Secondary precipitation in Al–Zn–Mg–(Ag) alloys

Secondary ageing of age-hardenable aluminium alloys occurs at temperatures below the solvus of GP zones after a preliminary ageing at a higher temperature. The phenomenon has technological interest, as it may be included in heat treatments giving a substantial benefit on the mechanical properties. In the present work, positron annihilation lifetime spectroscopy (PALS) is applied in combination with Vickers hardness measurements for an investigation on secondary ageing of Al–4wt.%Zn–3wt.%Mg–xAg, where x=0, 0.1, 0.2, 0.3, 0.5 wt.%. Ageing regimes have been characterised by the substantially different evolutions that are observed. The results shed light on the interplay between the formation of coherent solute aggregates (clusters or GP zones) and the precipitation of semi-coherent or incoherent precipitates, which are in competition to control the hardening effects. PALS data show that secondary ageing in the ternary Al–Zn–Mg alloys produces coherent aggregates even in the presence of a well-developed stage of semi-coherent or incoherent precipitation that is obtained if the alloys are first aged to peak hardness. In the presence of Ag, on the contrary, the effects of coherent aggregation during secondary ageing are observed only if the preliminary ageing is interrupted well before reaching peak hardness.     

GP-zones in Al–Zn–Mg alloys and their role in artificial aging

The structure of GP-zones in an industrial, 7xxx-series Al–Zn–Mg alloy has been investigated by transmission electron microscopy methods: selected area diffraction, conventional and high-resolution imaging. Two types of GP-zones, GP(I) and (II) are characterized by their electron diffraction patterns. GP(I)-zones are formed over a wide temperature range, from room temperature to 140–150°C, independently of quenching temperature. The GP(I)-zones are coherent with the aluminum matrix, with internal ordering of Zn and Al/Mg on the matrix lattice, suggested to be based on AuCu(I)-type sub-unit, and anti-phase boundaries. GP(II) are formed after quenching from temperatures above 450°C, by aging at temperatures above 70°C. The GP(II)-zones are described as zinc-rich layers on {111}-planes, with internal order in the form of elongated <110> domains. The structural relation to the η′-precipitate is discussed.     

Characterization of planar features in Mg–Y–Zn alloys

The planar features in a Mg–8Y–2Zn–0.6Zr (wt.%) alloy solution-treated at 500 °C for 1 h have been examined using conventional transmission electron microscopy and atomic-resolution high-angle annular dark-field scanning transmission electron microscopy. Three types of planar features are detected in the microstructure. The first type, which was previously reported to be an intrinsic stacking fault I₁ bounded by a Frank partial dislocation, is shown to be the 14H precipitate phase that is associated with Shockley partial dislocations. The second type is also a precipitate phase that has a single unit cell height and is associated with Shockley partial dislocations. The third type of planar feature comprises small ribbon-like stacking faults. These stacking faults are determined as intrinsic I₂ type bounded by two Shockley partial dislocations, which is further confirmed by computer simulation. The stacking fault energy associated with the faults is much smaller than that of pure magnesium.     

Strain induced GdH2 precipitate in Mg–Gd based alloys

A new rectangle-shape GdH₂ precipitate was identified in Mg–Gd based alloys after mechanical polishing or compressive deformation. The precipitate was mainly distributed near the dendrite or grain boundaries where gadolinium element was segregated owing to non-equilibrium solidification. It is confirmed that hydrogen-containing medium, deformation and gadolinium segregation were the prerequisites to form GdH₂ precipitate. The amount of GdH₂ precipitate was mostly associated with deformation and the gadolinium content. A model was introduced to explain the formation mechanism of GdH₂ precipitate. The hydrogen in GdH₂ precipitate principally came from the outside medium. Moreover, the diffusion and transportation of hydrogen were improved by the movement of dislocation.     

