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Corrosion of Commercial Mg–Al Alloys: AZ31B, AM60, and AZ91D

Aqueous corrosion, atmospheric corrosion, and ionic liquid dissolution studies were performed on commercial alloys AZ31B, AM60, and AZ91D and compared with previously reported results for single-phase binary Mg–Al alloys containing similar Al concentrations (αMg-2 at% Al, αMg-5 at% Al, and Mg-8 at% Al). Polarization studies in 0.6 M NaCl were used to characterize the aqueous free corrosion behavior during 20-h free immersion. Accelerated corrosion testing was performed using a rotating-disk electrode which revealed the evolution of an Al-rich mud-cracking and platelet morphology. Atmospheric droplet testing showed rapid pH increases that depended on the Al concentration in the alloy. Time-dependent contact angle measurements showed that the degree of droplet wetting increased during free corrosion by ~50° over 20 h in 0.6 M NaCl. Ionic liquid dissolution studies in 1:2 M choline chloride:urea deep eutectic solvent were performed in order to examine the current-voltage behavior of these alloys in the absence of water and hydrogen reduction. The results of these studies revealed the formation of nanowire corrosion morphologies within a honeycomb lattice structure which we attribute to selective dissolution of Mg via a two-dimensional stepflow process

25 ENERGY STORAGE↗

Highly deformable Mg–Al–Ca alloy with Al 2 Ca precipitates

Magnesium (Mg) is the lightest structural metal. However, the poor formability of Mg alloys to great extent limits their applications in making structural parts. Formability is strongly correlated to both high tensile elongation and large work hardening capacity. In this work, we report a new Mg-Al-Ca alloy in which a majority of deformable Al 2 Ca precipitates form while the formation of Laves phases of Mg 17 Al 12 and Mg 2 Ca seems suppressed. Al 2 Ca precipitates imped dislocation motion, leading to large work hardening. Then, Al 2 Ca precipitates deform with dislocations and stacking faults under the enhanced flow stress, which relieve local stress concentration and improve tensile elongation. In addition, solutes Al and Ca suppress twin nucleation while promoting non-basal dislocations in Mg. Our Mg-Al-Ca alloy demonstrates one of the highest combinations of tensile elongation and work hardening capacity among existing Mg alloys.

36 MATERIALS SCIENCE↗

Ordering in liquid and its heredity impact on phase transformation of Mg-Al-Ca alloys

It is a long-sought goal to achieve desired mechanical properties through tailoring phase formation in alloys, especially for complicated multi-phase alloys. In fact, unveiling nucleation of competitive crystalline phases during solidification hinges on the nature of liquid. Here we employ ab initio molecular dynamics simulations (AIMD) to reveal liquid configuration of the Mg-Al-Ca alloys and explore its effect on the transformation of Ca-containing Laves phase from Al 2 Ca to Mg 2 Ca with increasing Ca/Al ratio (r Ca/Al ). There is structural similarity between liquid and crystalline phase in terms of the local arrangement environment, and the connection schemes of polyhedras. The forming signature of Mg 2 Ca, as hinted by the topological and chemical short-range order originating from liquid, ascends monotonically with increasing r Ca/Al . However, Al 2 Ca crystal-like order increase at first and then decrease at the crossover of r Ca/Al = 0.74, corresponding to experimental composition of phase transition from Al 2 Ca to Mg 2 Ca. The origin of phase transformation across different compositions lies in the dense packing of atomic configurations and preferential bonding of chemical species in both liquid and solid. The present finding provides a feasible scenario for manipulating phase formation to achieve high performance alloys by tailoring the crystal-like order in liquid.

36 MATERIALS SCIENCE↗

Exploring the Microstructure-Property Relationship of Mg-Al-Mn alloys enhanced via Friction Stir Processing

Friction Stir Processing (FSP) is a solid-state thermomechanical processing technique that enables local grain refinement, densification, and homogenization of microstructure in metallic components. Here, FSP is applied to thin sheets of high-pressure die cast AM60 to address the porosity and heterogeneities inherent to the casting process. In this work, microstructure characterization is correlated to improvements in the static mechanical properties of the Mg-Al-Mn alloy system at various FSP processing conditions. Notably, there is a significant increase in the ductility and ultimate tensile stress of system following FSP. The dominant deformation mechanisms for the as-cast material and the FSP material are investigated. Finally, the fatigue life improvement is correlated to microstructure modifications that may lead to distinct behavior in crack initiation and crack propagation for the as-cast and FSP material.

