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.     

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     

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.     

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.     

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°.     

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.     

Effects of minor additions of Mg and Ag on precipitation phenomena in Al–4 mass% Cu

Calorimetric measurements and transmission electron microscopy have been used to study the effects of minor additions of Mg and Ag on mechanism and kinetics of precipitation in Al–4 mass% Cu. Isothermal studies at 30°C show that the rate of Guinier–Preston (Cu) zone formation is progressively reduced by the presence of Mg, or Mg?+?Ag, which is attributed to preferential trapping of vacancies so that their ability to assist diffusion of Cu atoms is reduced. At elevated temperatures, Mg enhances precipitation of θ′, whereas Mg?+?Ag stimulates formation of the Ω phase. Precipitation of S′ follows θ′ if Mg or Mg?+?Ag are present and pre-ageing increases the quantity of θ′ precipitated at the expense of S′. It has been confirmed that secondary precipitation occurs at low temperatures if alloys are first aged at elevated temperatures.     

Microstructural characterisation of Al–Si cast alloys containing rare earth additions

This paper presents a thorough study on the effect of rare earth elements, specifically La and Ce, on the microstructure characteristics of non-modified and Sr-modified A356 and A413 alloys. Several alloys were prepared by adding 1% La and 1% Ce either individually or in combination. Microstructural characterisation was carried out using optical microscopy, scanning electron microscopy and electron probe microanalysis as well as differential scanning calorimetry (DSC) analysis. The results showed that the individual and combined additions of La and Ce did not bring about any modification or even refinement in the eutectic Si structure. Moreover, these additions were found to negate the modification effect of Sr, particularly in the presence of La. The A356 and A413 alloys containing La and/or Ce displayed high phase volume fractions owing to the formation of Al–Si–La/Ce/(La,Ce) and Al–Ti–La/Ce intermetallic phases. DSC analysis revealed that the formation temperatures of these phases varied from 560 to 568 °C and 568 to 574 °C, respectively. This analysis also showed that the addition of La and Ce whether individually or in combination resulted in a depression in the eutectic temperature and a considerable increase in the solidification range, particularly for the A413 alloy.     

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.     

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.     

Solute-second phase interaction for Mg,Ag and Zn in Al–Li alloys

ABSTRACT

Early experiments have shown the promises of alloying with Mg?+?Ag (or Mg?+?Zn) on the performance of Al–Li alloys. To better understand the interaction between solutes and second phases in Al–Li alloys, Mg, Ag and Zn segregation to Al/δ′ interface as well as their substitution in δ′ bulk were investigated at the atomic level using first principles modelling and calculations. Energetics results and local charge analyses revealed that Mg, Ag and Zn can segregate to Al/δ′ interface by different preference, but have no significant influence on the interface adhesion. Ag and Zn can also dissolve into δ′ bulk, and enhance the local metallic bonding with nearest-neighboring Al atoms. Based on these results, a multi-fold benefit mechanism was suggested for the combined alloying with Mg?+?Ag (or Mg?+?Zn) in Al–Li alloys.     

Characteristic chemical shifts of quasicrystalline Zn–Mg–Zr alloys studied by EELS and SXES

Chemical shifts of the constituent atoms of primitive icosahedral quasicrystal (P-QC), face-centred icosahedral quasicrystal (F-QC) and 1/1-approximant (1/1-AP) of F-QC Zn–Mg–Zr alloys were investigated for the first time using high energy-resolution electron energy-loss spectroscopy (EELS) and soft-X-ray emission spectroscopy (SXES). Among Zn M-shell and Mg L-shell excitation EELS spectra of P-QC, F-QC and 1/1-AP alloys, only the quasicrystalline alloys showed a chemical shift towards the larger binding energy side. In Zn-L and Zr-L emission SXES spectra, the P-QC and F-QC alloys showed a chemical shift towards larger binding energy side. The magnitudes of the shifts in the Zn-L emission spectra of the quasicrystalline alloys were almost the same as for ZnO. These results strongly suggest a decrease in valence charge in quasicrystalline states. Therefore, it should be concluded that bonding in quasicrystalline states involves a characteristic increase in covalency compared with bonding in corresponding approximant and standard metal crystals.     

