Aberration-corrected HAADF-STEM investigations of precipitate structures in Al–Mg–Si alloys with low Cu additions

Precipitates in a lean Al–Mg–Si alloy with low Cu addition (~0.10 wt.%) were investigated by aberration-corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). Most precipitates were found to be disordered on the generally ordered network of Si atomic columns which is common for the metastable precipitate structures. Fragments of known metastable precipitates in the Al–Mg–Si–(Cu) alloy system are found in the disordered precipitates. It was revealed that the disordered precipitates arise as a consequence of coexistence of the Si-network. Cu atomic columns are observed to either in-between the Si-network or replacing a Si-network column. In both cases, Cu is the center in a three-fold rotational symmetry on the Si-network. Parts of unit cells of Q′ phase were observed in the ends of a string-type precipitates known to extend along dislocation lines. It is suggested that the string-types form by a growth as extension of the B′/Q′ precipitates initially nucleated along dislocation lines. Alternating Mg and Si columns form a well-ordered interface structure in the disordered Q′ precipitate. It is identical to the interface of the Q′ parts in the string-type precipitate.     

The effect of Cu on precipitation in Al–Mg–Si alloys

TEM investigations of two alloys isothermally heat treated at 175°C and 260°C show how Cu additions to the Al–Mg–Si system affect precipitation. Both alloys had a solute content Mg?+?Si?=?1.3 at.%, 0.127 at.% Cu, but with Mg/Si 0.8 and 1.25. Cu-containing Guinier-Preston (GP) zones and three types of Q′ precursors are identified as most common phases at peak-hardness conditions, whereas β″ accounts for maximum 30% of the total number of precipitates. The precursors have needle (L and S precipitates) or plate (C precipitate) morphologies. They consist of different arrangements of Al, Mg and Cu atoms on a grid defined by triangularly arranged Si planes parallel with and having the same period as {100} Al planes. The Si grid is composed of nearly hexagonal sub-cells of a?=?b?=?4.05?Å, c?=?4.05?Å. The Cu arrangement on the grid is often disordered in the needle precursors. The plate precursor is ordered, with a monoclinic unit cell of a?=?10.32?Å, b?=?8.1?Å, c?=?4.05?Å, γ?=?101°.     

In-situ study of precipitates in Al–Zn–Mg–Cu alloys using anomalous small-angle x-ray scattering

In the present work,the precipitate compositions and precipitate amounts of these elements(including the size distribution,volume fraction,and inter-precipitate distance) on the Cu-containing 7000 series aluminum alloys(7150 and 7085 Al alloys),are investigated by anomalous small-angle x-ray scattering(ASAXS) at various energies.The scattering intensity of 7150 alloy with T6 aging treatment decreases as the incident x-ray energy approaches the Zn absorption edge from the lower energy side,while scattering intensity does not show a noticeable energy dependence near the Cu absorption edge.Similar results are observed in the 7085 alloy in an aging process(120℃) by employing in-situ ASAXS measurements,indicating that the precipitate compositions should include Zn element and should not be strongly related to Cu element at the early stage after 10 min.In the aging process,the precipitate particles with an initial average size of ~ 8 ?A increase with aging time at an energy of 9.60 ke V,while the increase with a slower rate is observed at an energy of 9.65 ke V as near the Zn absorption edge.     

63Cu NMR analysis of microstructure evolution in Al–Cu–Mg alloys

⁶³Cu NMR spectroscopy has been used to detect metastable Guinier–Preston–Bagaryatsky (GPB) zones and nanoscale precipitates of equilibrium S-phase (Al₂CuMg) in dilute alloys of aluminium containing copper and magnesium with compositions which lie in the α?+?S phase field. The GPB zones are observed to form rapidly at room temperature with a time development closely related to the Vickers hardness. The final development of S-phase in the alloy has been confirmed by the observation of a line shape in the alloy identical to that observed in a specimen prepared from stoichiometric Al₂CuMg. Analysis of the hyperfine structure of the ⁶³Cu line shape observed for S-phase shows clearly that two Cu sites are present with approximately equal population. This result suggests that possibly two crystallographically distinct Al₂CuMg phases are present. The addition of small amounts of silver to Al–Cu–Mg alloys in the α?+?θ phase field is known to induce the formation of Ω-phase: a slight distortion of tetragonal θ-phase Al₂Cu. A hyperfine-structured ⁶³Cu line shape assigned to Ω-phase, indicating one distinct Cu site, has been observed in two separate Al–1.7?at.%?Cu–0.33?at.%?Mg alloys containing 0.1 and 0.18?at.%?Ag, but not in the same Al–Cu–Mg alloy without Ag.     