Garcia, David↗

Investigating Uranium Corrosion in Magnesium-containing Sludge Using X-ray Tomography - 20042

One of the current primary concerns within the British nuclear community is the decommissioning of legacy storage ponds in Sellafield Cumbria, where nuclear fuel cladding material (a Mg-Al alloy) resides along with fuel metallic swarf. Corrosion of the immersed metallic elements, which has been occurring over the storage period, has resulted in the formation of what is commonly known as Corroded Magnox Sludge. The behaviour of uranium metal within this particular environment and, more significantly, the identity of the corrosion products that may have formed is currently unknown. The present study attempts to shed some light on these aspects by investigating simplified surrogate systems, mimicking storage ponds. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Investigation of grain size and geometrically necessary dislocation density dependence of flow stress in Mg-4Al by using nanoindentation

Models for grain size dependence of flow stress typically ignore contributions from geometrically necessary dislocations (GNDs) in the grain boundary regions. Ashby had proposed the following equation for flow stress (τ) as a function of grain size (d) and effective plastic strain ($\bar{ε}$): $τ = τ_{0} + C'G\sqrt{^{b\bar{ε}}_{d}}$ using an unknown empirical coefficient, C’, In this study, the coefficient, C’, and equation for the grain size dependence of flow stress were investigated in Mg-4Al using nanoindentation. C’ ranges from 1.4 to 7.11 that is related to the hardness difference (∆H0) between the adjacent grains as $C' + 0.62\sqrt{ΔH_{0}}$. Ashby equation was used to predict uniaxial stress-strain curves in grain sizes of 55 µm, 187 µm, and 333 µm. The results showed lower flow stress and lower hardening rate compared to experimentally measured tensile stress-strain response. The discrepancy seems to be a result of hardening effect of SSDs. Here, we propose a modified Ashby equation that takes into account the hardening effect of SSDs and GNDs separately, resulting in a better agreement between calculated and experimentally measured values. This analysis demonstrates estimation of uniaxial stress-strain response using nanoindentation measurements that captures effects of grain size, and strain hardening from SSDs and GNDs. The combination of the revised equation and nanoindentation method will enable rapid exploration of stress-strain response of a diverse range of single-phase polycrystalline alloys.

36 MATERIALS SCIENCE↗

Quantification of grain boundary effects on the geometrically necessary dislocation density evolution and strain hardening of polycrystalline Mg 4Al using in situ tensile testing in scanning electron microscope and HR-EBSD

In situ tensile testing in a scanning electron microscope (SEM) in conjunction with high-resolution electron backscatter diffraction (HR-EBSD) under load was used to characterize the evolution of geometrically necessary dislocation (GND) densities at individual grain boundaries as a function of applied strain in a polycrystalline Mg—4Al alloy. The increase in GND density was investigated at plastic strains of 0 %, 0.6 %, 2.2 %, 3.3 % from the area including 76 grains and correlated with (i) geometric compatibility between slip systems across grain boundaries, and (ii) plastic incompatibility. We develop expressions for the grain boundary GND density evolution as a function of plastic strain and plastic incompatibility, from which uniaxial tensile stress-strain response of polycrystalline Mg—4Al are computed and compared with experimental measurement. The findings in this study contribute to understanding the mechanisms governing the strain hardening response of single-phase polycrystalline alloys and more reliable prediction of mechanical behaviors in diverse microstructures.

Geometrically necessary dislocations↗

Solid Phase Processing of Mg-Al-Mn-Ca for High Strength and Ductility

While rare-earth Mg alloys have remarkable properties for high strength applications, lower cost alternatives are necessary for the widespread industry use of Mg. Ca added Mg alloys have shown promise as an alternative to rare-earth alloys. Ca-based precipitates can reduce basal texture, reduce casting porosity, and increase mechanical strength. However, the accumulation of Ca-based precipitates along inter-dendritic regions can severely limit ductility. Here, we apply two solid phase processing techniques, friction stir processing and shear assisted processing and extrusion, to produce wrought microstructure sheet and extruded tubes from a cast Mg-Al-Mn-Ca alloy. Ductility of the alloy is enhanced by densification under applied force and elevated temperature, grain refinement, and refinement of (Al,Mg)-Ca based precipitate.

Garcia, David↗

Effect of Oxidizing Impurities on the Corrosion Behavior of Structural Alloys Exposed to MgCl 2 Molten Salt Vapor

The corrosion behavior of structural alloys SS304 and IN617 when exposed to vapors of MgCl 2 molten salt at 764 °C for 100 h in an argon atmosphere was investigated as a function of the level of oxidizing impurities (e.g., NaOH) present in the salt. Increasing the concentration of oxidizing impurities in the salt caused an increase in corrosion in both structural alloys, as measured by Cr depletion layers. A poorly adhered oxide scale layer containing Mg, Al, and Cr was observed on the surface of the metals, and local attack was observed as well. The Ni-based IN617 showed lower Cr depletion and less scale formation than the Fe-based SS304. These results demonstrate that oxidizing impurities in the molten salt will impact the vapor phase corrosion for structural members exposed to the molten salt headspace. This finding is highly relevant for understanding the effects of the vapor phase in molten salt applications, including molten salt thermal energy storage, molten salt nuclear reactors, and molten salt electrochemistry.

