Microstructural Evolution in a 6060 Extrudable Al-Alloy: Integrated Modeling and Experimental Validation.

Desirable properties including strength, ductility and extrudability of 6060 Al-alloys are highly dependent on processing to control the development of microstructural features. In this study, the process chain of an extrudable 6060 Al-alloy was modeled in an Integrated Computational Materials Engineering framework and validated experimentally via quantitative SEM-EDX and TEM. All critical processing stages were considered including casting, homogenization heating and holding, extrusion cooling and two-stage aging. Segregation and intermetallics formation were accurately predicted and experimentally verified in the as-cast condition. Diffusion simulations predicted the dissolution of intermetallics and completion of ß-AlFeSi to α-AlFeSi transformation during homogenization, in excellent agreement with quantitative SEM-EDX characterization. Precipitation simulations predicted the development of a ß″ strengthening dispersion during extrusion cooling and aging. Needle-shaped ß″ precipitates were observed and analyzed with quantitative high-resolution TEM, validating predictions. Ensuing precipitation strengthening was modeled in terms of aging time, presenting good agreement with yield strength measurements. Precipitate-Free Zones and coarse, metastable ß-type particles on dispersoids and grain boundaries were investigated. The proposed integrated modeling and characterization approach considers all critical processing stages and could be used to optimize processing of extrudable 6xxx Al-alloys, providing insight to mechanisms controlling microstructural evolution and resulting properties.

On the Use of a Cluster Identification Method and a Statistical Approach for Analyzing Atom Probe Tomography Data for GP Zones in Al-Zn-Mg(-Cu) Alloys.

Early-stage clustering in two Al-Mg-Zn(-Cu) alloys has been investigated using atom probe tomography and transmission electron microscopy. Cluster identification by the isoposition method and a statistical approach based on the pair correlation function have both been applied to estimate the cluster size, composition, and volume fraction from atom probe data sets. To assess the accuracy of the quantification of clusters of different mean sizes, synthesized virtual data sets were used, accounting for a simulated degraded spatial resolution. The quality of the predictions made by the two complementary methods is discussed, considering the experimental and simulated data sets.

Atomic Structure of Hardening Precipitates in Al-Mg-Si Alloys: Influence of Minor Additions of Cu and Zn.

Shifting toward sustainability and low carbon emission necessitates recycling. Aluminum alloys can be recycled from postconsumer scrap with approximately 5% of the energy needed to produce the same amount of primary alloys. However, the presence of certain alloying elements, such as copper and zinc, as impurities in recycled Al-Mg-Si alloys is difficult to avoid. This work has investigated the influence of tiny concentrations of Cu (0.05 wt %) and Zn (0.06 wt %), individually and in combination, on the precipitate crystal structures in Al-Mg-Si alloys in peak aged and overaged conditions. To assess whether such concentrations can affect the hardening precipitate structures, atomic resolution high-angle annular dark-field scanning transmission electron microscopy and atom probe tomography were adopted. The results indicate that low levels of Cu or Zn have a significant influence. Both elements showed a relatively high tendency to incorporate into precipitate structures, where Cu occupies specific atomic sites, creating its own local atomic configurations. However, Zn exhibited distinct behavior through the formation of extended local areas with 2-fold symmetry and mirror planes, not previously observed in precipitates in Al-Mg-Si alloys. Incorporation of Cu and/or Zn will influence the precipitates' electrochemical potential relative to matrix- and precipitate-free zones and thus the corrosion resistance. Furthermore, the presence of Cu/Zn structures (e.g., ß'Cu, Q'/C) enhances the thermal stability of these precipitates and, accordingly, the mechanical properties of the material. The results obtained from this work are highly relevant to the topic of recycling of aluminum alloys, where accumulation of certain alloying elements is almost unavoidable; thus, tight compositional control might be critical to avoid quality degradation.

AutomAl 6000: Semi-automatic structural labelling of HAADF-STEM images of precipitates in Al-Mg-Si(-Cu) alloys.