High-resolution transmission electron microscopy study on reversion of Al2CuMg precipitates in Al–Cu–Mg alloys under irradiation

Image deconvolution analyses showed that reversion of S-Al₂CuMg precipitates occurred in an Al–Cu–Mg alloy during high-resolution transmission electron microscopy observations. A fraction of Mg and Cu atoms in the precipitates diffused into Al matrix due to electron beam irradiation at 300 kV, resulting in structural/chemical reversion of the precipitates. The structural reversion of the S-Al₂CuMg precipitates is closely related with irradiation-induced displacement of atoms. The strong attraction between Cu and Mg atoms might assist the sub-threshold displacement of Cu atoms. One transitional structure is determined to be S′′-Al₁₀Cu₃Mg₃, a precursor of S-Al₂CuMg. Two other transitional structures, Al₃CuMg and Al₁₈Cu₅Mg₅ which have the same lattice parameters of a = c = 0.405 nm as that of S′′-Al₁₀Cu₃Mg₃, but different b values, are suggested.     

The effect of Zn on precipitation in Al–Mg–Si alloys

Effects of addition of Zn (up to 1 wt%) on microstructure, precipitate structure and intergranular corrosion (IGC) in an Al–Mg–Si alloys were investigated. During ageing at 185?°C, the alloys showed modest increases in hardness as function of Zn content, corresponding to increased number densities of needle-shaped precipitates in the Al–Mg–Si alloy system. No precipitates of the Al–Zn–Mg alloy system were found. Using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), the Zn atoms were incorporated in the precipitate structures at different atomic sites with various atomic column occupancies. Zn atoms segregated along grain boundaries, forming continuous film. It correlates to high IGC susceptibility when Zn concentration is ~1wt% and the materials in peak-aged condition.     

Study of ageing in Al–Mg–Si alloys by positron annihilation spectroscopy

In many common Al–Mg–Si alloys (6000 series) intermediate storage at or near ‘room temperature’ after solutionising leads to pronounced changes of the precipitation kinetics during the ensuing artificial ageing step at ≈180 °C. This is not only an annoyance in production, but also a challenge for researchers. We studied the kinetics of natural ‘room temperature’ ageing (NA) in Al–Mg–Si alloys by means of various different techniques, namely electrical resistivity and hardness measurement, thermoanalysis and positron lifetime and Doppler broadening (DB) spectroscopy to identify the stages in which the negative effect of NA on artificial ageing might appear. Positron lifetime measurements were carried out in a fast mode, allowing us to measure average lifetimes in below 1 min. DB measurements were carried out with a single detector and a ⁶⁸Ge positron source by employing high momentum analysis. The various measurements show that NA is much more complex than anticipated and at least four different stages can be distinguished. The nature of these stages cannot be given with certainty, but a possible sequence includes vacancy diffusion to individual solute atoms, nucleation of solute clusters, Mg agglomeration to clusters and coarsening or ordering of such clusters. Positron lifetime measurements after more complex ageing treatments involving storage at 0 °C, 20 °C and 180 °C have also been carried out and help to understand the mechanisms involved.     