25 ENERGY STORAGE↗

A new interatomic potential for mixed Mg-Al-Ga-In spinels

While density functional theory (DFT) has become the de facto approach for accurate simulation of materials at the atomic scale, there are many aspects of materials that are simply out of reach of DFT methods. In particular, finite temperature properties such as diffusivities, the structure and properties of grain boundaries and interfaces, and the study of defect properties in complex alloys are computationally challenging for DFT methods. Recently, a new class of spinels in which three cations order over two sublattices was discovered. In order to predict the properties of these types of structures, classical potentials are a must. Here, in this work, we derive a new classical potential for Mg-bearing spinels in which the B cations are Al, Ga, and/or In. The potential does well in describing the DFT energetics of various spinel structures as a function of chemistry and inversion. In particular, it reproduces the thermodynamically favorable MgAlGaO 4 structure while correctly predicting that neither MgAlInO 4 nor MgGaInO 4 are stable. Further, it reproduces physical trends in elastic properties as compared against experiment.

36 MATERIALS SCIENCE↗

Design of lightweight BCC multi-principal element alloys with enhanced hydrogen storage using a machine learning-driven genetic algorithm

Body-centered cubic (BCC) based multi-principal element alloy (MPEA) hydrides have demonstrated significant potential for compact and efficient hydrogen storage. In this work, we first leverage machine learning (ML) models to predict the hydrogen affinity, storage capacity and phase stability of BCC MPEAs, creating a unique hydrogen-to-metal (H/M) predictor for materials with unprecedented performance. We developed a metaheuristic optimizer high-throughput framework by interfacing ML models with a genetic algorithm for the accelerated search of {Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo} based lightweight BCC MPEAs with improved hydrogen storage characteristics. We report five new MPEAs with a predicted gravimetric hydrogen storage capacity of around 3.5 wt% or more, including Cr 0.09 Mg 0.73 Ti 0.18 (4.25 wt% H) and Cr 0.21 Nb 0.11 Ti 0.35 V 0.33 (3.5 wt% H). The electronic structure of the top-performing composition, Cr 0.09 Mg 0.73 Ti 0.18 , was analyzed using density functional theory (DFT) to understand the reasons for its improved hydrogen storage properties compared to TiFe (1.90 wt% H), LaNi 5 (1.37 wt% H) or BCC MPEAs like TiVNbCr (3.70 wt% H). Temperature-dependent molecular dynamics (MD) studies were further performed on optimized BCC MPEAs to qualitatively study hydrogen mobility and analyze the effect of different elemental composition on bulk hydrogen diffusion. Our findings demonstrate how a ML assisted genetic algorithm framework can be used for efficient search of stable, lightweight and cost-effective MPEAs while minimizing the need for expensive ab initio calculations.

DFT↗

Microstructural basis for improved corrosion resistance of laser surface processed AZ31 Mg alloy

Despite their excellent strength to weight ratio, wider use of Mg alloys for light weighting applications is limited by their poor corrosion resistance, especially in chloride ion-containing environments. The present study shows improved corrosion resistance imparted by laser surface processing (LSP) of a commercial AZ31 (Mg-3Al-1Zn) alloy. Nanosecond laser processing at three different power settings was carried out on the surface of a 1 mm thick rolled AZ31 sheet. Corrosion testing based on ASTM B117 method and several other electrochemical tests indicates substantial enhancement of corrosion resistance in LSP-treated AZ31. The underlying reason behind improved corrosion resistance of LSP-AZ31 surface has been identified using a variety of characterization tools (SEM, TEM, XPS). Formation of a ~0.5 µm thick mixed metal (Mg, Al) oxide surface film together with refinement in the size and number density of Al-Mn intermetallic particles appear to be playing a major role towards improved corrosion resistance after LSP treatment of AZ31 alloy.

Jana, Saumyadeep↗

Irradiation-induced amorphization of UO 2 films prepared by spraying-assisted combustion synthesis

Spraying-assisted combustion synthesis with uranyl nitrate – acetylacetone – 2-methoxyethanol solutions was used to prepare UO 2 films on an aluminum alloy substrate. The tuning of the spraying parameters and annealing temperatures allowed the preparation of UO 2 films with thicknesses varying from 10–300 nm and 5–10 nm UO 2 grain size. High-resolution electron microscopy and X-ray photoelectron spectroscopy showed that increasing the annealing temperature promotes Mg diffusion from the substrate into the films. The incorporation of Mg reduced the overall crystallinity of the films. The irradiation with Ar 2+ ions (1.7 MeV energy and a fluence of 2 × 10 16 ions/cm 2 ) did not degrade the quality of the films. However, the Mg content significantly influenced the irradiation-induced restructuring of the UO 2 films. Irradiated films with low or no Mg content exhibit high crystallinity, and the UO 2 /Al interfacial layer becomes highly porous. Films with higher Mg content are mostly amorphized after irradiation. The origin of irradiation-induced amorphization was related to the formation of Mg y U 1-y O 2±x solid solutions. Chemically complex, pore-free, and amorphous Mg-Al-O film/substrate interfacial layers enable continuous Mg diffusion during irradiation. As a result, the gradual increase in Mg amounts triggers irradiation-induced precipitation of a crystalline MgO-rich phase within the amorphous films.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