Effect of a plasmaelectrolytic coating on the strength retention of in vivo and in vitro degraded magnesium implants

The strength decrease in magnesium implants was studied in vitro and in vivo, with and without a protective plasmaelectrolytic coating. In vivo, degradation was examined by implanting rectangular plates on top of the nasal bone of miniature pigs. The presence of gas pockets in the soft tissue surrounding the implants was evaluated with intermediate X-rays and computed X-ray tomography scans before euthanasia. After 12 and 24weeks of in vivo degradation, the large rectangular plates were removed and mechanically tested in three-point bending. In vitro, identical plates were immersed in simulated body fluid for 4, 8 and 12weeks. In vitro and in vivo results showed that onset of gas release can be delayed by the plasmaelectrolytic coating. Mass loss and strength retention during in vivo degradation is about four times slower than during in vitro degradation for the chosen test conditions. Despite the slow degradation of the investigated WE43 alloy, the occurrence of gas pockets could not be completely avoided. Nevertheless, uniformity of degradation and reliable strength retention make this alloy a prime candidate for the use of magnesium in cranio-maxillofacial surgery.

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.

Application of chemical thermodynamics to the study of alloy formation, progress report for ...

"Work performed under Contract No. AT(30-1)-647"--p.2 of cover.

Stress corrosion cracking and hydrogen embrittlement of an Al-Zn-Mg-Cu alloy

The age hardening, stress corrosion cracking (SCC) and hydrogen embrittlement (HE) of an Al-Zn-Mg-Cu 7175 alloy were investigated experimentally. There were two peak-aged states during ageing. For ageing at 413 K, the strength of the second peak-aged state was slightly higher than that of the first one, whereas the SCC susceptibility was lower, indicating that it is possible to heat treat 7175 to high strength and simultaneously to have high SCC resistance. The SCC susceptibility increased with increasing Mg segregation at the grain boundaries. Hydrogen embrittlement (HE) increased with increased hydrogen charging and decreased with increasing ageing time for the same hydrogen charging conditions. Computer simulations were carried out of (a) the Mg grain boundary segregation using the embedded atom method and (b) the effect of Mg and H segregation on the grain boundary strength using a quasi-chemical approach. The simulations showed that (a) Mg grain boundary segregation in Al-Zn-Mg-Cu alloys is spontaneous, (b) Mg segregation decreases the grain boundary strength, and (c) H embrittles the grain boundary more seriously than does Mg. Therefore, the SCC mechanism of Al-Zn-Mg Cu alloys is attributed to the combination of HE and Mg segregation induced grain boundary embrittlement. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

On the role of magnesium and nitrogen in the infiltration of aluminium by aluminium for rapid prototyping applications

Selective laser sintering has been used to fabricate an aluminium alloy powder preform which is subsequently debound and infiltrated with a second aluminium alloy. This represents a new rapid manufacturing system for aluminium that can be used to fabricate large, intricate parts. The base powder is an alloy such as AA6061. The infiltrant is a binary or higher-order eutectic based on either Al-Cu or At-Si. To ensure that infiltration occurs without loss of dimensional precision, it is important that a rigid skeleton forms prior to infiltration. This can be achieved by the partial transformation of the aluminium to aluminium nitride. In order for this to occur throughout the component, magnesium powder must be added to the alumina support powder which surrounds the part in the furnace. The magnesium scavenges the oxygen and thereby creates a microclimate in which aluminium nitride can form. The replacement of the ionocovalent Al2O3 with the covalent AlN on the surface of the aluminium powders also facilitates wetting and thus spontaneous and complete infiltration. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Grain coarsening of magnesium alloys by beryllium

A trace of beryllium can lead to dramatic grain coarsening in Mg-Al alloys at normal cooling rates. It is, however, unclear whether this effect applies to aluminium-free magnesium alloys or not. This work shows that a trace of beryllium also causes considerable grain coarsening in Mg-Zn, Mg-Ca, Mg-Ce and Mg-Nd alloys and hinders grain refinement of magnesium alloys by zirconium as well. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A critical review of the stress corrosion cracking (SCC) of magnesium alloys

This review aims to provide a foundation for the safe and effective use of magnesium (Mg) alloys, including practical guidelines for the service use of Mg alloys in the atmosphere and/or in contact with aqueous solutions. This is to provide support for the rapidly increasing use of Mg in industrial applications, particularly in the automobile industry. These guidelines should be firmly based on a critical analysis of our knowledge of SCC based on (1) service experience, (2) laboratory testing and (3) understanding of the mechanism of SCC, as well as based on an understanding of the Mg corrosion mechanism.

The effect of manganese on the grain size of commercial AZ31 alloy

The effect of manganese on gain refinement of a commercial AZ31 alloy has been investigated using an Al-60%Mn master alloy splatter as an alloying additive at 730 degrees C in aluminium titanite crucibles. It is shown that grain refinement by manganese is readily achievable in AZ31. Electron microprobe analyses reveal that prior to the addition of extra manganese the majority of the intermetallic particles found in AZ31 are of the AL(8)Mn(5) type. However, after the addition of extra manganese in the range from 0.1% to 0.8%, the predominant group of intermetallic particles changes to the metastable AlMn type. This leads to a hypothesis that the metastable AlMn intermetallic particles are more effective than Al8Mn5 as nucleation sites for magnesium grains. The hypothesis is supported by the observation that a long period of holding at 730 degrees C leads to an increase in grain size, due probably to the transformation of the metastable AlMn to the stable Al8Mn5. The hypothesis has also been used to understand the mechanism of grain refinement by superheating.

Influence of geometry on galvanic corrosion of AZ91D coupled to steel

The influence of geometric factors on the galvanic current density distribution for AZ91D coupled to steel was investigated using experimental measurements and a BEM model. The geometric factors were area ratio of anode/cathode, insulation distance between anode and cathode, depth of solution film covering the galvanic couple and the manner of interaction caused by two independent interacting galvanic couples. The galvanic current density distribution calculated from the BEM model was in good agreement with the experimental measurements. The galvanic current density distribution caused by the interaction of two independent galvanic couples can be reasonably predicted as the linear addition of the galvanic current density caused by each individual galvanic couple. (c) 2005 Elsevier Ltd. All rights reserved.

Stress corrosion cracking and hydrogen diffusion in magnesium

Evaluation of recent data for hydrogen (H) diffusion in magnesium (Mg) yielded a new equation for the diffusion coefficient of H in Mg. This indicates that there can be significant H transport ahead of a stress corrosion crack in Mg at ambient temperature and that H may be involved in the mechanism of stress corrosion cracking in Mg.

Light alloy castings for automotive applications: The case of Al vs Mg

The economical and environmental effects of mass reduction through Al and Mg primary alloys substitutions for cast iron and steel in automotive components are discussed using MF. Ashby's penalty functions method The viability of Mg alloy substitutions for existing Al alloy cast components is also considered. The cost analysis shows that direct, equal-volume, Al alloy substitutions for cast iron and steel are the most feasible in terms of the CAFE liability, followed by substitutions involving flat panels of prescribed stiffness. When the creation of CO2 associated to the production of Al and Mg is considered, the potential gasoline savings over the lifespan of the car compensate for the intrinsic environmental burden of Al in all applications, while electrolytic Mg substitutions for cast iron and steel are feasible for equal volume and panels only. Magnesium produced by the Pidgeon thermal process appears to be too primary energy intensive to be competitive in structural applications. Magnesium substitutions for existing Al alloy beams and panels are generally unviable. The current higher recycling efficiency of Al casting alloys confers Al a significant advantage over Mg alloys.