In situ transmission electron microscopy as a toolbox for the emerging science of nanometallurgy.

Potential applications of nanomaterials range from electronics to environmental technology, thus a better understanding of their manufacturing and manipulation is of paramount importance. The present study demonstrates a methodology for the use of metallic nanomaterials as reactants to examine nanoalloying in situ within a transmission electron microscope. The method is further utilised as a starting point of a metallurgical toolbox, e.g. to study subsequent alloying of materials by using a nanoscale-sized chemical reactor for nanometallurgy. Cu nanowires and Au nanoparticles are used for alloying with pure Al, which served as the matrix material in the form of electron transparent lamellae. The results showed that both the Au and Cu nanomaterials alloyed when Al was melted in the transmission electron microscope. However, the eutectic reaction was more pronounced in the Al-Cu system, as predicted from the phase diagram. Interestingly, the mixing of the alloying agents occurred independently of the presence of an oxide layer surrounding the nanowires, nanoparticles, or the Al lamellae while performing the experiments. Overall, these results suggest that transmission electron microscope-based in situ melting and alloying is a valuable lab-on-a-chip technique to study the metallurgical processing of nanomaterials for the future development of advanced nanostructured materials.

Fast differential scanning calorimetry to mimic additive manufacturing processing: specific heat capacity analysis of aluminium alloys.

Eutectic AlSi12, commonly used in casting and in additive manufacturing, is investigated with Fast Differential Scanning Calorimetry to determine the impact of different cooling rates from the liquid state upon the apparent specific heat capacity on subsequent heating. A heat flow correction strategy is developed and refined for the reliable and precise measurement of sample heat flow using chip sensors and assessed by the evaluation of results on pure (99.999%) aluminium. That strategy is then applied to the study of the AlSi12 eutectic alloy, and rate-dependent perturbations in the measured apparent specific heat capacity are discussed in terms of Si supersaturation and precipitation. Several cooling rates were implemented from - 100 to - 30,000 K s-1, and subsequent heating ranged from + 1000 to + 30,000 K s-1. After rapid cooling, a drop in AlSi12 apparent specific heat capacity is found on heating above ~ 400 °C; even at rates of + 10,000 K s-1, a result which has high relevance in metal additive manufacturing where similarly fast temperature cycles are involved. The Literature data, temperature modulated DSC and CALPHAD simulations on the heat capacity of AlSi12 are used to provide comparative context to the results from Fast Differential Scanning Calorimetry.

Characterization of Zr-Containing Dispersoids in Al-Zn-Mg-Cu Alloys by Small-Angle Scattering.

The characterization of Zr-containing dispersoids in aluminum alloys is challenging due to their broad size distribution, low volume fraction, and heterogeneous distribution within the grains. In this work, small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) were compared to scanning electron microscopy (SEM) and transmission electron microscopy (TEM) regarding their capability to characterize Zr-containing dispersoids in aluminum alloys. It was demonstrated that both scattering techniques are suitable tools to characterize dispersoids in a multi-phase industrial 7xxx series aluminum alloy. While SAXS is more sensitive than SANS due to the high electron density of Zr-containing dispersoids, SANS has the advantage of being able to probe a much larger sample volume. The combination of both scattering techniques allows for the verification that the contribution from dispersoids can be separated from that of other precipitate phases such as the S-phase or GP-zones. The size distributions obtained from SAXS, SANS and TEM showed good agreement. The SEM-derived size distributions were, however, found to significantly deviate from those of the other techniques, which can be explained by considering the resolution-limited restrictions of the different techniques.

Irradiation stability and induced ferromagnetism in a nanocrystalline CoCrCuFeNi highly-concentrated alloy.

