Calcite saturation and yield and Mg/Ca, Mn/Ca, Al/Ca, Fe/Ca for four species of planktic foraminifera cleaned using Mg-cleaning and Cd-cleaning methods

Four species of planktic foraminifera from core-tops spanning a depth transect on the Ontong Java Plateau were prepared for Mg/Ca analysis both with (Cd-cleaning) and without (Mg-cleaning) a reductive cleaning step. Reductive cleaning caused etching of foraminiferal calcite, focused on Mg-rich inner calcite, even on tests which had already been partially dissolved at the seafloor. Despite corrosion, there was no difference in Mg/Ca of Pulleniatina obliquiloculata between cleaning methods. Reductive cleaning decreased Mg/Ca by an average (all depths) of ~ 4% for Globigerinoides ruber white and ~ 10% for Neogloboquadrina dutertrei. Mg/Ca of Globigerinoides sacculifer (above the calcite saturation horizon only) was 5% lower after reductive cleaning. The decrease in Mg/Ca due to reductive cleaning appeared insensitive to preservation state for G. ruber, N. dutertrei and P. obliquiloculata. Mg/Ca of Cd-cleaned G. sacculifer appeared less sensitive to dissolution than that of Mg-cleaned. Mg-cleaning is adequate, but SEM and contaminants (Al/Ca, Fe/Ca and Mn/Ca) show that Cd-cleaning is more effective for porous species. A second aspect of the study addressed sample loss during cleaning. Lower yield after Cd-cleaning for G. ruber, G. sacculifer and N. dutertrei confirmed this to be the more aggressive method. Strongest correlations between yield and Delta[CO3^2-] in core-top samples were for Cd-cleaned G. ruber (r = 0.88, p = 0.020) and Cd-cleaned P. obliquiloculata (r = 0.68, p = 0.030). In a down-core record (WIND28K) correlation, r, between yield values > 30% and dissolution index, XDX, was -0.61 (p = 0.002). Where cleaning yield < 30% most Mg-cleaned Mg/Ca values were biased by dissolution.

Continuum models of the mechanical behavior of rolled and die-cast magnesium alloys