Origin of tweed in Au–Cu–Al alloys

The premartensitic tweed in Au–Cu–Al alloys, contrary to previous thought that resort to defects, is confirmed to be associated with the coherent embryos of an intermediate phase (I phase) embedded in parent phase. The parent?→?I phase transformation temperature was measured by differential scanning calorimeter and dynamic mechanical analysers, which shifts from 82.3 to 557.6?°C depending on the alloy composition. X-ray diffraction and transmission electron microscopes (TEM) results show that the parent?→?I phase transformation is a charge density wave transition that cannot be suppressed even by melt-spun method, which shows obvious compositional inhomogeneity between I phase and parent. The results imply that the parent?→?I phase transition is a fast displacive transformation coupled with diffusion. Moreover, accompanying the parent?→?I phase transformation, alloys demonstrate diversified microstructure revealed by TEM observation, from tweed to chessboard nanowires or twins. These findings provide the experimental evidence for that parent?→?I phase transformation in Au–Cu–Al alloys is originated from pseudospinodal decomposition as theoretically predicted.     

Atomistic details of precipitates in lean Al–Mg–Si alloys with trace additions of Ag and Ge studied by HAADF-STEM and DFT

Abstract

Bonding energies and volume misfits for alloying elements and vacancies in multicomponent Al–Mg–Si alloys have been calculated using density functional theory (DFT). A detailed atomic scale analysis has been done for characteristic precipitate structures, using high-angle annular dark-field scanning transmission electron microscopy. Two new stacking configurations of the important strengthening phase β′′ were discovered in the Ge-added alloy. All three stacking variations were found to be energetically favourable to form from DFT calculations. The second stacking configuration, β₂′′, contains vacated columns in its unit cell, consequently requiring less solute to create the same volume fraction of precipitate needles. DFT suggests a lower formation enthalpy per atom for β₂′′ when Si is exchanged with Ge. In the alloy containing Ag additions, a new Q’/C-like local configuration containing Ag instead of Cu was discovered, also this phase was deemed energetically favourable from DFT.     

HAADF-STEM study of β′-type precipitates in an over-aged Al–Mg–Si–Ag alloy

Coarse, rod-shaped precipitates growing along ?100?Al directions in an Al–1.0?wt% Mg₂Si alloy with 0.5?wt% Ag additions were investigated by high-resolution high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM). All investigated precipitates had complex structures, being composed of domains separated by anti-phase resembling boundaries. The domains consist of a modified hexagonal β′-type structure that contains a considerable amount of Ag. Based on HAADF-STEM images, an average atomic model with space group P-62?m (189) and composition Al₃Mg₃Si₂Ag is proposed, having Al incorporation and Ag replacing certain Si atomic columns. Co-existence with the Ag-free β′-Mg₉Si₅ phase has been observed for some precipitates. The boundaries may be described as full or half units of the orthorhombic U2-AlMgSi precipitate phase. The HAADF-STEM images indicate partial replacements of Al atoms by Ag, in both the β′-type domains and the U2-type boundaries. Ag enrichment of the Al matrix near the precipitate/Al interface was observed for all the investigated precipitates     

Radiation-stimulated diffusion in Al–Si alloys

A di-vacancy low-temperature diffusion is proposed to explain diffusion-controlled processes in Al–Si alloys responsible for neutron-induced silicon precipitation. Ab initio calculations of potential barriers for Si atom hopping in aluminium lattice showed that in the case of di-vacancy diffusion, they are small compared with that of mono-vacancy diffusion. The low temperature diffusivity of mono-vacancies is too small to account for the measured Si diffusivities in aluminium. The dependencies of radiation-stimulated diffusion on the neutron flux and on the temperature are obtained and can be used for the experimental verification of the developed model.     

Thermal and microstructural investigation of Cu–Al–Mn–Mg shape memory alloys

There are many studies to improve the properties of Cu–Al–Mn shape memory alloys, such as high transformation temperatures, ductility and workability. Most of them have been performed by adding a quaternary component to the alloy. In this study, the effect of trace Mg addition on transformation temperatures and microstructures of three different quaternary Cu–Al–Mn–Mg alloys has been investigated using thermal analysis, optical microscopy and XRD techniques. The transformation temperatures are within the range of 120–180 °C, and they have not changed significantly on decreasing the Mn content, replacing with Mg. The fine precipitates have been observed in the alloys with the Mg content up to 1.64 at%. Calculated entropy change and XRD analysis reveal that the alloys with high Al content have mainly 18R-type structure which could be responsible for good ductility and workability.     