In the field of radiation damage of crystalline solids, new highly-concentrated alloys (HCAs) are now considered to be suitable candidate materials for next generation fission/fusion reactors due to recently recorded outstanding radiation tolerance. Despite the preliminarily reported extraordinary properties, the mechanisms of degradation, phase instabilities and decomposition of HCAs are still largely unexplored fields of research. Herein, we investigate the response of a nanocrystalline CoCrCuFeNi HCA to thermal annealing and heavy ion irradiation in the temperature range from 293 to 773 K with the objective to analyze the stability of the nanocrystalline HCA in extreme conditions. The results led to the identification of two regimes of response to irradiation: (i) in which the alloy was observed to be tolerant under extreme irradiation conditions and (ii) in which the alloy is subject to matrix phase instabilities. The formation of FeCo monodomain nanoparticles under these conditions is also reported and a differential phase contrast study in the analytical electron-microscope is carried out to qualitatively probe its magnetic properties.

Lean Wrought Magnesium Alloys.

Lean magnesium alloys are considered attractive candidates for easy and economical hot forming. Such wrought alloys, defined here as materials with a maximum alloying content of one atomic or two weight percent, are known to achieve attractive mechanical properties despite their low alloy content. The good mechanical properties and the considerable hardening potential, combined with the ease of processing, make them attractive for manufacturers and users alike. This results in potential uses in a wide range of applications, from rolled or extruded components to temporary biomedical implants. The characteristic behavior of these alloys and the optimal use of suitable alloying elements are discussed and illustrated exemplarily.

Influence of Fe and Mn on the Microstructure Formation in 5xxx Alloys-Part II: Evolution of Grain Size and Texture.

In recent decades, microstructure and texture engineering has become an indispensable factor in meeting the rising demands in mechanical properties and forming behavior of aluminum alloys. Alloying elements, such as Fe and Mn in AlMg(Mn) alloys, affect the number density, size and morphology of both the primary and secondary phases, thus altering the grain size and orientation of the final annealed sheet by Zener pinning and particle stimulated nucleation (PSN). The present study investigates the grain size and texture of four laboratory processed AlMg(Mn) alloys with various Fe and Mn levels (see Part I). Common models for deriving the Zener-limit grain size are discussed in the light of the experimental data. The results underline the significant grain refinement by dispersoids in high Mn alloys and show a good correlation with the Smith-Zener equation, when weighting the volume fraction of the dispersoids with an exponent of 0.33. Moreover, for high Fe alloys a certain reduction in the average grain size is obtained due to pinning effects and PSN of coarse primary phases. The texture analysis focuses on characteristic texture transformations occurring with pinning effects and PSN. However, the discussion of the texture and typical PSN components is only possible in terms of trends, as all alloys exhibit an almost random distribution of orientations.

Influence of Fe and Mn on the Microstructure Formation in 5xxx Alloys-Part I: Evolution of Primary and Secondary Phases.

The increasing demands for Al sheets with superior mechanical properties and excellent formability require a profound knowledge of the microstructure and texture evolution in the course of their production. The present study gives a comprehensive overview on the primary- and secondary phase formation in AlMg(Mn) alloys with varying Fe and Mn additions, including variations in processing parameters such as solidification conditions, homogenization temperature, and degree of cold rolling. Higher Fe alloying levels increase the primary phase fraction and favor the needle-shaped morphology of the constituent phases. Increasing Mn additions alter both the shape and composition of the primary phase particles, but also promote the formation of dispersoids as secondary phases. The size, morphology, and composition of primary and secondary phases is further affected by the processing parameters. The average dispersoid size increases significantly with higher homogenization temperature and large primary particles tend to fragment during cold rolling. The microstructures of the final soft annealed states reflect the important effects of the primary and secondary phase particles on their evolution. The results presented in this paper regarding the relevant secondary phases provide the basis for an in-depth discussion of the mechanisms underlying the microstructure formation, such as Zener pinning, particle stimulated nucleation, and texture evolution, which is presented in Part II of this study.

A Fast and Implantation-Free Sample Production Method for Large Scale Electron-Transparent Metallic Samples Destined for MEMS-Based In Situ S/TEM Experiments.