En los últimos años ha habido una fuerte tendencia a disminuir las emisiones de CO2 y su negativo impacto medioambiental. En la industria del transporte, reducir el peso de los vehículos aparece como la mejor opción para alcanzar este objetivo. Las aleaciones de Mg constituyen un material con gran potencial para el ahorro de peso. Durante la última década se han realizado muchos esfuerzos encaminados a entender los mecanismos de deformación que gobiernan la plasticidad de estos materiales y así, las aleaciones de Mg de colada inyectadas a alta presión y forjadas son todavía objeto de intensas campañas de investigación. Es ahora necesario desarrollar modelos que contemplen la complejidad inherente de los procesos de deformación de éstos. Esta tesis doctoral constituye un intento de entender mejor la relación entre la microestructura y el comportamiento mecánico de aleaciones de Mg, y dará como resultado modelos de policristales capaces de predecir propiedades macro- y microscópicas. La deformación plástica de las aleaciones de Mg está gobernada por una combinación de mecanismos de deformación característicos de la estructura cristalina hexagonal, que incluye el deslizamiento cristalográfico en planos basales, prismáticos y piramidales, así como el maclado. Las aleaciones de Mg de forja presentan texturas fuertes y por tanto los mecanismos de deformación activos dependen de la orientación de la carga aplicada. En este trabajo se ha desarrollado un modelo de plasticidad cristalina por elementos finitos con el objetivo de entender el comportamiento macro- y micromecánico de la aleación de Mg laminada AZ31 (Mg-3wt.%Al-1wt.%Zn). Este modelo, que incorpora el maclado y tiene en cuenta el endurecimiento por deformación debido a las interacciones dislocación-dislocación, dislocación-macla y macla-macla, predice exitosamente las actividades de los distintos mecanismos de deformación y la evolución de la textura con la deformación. Además, se ha llevado a cabo un estudio que combina difracción de electrones retrodispersados en tres dimensiones y modelización para investigar el efecto de los límites de grano en la propagación del maclado en el mismo material. Ambos, experimentos y simulaciones, confirman que el ángulo de desorientación tiene una influencia decisiva en la propagación del maclado. Se ha observado que los efectos no-Schmid, esto es, eventos de deformación plástica que no cumplen la ley de Schmid con respecto a la carga aplicada, no tienen lugar en la vecindad de los límites de baja desorientación y se hacen más frecuentes a medida que la desorientación aumenta. Esta investigación también prueba que la morfología de las maclas está altamente influenciada por su factor de Schmid. Es conocido que los procesos de colada suelen dar lugar a la formación de microestructuras con una microporosidad elevada, lo cuál afecta negativamente a sus propiedades mecánicas. La aplicación de presión hidrostática después de la colada puede reducir la porosidad y mejorar las propiedades aunque es poco conocido su efecto en el tamaño y morfología de los poros. En este trabajo se ha utilizado un enfoque mixto experimentalcomputacional, basado en tomografía de rayos X, análisis de imagen y análisis por elementos finitos, para la determinación de la distribución tridimensional (3D) de la porosidad y de la evolución de ésta con la presión hidrostática en la aleación de Mg AZ91 (Mg- 9wt.%Al-1wt.%Zn) colada por inyección a alta presión. La distribución real de los poros en 3D obtenida por tomografía se utilizó como input para las simulaciones por elementos finitos. Los resultados revelan que la aplicación de presión tiene una influencia significativa tanto en el cambio de volumen como en el cambio de forma de los poros que han sido cuantificados con precisión. Se ha observado que la reducción del tamaño de éstos está íntimamente ligada con su volumen inicial. En conclusión, el modelo de plasticidad cristalina propuesto en este trabajo describe con éxito los mecanismos intrínsecos de la deformación de las aleaciones de Mg a escalas meso- y microscópica. Más especificamente, es capaz de capturar las activadades del deslizamiento cristalográfico y maclado, sus interacciones, así como los efectos en la porosidad derivados de los procesos de colada. ---ABSTRACT--- The last few years have seen a growing effort to reduce CO2 emissions and their negative environmental impact. In the transport industry more specifically, vehicle weight reduction appears as the most straightforward option to achieve this objective. To this end, Mg alloys constitute a significant weight saving material alternative. Many efforts have been devoted over the last decade to understand the main mechanisms governing the plasticity of these materials and, despite being already widely used, high pressure die-casting and wrought Mg alloys are still the subject of intense research campaigns. Developing models that can contemplate the complexity inherent to the deformation of Mg alloys is now timely. This PhD thesis constitutes an attempt to better understand the relationship between the microstructure and the mechanical behavior of Mg alloys, as it will result in the design of polycrystalline models that successfully predict macro- and microscopic properties. Plastic deformation of Mg alloys is driven by a combination of deformation mechanisms specific to their hexagonal crystal structure, namely, basal, prismatic and pyramidal dislocation slip as well as twinning. Wrought Mg alloys present strong textures and thus specific deformation mechanisms are preferentially activated depending on the orientation of the applied load. In this work a crystal plasticity finite element model has been developed in order to understand the macro- and micromechanical behavior of a rolled Mg AZ31 alloy (Mg-3wt.%Al-1wt.%Zn). The model includes twinning and accounts for slip-slip, slip-twin and twin-twin hardening interactions. Upon calibration and validation against experiments, the model successfully predicts the activity of the various deformation mechanisms and the evolution of the texture at different deformation stages. Furthermore, a combined three-dimensional electron backscatter diffraction and modeling approach has been adopted to investigate the effect of grain boundaries on twin propagation in the same material. Both experiments and simulations confirm that the misorientation angle has a critical influence on twin propagation. Non-Schmid effects, i.e. plastic deformation events that do not comply with the Schmid law with respect to the applied stress, are absent in the vicinity of low misorientation boundaries and become more abundant as misorientation angle increases. This research also proves that twin morphology is highly influenced by the Schmid factor. Finally, casting processes usually lead to the formation of significant amounts of gas and shrinkage microporosity, which adversely affect the mechanical properties. The application of hydrostatic pressure after casting can reduce the porosity and improve the properties but little is known about the effects on the casting’s pores size and morphology. In this work, an experimental-computational approach based on X-ray computed tomography, image analysis and finite element analysis is utilized for the determination of the 3D porosity distribution and its evolution with hydrostatic pressure in a high pressure diecast Mg AZ91 alloy (Mg-9wt.%Al-1wt.%Zn). The real 3D pore distribution obtained by tomography is used as input for the finite element simulations using an isotropic hardening law. The model is calibrated and validated against experimental stress-strain curves. The results reveal that the pressure treatment has a significant influence both on the volume and shape changes of individuals pores, which have been precisely quantified, and which are found to be related to the initial pore volume. In conclusion, the crystal plasticity model proposed in this work successfully describes the intrinsic deformation mechanisms of Mg alloys both at the mesoscale and the microscale. More specifically, it can capture slip and twin activities, their interactions, as well as the potential porosity effects arising from casting processes.