When the Al-Mg-Si(-Cu) alloy system is subjected to age hardening, different types of precipitates nucleate depending on the composition and thermomechanical treatment. The main hardening precipitates extend as needles, laths or rods along the <100> directions in the aluminium matrix. It has been found that the structures of all metastable precipitates may be generalized as stacks of <100> columns, where most of these columns are replaced by solute elements. In the precipitates, a column relates to neighbour columns by a set of simple structural principles, which allows identification of species and relative longitudinal displacement over the (100) cross-section. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) is an important tool for studying such precipitates. With the goal of analysing atomic resolution HAADF-STEM images of precipitate cross-sections in the Al-Mg-Si(-Cu) system, we have developed the stand-alone software AutomAl 6000, which features a column characterization algorithm based on the symbiosis of a statistical model and the structural principles formulated in a digraph-like framework. The software can semi-autonomously determine the 3D column positions in the image, as well as column species. In turn, AutomAl 6000 can then display, analyse and/or export the structure data. This paper describes the methodology of AutomAl 6000 and applies it on three different HAADF-STEM images, which demonstrate the methodology. The software, as well as other resources, are available at http://automal.org. The source code is also directly available from https://github.com/Haawk666/AutomAl-6000.

Data on atomic structures of precipitates in an Al-Mg-Cu alloy studied by high resolution transmission electron microscopy and first-principles calculations.

The dataset refers to the research article "Precipitation processes and structural evolutions of various GPB zones and two types of S phases in a cold-rolled Al-Mg-Cu alloy" [1]. Transmission electron microscopy (TEM) and density functional theory (DFT) were used to investigate precipitates in an Al-Cu-Mg alloy aged at 443 K for various times. High-angle annular dark-field scanning TEM (HAADF-STEM) images in <100> Al orientations were analyzed. Characteristic contrast and symmetries of columns [2] yielded atoms and positions, used to build precipitate models which could be refined and compared with solid solution reference energies. A calculation cell is an Al supercell compatible with symmetry and morphology of a precipitate, which is fully or partly surrounded by Al, allowing periodicity continuation via neighbor cells. The given crystallographic data include two S-phase variants and Guinier-Preston-Bagaryatsky (GPB) zones, of which the "GPBX" is new.

Atomic-resolution chemical mapping of ordered precipitates in Al alloys using energy-dispersive X-ray spectroscopy.

Scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray spectroscopy (EDS) is a common technique for chemical mapping in thin samples. Obtaining high-resolution elemental maps in the STEM is jointly dependent on stepping the sharply focused electron probe in a precise raster, on collecting a significant number of characteristic X-rays over time, and on avoiding damage to the sample. In this work, 80kV aberration-corrected STEM-EDS mapping was performed on ordered precipitates in aluminium alloys. Probe and sample instability problems are handled by acquiring series of annular dark-field (ADF) images and simultaneous EDS volumes, which are aligned and non-rigidly registered after acquisition. The summed EDS volumes yield elemental maps of Al, Mg, Si, and Cu, with sufficient resolution and signal-to-noise ratio to determine the elemental species of each atomic column in a periodic structure, and in some cases the species of single atomic columns. Within the uncertainty of the technique, S and ß" phases were found to have pure elemental atomic columns with compositions Al2CuMg and Al2Mg5Si4, respectively. The Q' phase showed some variation in chemistry across a single precipitate, although the majority of unit cells had a composition Al6Mg6Si7.2Cu2.

Elemental electron energy loss mapping of a precipitate in a multi-component aluminium alloy.

The elemental distribution of a precipitate cross section, situated in a lean Al-Mg-Si-Cu-Ag-Ge alloy, has been investigated in detail by electron energy loss spectroscopy (EELS) and aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). A correlative analysis of the EELS data is connected to the results and discussed in detail. The energy loss maps for all relevant elements were recorded simultaneously. The good spatial resolution allows elemental distribution to be evaluated, such as by correlation functions, in addition to being compared with the HAADF image. The fcc-Al lattice and the hexagonal Si-network within the precipitates were resolved by EELS. The combination of EELS and HAADF-STEM demonstrated that some atomic columns consist of mixed elements, a result that would be very uncertain based on one of the techniques alone. EELS elemental mapping combined with a correlative analysis have great potential for identification and quantification of small amounts of elements at the atomic scale.