Texture transition in Al–Mg alloys: effect of magnesium

ABSTRACT

The evolution of deformation texture and microstructure in commercially pure Al (cp-Al) and two Al–Mg alloys (Al–4Mg and Al–6Mg) during cold rolling to a very large strain (true strain ε_t? ≈?3.9) was investigated. The development of deformation texture in cp-Al, after rolling, can be considered as pure metal or Copper-type, which is characterised mainly by the presence of Cu {112}<111>, Bs {110}<112> and S {123}<634> components. The deformation microstructure clearly indicates that deformation mechanism in this case remains slip dominated throughout the deformation range. In the Al–4Mg alloy, the initial slip mode of deformation is finally taken over by mechanism involving both slip and Copper-type shear bands, at higher deformation levels. In contrast, in the Al–6Mg alloy, the slip and twin mode of deformation in the initial stage is replaced by slip and Brass-type shear bands at higher deformation levels. Although a Copper-type deformation texture forms in the two Al–Mg alloys at the initial stage of deformation, there is a significant increase in the intensity of the Bs component and a noticeable decrease in the intensity of the Cu component at higher levels of deformation, particularly in the Al–6Mg alloy. This phenomenon indicates the possibility of transition of the deformation texture from Cu-type to Bs-type, which is concurrent with the addition of Mg. Using visco-plastic self-consistent modelling, the evolution of deformation texture could be simulated for all three materials.     

Early stage ageing effects and shallow positron traps in Al–Mg–Si alloys

Room temperature ageing, so-called natural ageing, of Al–Mg–Si alloys has a subtle but striking influence on the mechanical properties achievable by subsequent ageing at more elevated temperatures. Though strongly debated, different clustering processes are generally accepted to give rise to this effect. Using temperature-dependent positron lifetime measurements of naturally aged Al–Mg–Si alloys, it is shown that in the early stages of ageing, small clusters of alloying atoms without embedded vacancies take part in the decomposition process. These clusters serve as shallow positron traps with a binding energy of about 55(10) meV, grow in the course of natural ageing and transform to deep positron traps with binding energies well above thermal energies. Thus, results of positron annihilation spectroscopy techniques need to be interpreted carefully with respect to the microstructure of age-hardenable Al alloys. Moreover, it is shown that a simple approach to bind positron states using a three-dimensional potential well and (bulk) positron affinities cannot explain the present findings.     

Effect of growth rate and Mg content on dendrite tip characteristics of Al–Cu–Mg ternary alloys

An experimental analysis is presented to correlate the secondary dendrite arm spacing λ ₂ and dendrite tip radius R with growth rate V and Mg content C _0-Mg of Al–Cu–Mg ternary alloys. Under constant temperature gradient G (4.84±0.13 K mm⁻¹), a series of directional solidification experiments were performed at five different growth rates V (16.7–83.3 μm/s) and five different Mg contents C _0-Mg in Al–5 wt.% Cu–(0.5–5) wt.% Mg alloys. Solid–liquid interface was investigated from the longitudinal sections of the quenched samples, and λ ₂ and R were measured on the dendrite tips. The dependencies of λ ₂ and R on V and C _0-Mg were determined. The experimental results showed that the values of λ ₂ and R decrease as V and C _0-Mg increase at a constant G. The present exponent values related to V are found to be slightly lower than the values of the theoretical models and previous experimental works; however, C _0-Mg exponent values are found to be much lower than the theoretical models and previous experimental works. The ratio of the secondary dendrite arm spacing to the dendrite tip radius is 2.09±0.15, in good agreement with the scaling law. At a constant C _0-Mg, the values of VR ² were found to slightly increase with the ascending V. However, as C _0-Mg increases, the values of VR ² decrease.     