Measuring the critical resolved shear stresses in Mg alloys by instrumented nanoindentation

One of the main limiting factors in the development of new magnesium (Mg) alloys with enhanced mechanical behavior is the need to use vast experimental campaigns for microstructure and property screening. For example, the influence of new alloying additions on the critical resolved shear stresses (CRSSs) is currently evaluated by a combination of macroscopic single-crystal experiments and crystal plasticity finite-element simulations (CPFEM). This time-consuming process could be considerably simplified by the introduction of high-throughput techniques for efficient property testing. The aim of this paper is to propose a new and fast, methodology for the estimation of the CRSSs of hexagonal close-packed metals which, moreover, requires small amounts of material. The proposed method, which combines instrumented nanoindentation and CPFEM modeling, determines CRSS values by comparison of the variation of hardness (H) for different grain orientations with the outcome of CPFEM. This novel approach has been validated in a rolled and annealed pure Mg sheet, whose H variation with grain orientation has been successfully predicted using a set of CRSSs taken from recent crystal plasticity simulations of single-crystal experiments. Moreover, the proposed methodology has been utilized to infer the effect of the alloying elements of an MN11 (Mg–1% Mn–1% Nd) alloy. The results support the hypothesis that selected rare earth intermetallic precipitates help to bring the CRSS values of basal and non-basal slip systems closer together, thus contributing to the reduced plastic anisotropy observed in these alloys

Investigation of the Ti-Al-Cb system as a source of alloys for use at 1200⁰-1800⁰F

"Materials Central, Contract No. AF 33(616)-6125, Project No. 7351."

Evaluation of silicon twinning in hypo-eutectic Al-Si alloys

It is generally accepted that growth of eutectic silicon in aluminium-silicon alloys occurs by a twin plane re-entrant edge (TPRE) mechanism. It has been proposed that modification of eutectic silicon by trace additions occurs due to a massive increase in the twin density caused by atomic effects at the growth interface. In this study, eutectic microstructures and silicon twin densities in samples modified by elemental additions of barium (Ba), calcium (Ca), yttrium (Y) and ytterbium (Yb) (elements chosen due to a near-ideal atomic radii for twinning) in an A356.0 alloy have been determined by optical microscopy, thermal analysis, X-ray diffractometry (XRD) and transmission electron microscopy (TEM). Addition of barium or calcium caused the silicon structure to transform to a fine fibrous morphology, while the addition of yttrium or ytterbium resulted in a refined plate-like eutectic structure. Twin densities in all modified samples are higher than in unmodified alloys, and there are no significant differences between fine fibrous modification (by Ba and Ca) and refined plate-like modification (by Y and Yb). The twin density in all modified samples is less than expected based on the predictions by the impurity induced twining model. Based on these results it is difficult to explain the modification with Ba, Ca, Y and Yb by altered twin densities alone.

Effects of boron-strontium interactions on eutectic modification in Al-10 mass%Si alloys

The effects of boron and strontium interactions on the eutectic silicon in hypoeutectic Al-Si alloys have been studied. Samples were prepared from an AI-I 0 mass%Si base alloy with different Al-B additions, alone and in combination with strontium. In alloys containing no strontium, boron additions do not cause modification of the eutectic silicon, while in strontium containing alloys, boron additions reduce the level of modification of the eutectic silicon. Thermal analysis parameters and eutectic silicon microstructures were investigated with respect to the Sr to B ratio. In order to modify the eutectic silicon, a Sr/B ratio exceeding 0.4 is required.

Effects of boron on eutectic modification of hypoeutectic Al-Si alloys

The effects of boron on the eutectic modification and solidification mode of hypoeutectic Al-Si alloys have been studied adding different boride phases. The results show that boron does not cause modification of the eutectic silicon. Boron-containing samples display eutectic nucleation and growth characteristics similar to that of unmodified alloys. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.