Germanium network connecting precipitates in an Mg-rich Al-Mg-Ge alloy.

Precipitates in an Al-0.87Mg-0.43Ge (at.%) alloy, heat-treated for 16 h at 200 degrees C, were investigated by transmission electron microscopy and annular dark-field scanning transmission electron microscopy (ADF-STEM). Earlier studies of Al-Mg-Si-(Cu) have shown that an Si network exists within all precipitates. Here, it was investigated whether the heavier, more easily detectable germanium atom would behave similarly. The precipitates were more similar to those found in Al-Mg-Si-Cu alloys with a high fraction of disordered phases than to ternary Al-Mg-Si. All precipitate cross-sections along [001]Al imaged by ADF-STEM showed that Ge atoms arrange in triangular columns separated by approximately 0.4 nm. Along these columns, the precipitate's 0.405-nm periodicity and coherency (along its needle axis) imply a Ge plane periodicity of 0.405 nm. A germanium network, therefore, exists in all precipitates in this alloy, with a hexagonal sub-cell (SC) a = b approximately 0.4 nm, c = 0.405 nm, which is very similar to the Si network in Al-Mg-Si-(Cu). The network always appears as ordered. Disorder in a precipitate must, therefore, be caused by the other atoms in the structure between Ge atoms. One difference between precipitates of the ternary systems Al-Mg-Ge and Al-Mg-Si is the orientation of the diamond element network (SC) base in {001}Al. In Al-Mg-Ge, a <100>SC edge falls along <100>Al. This coincides with the orientation in some precipitates in quaternary Al-Mg-Si-Cu. In ternary Al-Mg-Si, one SC base is parallel with a <510>Al direction.

Single-walled and multi-walled carbon nanotubes promote allergic immune responses in mice.

The adjuvant effect of particles on allergic immune responses has been shown to increase with decreasing particle size and increasing particle surface area. Like ultrafine particles, carbon nanotubes (CNTs) have nano-sized dimensions and a large relative surface area and might thus increase allergic responses. Therefore, we examined whether single-walled (sw) and multi-walled (mw) CNTs have the capacity to promote allergic responses in mice, first in an sc injection model and thereafter in an intranasal model. Balb/cA mice were exposed to three doses of swCNT, mwCNT, as well as ultrafine carbon black particles (ufCBPs, Printex90) during sensitization with the allergen ovalbumin (OVA). Five days after an OVA booster, OVA-specific IgE, IgG1, and IgG2a antibodies in serum and the numbers of inflammatory cells and cytokine levels in bronchoalveolar lavage fluid (BALF) were determined. Furthermore, ex vivo OVA-induced cytokine release from mediastinal lymph node (MLN) cells was measured. In separate experiments, differential cell counts were determined in BALF 24 h after a single intranasal exposure to the particles in the absence of allergen. We demonstrate that both swCNT and mwCNT together with OVA strongly increased serum levels of OVA-specific IgE, the number of eosinophils in BALF, and the secretion of Th2-associated cytokines in the MLN. On the other hand, only mwCNT and ufCBP with OVA increased IgG2a levels, neutrophil cell numbers, and tumor necrosis factor-alpha and monocyte chemoattractant protein-1 levels in BALF, as well as the acute influx of neutrophils after exposure to the particles alone. This study demonstrates that CNTs promote allergic responses in mice.

Quantification of small, convex particles by TEM.

It is shown how size distributions of arbitrarily oriented, convex, non-overlapping particles extracted from conventional transmission electron microscopy (TEM) images may be determined by a variation of the Schwartz-Saltykov method. In TEM, particles cut at the surfaces have diminished projections, which alter the observed size distribution. We represent this distribution as a vector and multiply it with the inverse of a matrix comprising thickness-dependent Scheil or Schwartz-Saltykov terms. The result is a corrected size distribution of the projections of uncut particles. It is shown how the real (3D) distribution may be estimated when particle shape is considered. Computer code to generate the matrix is given. A log-normal distribution of spheres and a real distribution of pill-box-shaped dispersoids in an Al-Mg-Si alloy are given as examples. The errors are discussed in detail.