Thermodynamics and surface properties of liquid Al–Ga and Al–Ge alloys

The surface properties of Al–Ga and Al–Ge liquid alloys have been theoretically investigated at a temperature of 1100 K and 1220 K respectively. For the Al–Ga system, the quasi chemical model for regular alloy and a model for phase segregating alloy systems were applied, while for the Al–Ge system the quasi chemical model for regular and compound forming binary alloys were applied. In the case of Al–Ga, the models for the regular alloys and that for the phase segregating alloys produced the same value of order energy and same values of thermodynamic and surface properties, while for the Al–Ge system, the model for the regular alloy reproduced better the thermodynamic properties of the alloy. The model for the compound forming systems showed a qualitative trend with the measured values of the thermodynamic properties of the Al–Ge alloy and suggests the presence of a weak complex of the form Al₂Ge₃. The surface concentrations for the alloys show that Ga manifests some level of surface segregation in Al–Ga liquid alloy while the surface concentration of Ge in Al–Ge liquid alloy showed a near Roultian behavior below 0.8 atomic fraction of Ge.     

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.     

High glass formability for Cu–Hf–Ti alloys with small additions of Y and Si

The effects of small substitutions of Si and Y on the glass-forming ability of a Cu₅₅Hf₂₅Ti₂₀ glassy alloy are reported and discussed. Fully glassy rods with diameters up to 7 and 6.5 mm were produced for Cu_54.5Hf₂₅Ti₂₀Si_0.5 and Cu_{55? x} Hf₂₅Ti₂₀Y_0.3 alloys, respectively. The addition of Si enlarged ΔT_x (= T_x ? T _g, where T _g and T_x are crystallisation and glass transition temperatures, respectively) considerably, from 25 to 53 K for the Cu₅₄Hf₂₅Ti₂₀Si₁ alloy. However, the results showed that the parameters obtained from thermal analysis, such as T _rg , ΔT_x and γ[= T_x /(T _g + T _l)] are not reliably correlated with the glass-forming ability (GFA), at least for these bulk glass-forming alloys. The scavenging effects of the Y and Si, in particular the possibility of Y reducing the oxides, could be responsible for enhancing the GFA. It is proposed that the effectiveness of small additions of Si in enhancing the GFA may be the result of the possible formation of HfSiO₄ having a very large negative enthalpy of formation and, as a strong network former, it would form glassy particles which would be ineffective as nucleating agents.     

Chemical shifts of metallic and non-metallic Al–Re–Si approximant crystals studied by EELS and SXES

Chemical shifts of approximant crystals of 1/0-Al₁₂Re (1/0-metallic), 1/1-Al₇₃Re₁₅Si₁₂ (1/1-metallic) and 1/1-Al₇₃Re₁₇Si₁₀ (1/1-non-metallic) were examined by using electron energy-loss spectroscopy (EELS) and soft-X-ray emission spectroscopy (SXES). Al L-shell excitation EELS spectra of these alloys showed an apparent chemical shift only for the 1/1-non-metallic alloy to the larger binding energy side by 0.2?eV. Al-Kα, Re-Mα and Si-Kα emission SXES spectra also showed a shift to the larger binding energy side only for 1/1-non-metallic alloy. 1/0-metallic and 1/1-metallic alloys did not show any chemical shift in EELS and SXES experiments. Chemical shifts were observed only in larger binding energy side compared with pure materials. This implies the decrease of valence charge at constituent atomic sites of 1/1-non-metallic alloy compared with 1/0-metallic, 1/1-metallic and pure materials. The decreased charges should distribute intermetallic sites, which should be related to a formation of covalent bonding among Al atomic sites reported by maximum-entropy method (MEM)/Rietveld analysis on this material. This relation between chemical shift and covalent bonding nature of this approximant alloy may support the presence of covalent bonding in Al-based quasicrystals.