Microelectromechanical systems (MEMS) are currently supporting ground-breaking basic research in materials science and metallurgy as they allow in situ experiments on materials at the nanoscale within electron microscopes in a wide variety of different conditions such as extreme materials dynamics under ultrafast heating and quenching rates as well as in complex electro-chemical environments. Electron-transparent sample preparation for MEMS e-chips remains a challenge for this technology as the existing methodologies can introduce contaminants, thus disrupting the experiments and the analysis of results. Herein we introduce a methodology for simple and fast electron-transparent sample preparation for MEMS e-chips without significant contamination. The quality of the samples as well as their performance during a MEMS e-chip experiment in situ within an electron microscope are evaluated during a heat treatment of a crossover AlMgZn(Cu) alloy.

Prototypic Lightweight Alloy Design for Stellar-Radiation Environments.

The existing literature data shows that conventional aluminium alloys may not be suitable for use in stellar-radiation environments as their hardening phases are prone to dissolve upon exposure to energetic irradiation, resulting in alloy softening which may reduce the lifetime of such materials impairing future human-based space missions. The innovative methodology of crossover alloying is herein used to synthesize an aluminium alloy with a radiation resistant hardening phase. This alloy-a crossover of 5xxx and 7xxx series Al-alloys-is subjected to extreme heavy ion irradiations in situ within a TEM up to a dose of 1 dpa and major experimental observations are made: the Mg32(Zn,Al)49 hardening precipitates (denoted as T-phase) for this alloy system surprisingly survive the extreme irradiation conditions, no cavities are found to nucleate and displacement damage is observed to develop in the form of black-spots. This discovery indicates that a high phase fraction of hardening precipitates is a crucial parameter for achieving superior radiation tolerance. Based on such observations, this current work sets new guidelines for the design of metallic alloys for space exploration.

Microstructural Change during the Interrupted Quenching of the AlZnMg(Cu) Alloy AA7050.

This study reports on the effect of interrupted quenching on the microstructure and mechanical properties of plates made of the AlZnMg(Cu) alloy AA7050. Rapid cooling from the solution heat treatment temperature is interrupted at temperatures between 100 and 200 °C and continued with a very slow further cooling to room temperature. The final material's condition is achieved without or with subsequent artificial ageing. The results show that an improvement in the strength-toughness trade-off can be obtained by using this method. Interrupted quenching at 125 °C with peak artificial ageing leads to a yield strength increase of 27 MPa (538 MPa to 565 MPa) compared to the reference material at the same fracture toughness level. A further special case is the complete omission of an artificial ageing treatment with interrupted quenching at 200 °C. This heat treatment exhibits an 20% increase in fracture toughness (35 to 42 MPa m-1/2) while retaining a sufficient yield strength of 512 MPa for industrial applications. A detailed characterization of the relevant microstructural parameters like present phases, phase distribution and precipitate-free zones is performed using transmission electron microscopy and atom probe tomography.

Mg-Alloys for Forging Applications-A Review.

Interest in magnesium alloys and their applications has risen in recent years. This trend is mainly evident in casting applications, but wrought alloys are also increasingly coming into focus. Among the most common forming processes, forging is a promising candidate for the industrial production of magnesium wrought products. This review is intended to give a general introduction into the forging of magnesium alloys and to help in the practical realization of forged products. The basics of magnesium forging practice are described and possible problems as well as material properties are discussed. Several alloy systems containing aluminum, zinc or rare earth elements as well as biodegradable alloys are evaluated. Overall, the focus of the review is on the process control and processing parameters, from stock material to finished parts. A discussion of the mechanical properties is included. These data have been comprehensively reviewed and are listed for a variety of magnesium forging alloys.

Ageing Behaviour of Al-Mg-Si Alloys After Cryogenic and Room Temperature Deformation.

The aim of this study is to investigate the effects of cryogenic and room temperature pre-deformation on subsequent artificial ageing of Al-Mg-Si alloys. Naturally aged and pre-aged samples were strained to 5%, 10% and 20% at RT (25 °C) and under liquid nitrogen, and artificially aged at 185 °C. Pre-deformation generally increases ageing kinetics for both the naturally aged and pre-aged alloys, which increase in proportion to the degree of pre-deformation, and which are slightly more pronounced for the cryogenic condition. The peak strength is constant, except for when a low degree of pre-deformation is used, in which case it is slightly reduced. Cryogenically deformed samples show an increased strength and hardness, compared to samples pre-deformed at RT, when subjected to an equal magnitude of strain. This difference is reduced during artificial ageing. Synchrotron measurements reveal that this behaviour can be linked to the greater dislocation density, which is not completely recovered even after prolonged ageing at 185 °C.

