0 wt% fines), and proceeding through experiment 2 (6.5 wt% fines), experiment 3 (10.5 wt% fines), and experiment 4 (28.7 wt% fines). All mixed beds were tested for their erosion behavior at predefined flow velocities varying in the range of U 1-5=10-30 cm/s. The experiments show that, with increasing fine content, the smaller particles increasingly fill the spaces between the larger particles. As a consequence, pore water inflow into the sediment is increasingly blocked, i.e., there is a decrease in pore water flow velocity and, hence, in the flow momentum available to entrain particles. These findings are portrayed in a new conceptual model of enhanced sediment bed stabilization.