Precipitation and solute distribution in an interrupted-aged Al–Mg–Si–Cu alloy

Quantitative analysis of the precipitate species and solute distribution was carried out on Al–Mg–Si–Cu alloy 6061 aged to peak hardness using a conventional T6 heat treatment and the so-called T6I6 heat treatments. In this latter, a dwell period at reduced temperature (65°C) is introduced into the T6 ageing cycle (at 177°C or 150°C) which modifies the microstructure and results in the simultaneous improvement of both tensile properties and fracture toughness. Analysis of three-dimensional atom probe data reveals that the superior mechanical properties of the T6I6/177 temper are achieved by a combined effect of a greater consumption of solute atoms by precipitates, an increased number density of fine precipitates and the presence of greater fractions of the effective strengthening precipitates in the final microstructure. Three types of precipitates were found to be characteristic of the peak aged conditions: β′′ precipitates, Guinier–Preston zones and Mg–Si(–Cu) co-clusters. The composition of the strengthening precipitates was found to vary over a wide range for the different heat treatment schedules, corresponding to a variation in the number density of stable nuclei, without any accompanying change in their morphology. All precipitates were found to contain substantial quantities of aluminium. The results also indicate that the strengthening precipitates are preferentially formed from Si-rich nuclei that contain Cu atoms, as opposed to Cu-free nuclei.     

Electron irradiation-enhanced core/shell organization of Al(Cr,Fe, Mn)Si dispersoids in Al–Mg–Si alloys

The age hardening 6061-T6 aluminium alloy has been chosen as structural material for the core vessel of the material testing Jules Horowitz nuclear reactor. The alloy contains incoherent Al(Cr, Fe, Mn)Si dispersoids whose characterization by energy-filtered transmission electron microscopy (EFTEM) analysis shows a core/shell organization tendency where the core is (Mn, Fe) rich, and the shell is Cr rich. The present work studies the stability of this organization under irradiation. TEM characterization on the same particles, before and after 1 MeV electron irradiation, reveals that the core/shell organization is enhanced after irradiation. It is proposed that the high level of point defects, created by irradiation, ensures a radiation-enhanced diffusion process favourable to the unmixing forces between (Fe, Mn) and Cr. Shell formation may result in the low-energy interface segregation of Cr atoms within the (Fe, Mn) system combined with the unmixing of Cr, Fe and Mn components.     

Fundamental understanding of Na-induced high temperature embrittlement in Al–Mg alloys

Sodium is an undesirable impurity in aluminium–magnesium alloys. In trace amounts it leads to high temperature embrittlement (HTE), due to intergranular fracture, which results in edge cracking during hot rolling. In the present work, the results of a thermodynamic investigation to elucidate the mechanism are presented. Correlations between HTE, phase formation, temperature and composition in Al–Mg alloys were determined. It is suggested that: (i) HTE is related to the formation of an intergranular Na-rich liquid phase, which significantly weakens the strength of grain boundaries; (ii) for a given Mg content, there exists a maximum Na content above which HTE cannot be avoided; and (iii) for a given alloy, a proper hot-rolling temperature should be chosen with respect to Na and Mg contents to suppress HTE. The HTE sensitive zone and a hot-rolling safe zone of Al–Mg–Na alloys are defined as functions of processing temperature and alloy composition. The tendency of HTE formation was evaluated based on thermodynamic simulations of phase fraction of the intergranular Na-rich liquid phase.     

HRTEM and HAADF-STEM tomography investigation of the heterogeneously formed S (Al2CuMg) precipitates in Al–Cu–Mg alloy

The distribution of variants and three-dimensional (3D) configurations of the heterogeneously formed S (Al₂CuMg) precipitates at dislocations, grain boundaries and the Al₂₀Cu₂Mn₃ dispersoid/Al interfaces were studied in this research. By means of high resolution transmission electron microscopy, we systematically investigated the orientation relationships (ORs) between these heterogeneously formed S precipitates and the Al matrix, and further unraveled that the preferred orientation of S variants at grain boundaries and at dispersoid/Al interfaces are respectively associated with the OR between the precipitate habit plane and the grain boundary plane, and the OR between the precipitate habit plane and the interface plane. The inherent characteristic of the crystal structure of the S phase, i.e. the symmetry of the pentagonal subunit, was considered to be the fundamental factor determining the preference of the variant pair. By using high angle annular dark field scanning transmission electron microscopy tomography, we successively obtained the 3D reconstruction of the S precipitates at these defects. Both the morphology of an individual S precipitate and the overall configuration of the S precipitates nucleated at these defects can be clearly observed without misunderstandings induced by the overlap and projection effects of the conventional two-dimensional methods.