Evolution of Microstructure and Texture in Laboratory- and Industrial-Scaled Production of Automotive Al-Sheets.

With the rising importance of aluminum sheets for automotive applications, the influence of microstructure and texture on mechanical properties and on forming behavior has gained re-increased interest in recent years. This paper provides an introduction to the topic and demonstrates the evolution of microstructure and texture in the standard alloys EN AW-5182 and EN AW-6016 for different processing scales. Moreover, strategies for texture and microstructure characterization of automotive Al-sheets are discussed. As the development of alloys or processes usually starts in laboratory facilities, the transferability to the industrial scale of the results thereof is studied. A detailed analysis of the entire processing chain shows good conformity of careful laboratory production with the industrial production concerning microstructure as well as qualitative and quantitative texture evolution for EN AW-5182. While comparable grain sizes can be achieved in final annealed sheets of EN AW-6016, quantitative discrepancies in texture occur between the different production scales for some sample states. The results are discussed in light of the basics of plasticity and recrystallisation including the effect of solutes, primary phases, and secondary phases in the alloys.

Size-dependent diffusion controls natural aging in aluminium alloys.

A key question in materials science is how fast properties evolve, which relates to the kinetics of phase transformations. In metals, kinetics is primarily connected to diffusion, which for substitutional elements is enabled via mobile atomic-lattice vacancies. In fact, non-equilibrium vacancies are often required for structural changes. Rapid quenching of various important alloys, such as Al- or Mg-alloys, results for example in natural aging, i.e. slight movements of solute atoms in the material, which significantly alter the material properties. In this study we demonstrate a size effect of natural aging in an AlMgSi alloy via atom probe tomography with near-atomic image resolution. We show that non-equilibrium vacancy diffusional processes are generally stopped when the sample size reaches the nanometer scale. This precludes clustering and natural aging in samples below a certain size and has implications towards the study of non-equilibrium diffusion and microstructural changes via microscopy techniques.

Influence of Zn and Sn on the Precipitation Behavior of New Al-Mg-Si Alloys.

In this study, we demonstrate how Zn and Sn influence hardening behavior and cluster formation during pre-aging and paint bake treatment in Al-Mg-Si alloys via hardness tests, tensile tests, and atom probe tomography. Compared to the standard alloy, the Sn-modified variant shows reduced cluster size and yield strength in the pre-aged condition. During the paint bake cycle, the clusters start to grow very fast and the alloy exhibits the highest strength increment. This behavior is attributed to the high vacancy binding energy of Sn. Adding Zn increases the formation kinetics and the size of Mg-Si co-clusters, generating higher yield strength values for both the pre-aged and paint baked conditions. Simultaneous addition of Zn and Sn creates a synergistic effect and produces an alloy that exhibits moderate strength (and good formability) in the pre-aged condition and accelerated hardening behavior during the paint bake cycle.

Exceptional Strengthening of Biodegradable Mg-Zn-Ca Alloys through High Pressure Torsion and Subsequent Heat Treatment.

In this study, two biodegradable Mg-Zn-Ca alloys with alloy content of less than 1 wt % were strengthened via high pressure torsion (HPT). A subsequent heat treatment at temperatures of around 0.45 Tm led to an additional, sometimes even larger increase in both hardness and tensile strength. A hardness of more than 110 HV and tensile strength of more than 300 MPa were achieved in Mg-0.2Zn-0.5Ca by this procedure. Microstructural analyses were conducted by scanning and transmission electron microscopy (SEM and TEM, respectively) and atom probe tomography (APT) to reveal the origin of this strength increase. They indicated a grain size in the sub-micron range, Ca-rich precipitates, and segregation of the alloying elements at the grain boundaries after HPT-processing. While the grain size and segregation remained mostly unchanged during the heat treatment, the size and density of the precipitates increased slightly. However, estimates with an Orowan-type equation showed that precipitation hardening cannot account for the strength increase observed. Instead, the high concentration of vacancies after HPT-processing is thought to lead to the formation of vacancy agglomerates and dislocation loops in the basal plane, where they represent particularly strong obstacles to dislocation movement, thus, accounting for the considerable strength increase observed. This idea is substantiated by theoretical considerations and quenching experiments, which also show an increase in hardness when the same heat treatment is applied.

Effect of Thermal Treatments on Sn-Alloyed Al-Mg-Si Alloys.

Sn-alloying, by deploying comparatively high vacancy binding energy, mitigates the undesired natural aging behavior of 6xxx-alloys. Targeted selection of pre-aging parameters can have a positive influence on natural aging and paint-bake performance. In this study, we aimed to combine the two approaches of Sn-alloying and pre-aging. Our results indicate that alloys modified with 100 at.-ppm Sn require altered heat treatment. In terms of solution aging and quenching, we show that the cooling rate needed depends on the types of alloy. The rate must be adapted, according to the number of intermetallic particles, to guarantee a sufficiently high level of Sn atoms in solid solution. The rather high number of intermetallic phases in alloy EN-AW-6061 means that it requires fast quenching, while the comparatively low number of precipitate-forming elements in alloy EN-AW-6016 makes it less sensitive to quenching variations. We also show that Sn reduces pre-aging kinetics. The optimal pre-aging temperature and time were consequently found to increase when Sn is added. We also studied the effect of adding a further thermal spike to the usual long-term pre-aging, at different positions within the processing route. The results we present are discussed based on a simulation of vacancy evolution in the alloy when subjected to these treatments.

Effect of Compositional and Processing Variations in New 5182-Type AlMgMn Alloys on Mechanical Properties and Deformation Surface Quality.

Laboratory-scale sheets of 5182-type AlMgMn alloys with varying Mg and Mn contents and additions of different amounts of Zn, Cu, Zr and Er were studied. The sheets were produced using two different cold-rolling degrees and two soft-annealing treatment procedures: air-circulated furnace annealing at 370 °C with subsequent furnace cooling, and salt-bath annealing with subsequent water quenching. Mechanical properties and deformation surface quality were studied via tensile tests with simultaneous visual surface characterization. The influence of the chemical composition and the processing route on grain size, mechanical properties, and surface quality is discussed in the study. A reduction in the Mg content improves the surface quality after plastic deformation, but at the expense of the mechanical properties. The results suggest the presence of an optimum Mn content in terms of optical appearance and mechanical properties. Adding Zr largely inhibits recrystallization, which is reflected in a textured microstructure. Adding Er affects neither the surface quality nor the mechanical properties. Specific combinations of Zn or Cu addition, cold-rolling degree, and heat treatment generate significant improvements in the mechanical and optical properties. In general, annealing at high temperature with subsequent quenching leads to enhanced surface quality and mechanical properties, and adding Zn enables further noteworthy improvements.

Property Criteria for Automotive Al-Mg-Si Sheet Alloys.

In this study, property criteria for automotive Al-Mg-Si sheet alloys are outlined and investigated in the context of commercial alloys AA6016, AA6005A, AA6063 and AA6013. The parameters crucial to predicting forming behavior were determined by tensile tests, bending tests, cross-die tests, hole-expansion tests and forming limit curve analysis in the pre-aged temper after various storage periods following sheet production. Roping tests were performed to evaluate surface quality, for the deployment of these alloys as an outer panel material. Strength in service was also tested after a simulated paint bake cycle of 20 min at 185 °C, and the corrosion behavior was analyzed. The study showed that forming behavior is strongly dependent on the type of alloy and that it is influenced by the storage period after sheet production. Alloy AA6016 achieves the highest surface quality, and pre-ageing of alloy AA6013 facilitates superior strength in service. Corrosion behavior is good in AA6005A, AA6063 and AA6016, and only AA6013 shows a strong susceptibility to intergranular corrosion. The results are discussed below with respect to the chemical composition, microstructure and texture of the Al-Mg-Si alloys studied, and decision-making criteria for appropriate automotive sheet alloys for specific applications are presented.