A simulation study of the shape of β′ precipitates in Mg–Y and Mg–Gd alloys

The metastable β′ phase is a key strengthening precipitate phase in a range of Mg–RE (RE: rare-earth elements) based alloys. The morphology of the β′ precipitates changes from a faceted and nearly equiaxed shape in Mg–Y alloys to a truncated lenticular shape in Mg–Gd alloys. In this work, we study effects of interfacial energy and coherency elastic strain energy on the morphology of β′ precipitates in binary Mg–Y and Mg–Gd alloys using a combination of first-principles calculations and phase-field simulations. Without any free-fitting parameters and using the first-principles calculations, CALPHAD databases and experimental characterizations as model inputs (lattice parameters of the β′ phase, elastic constants and chemical free energy of Mg matrix and interfacial energies of the coherent β′/Mg matrix interfaces), the phase-field simulations predict equilibrium shapes of β′ precipitates of different sizes that agree well with experimental observations. Factors causing the difference in the equilibrium shape of β′-Mg₇Y and β′-Mg₇Gd precipitates are identified, and possible approaches to increase the aspect ratio of the β′ precipitates and thus to enhance the strength of Mg–RE alloys are discussed.     

Phases and microstructures of high Zn-containing Al–Zn–Mg–Cu alloys

Phases and microstructures of three high Zncontaining Al–Zn–Mg–Cu alloys were investigated by means of thermodynamic calculation method, optica microscopy(OM), scanning electron microscopy(SEM)energy dispersive spectroscopy(EDS), X-ray diffraction(XRD), and differential scanning calorimetry(DSC) analysis. The results indicate that similar dendritic network morphologies are found in these three Al–Zn–Mg–Cu alloys. The as-cast 7056 aluminum alloy consists of aluminum solid solution, coarse Al/Mg(Cu, Zn, Al)_2 eutectic phases, and fine intermetallic compounds g(MgZn_2). Both of as-cast 7095 and 7136 aluminum alloys involve a(Al)eutectic Al/Mg(Cu, Zn, Al)_2, intermetallic g(MgZn_2), and h(Al_2Cu). During homogenization at 450 °C, fine g(MgZn_2) can dissolve into matrix absolutely. After homogenization at 450 °C for 24 h, Mg(Cu, Zn, Al)_2 phase in 7136 alloy transforms into S(Al_2Cu Mg) while no change is found in 7056 and 7095 alloys. The thermodynamic calculation can be used to predict the phases in high Zncontaining Al–Zn–Mg–Cu alloys.     

Crystal structure and stability of complex precipitate phases in Al–Cu–Mg–(Si) and Al–Zn–Mg alloys

We demonstrate how first-principles total energy calculations may be used to elucidate both the crystal structures and formation enthalpies of complex precipitates in multicomponent Al alloys. For the precipitates, S(Al–Cu–Mg), η′ (Al–Zn–Mg), and Q(Al–Cu–Mg–Si), energetics were computed for each of the models of the crystal structures available in the literature allowing a critical assessment of the validity of the models. In all three systems, energetics were also calculated for solid solution phases as well as other key phases (e.g., equilibrium phases, GP zones) in each precipitation sequence. For both the S and η′ phases, we find that recently proposed structures (based on electron microscopy) produce unreasonably high energies, and thus we suggest that these models should be re-evaluated. However, for all three precipitates, we find that structures based on X-ray diffraction refinements provide both reasonable energetics and structural parameters, and therefore the first-principles results lend support to these structural refinements. Further, we predict energy-lowering site occupations and stoichiometries of the precipitate phases, where experimental information is incomplete. This work suggests that first-principles total energy calculations can be used in the future as a complementary technique with diffraction or microscopy for studying precipitate structures and stabilities.     

Enhanced creep performance in an Al–Cu–Mg–Ag alloy through underageing

Tests at 130 °C and 150 °C have shown that the creep resistance of an Al–Cu–Mg–Ag alloy is significantly increased if it is heat-treated at an elevated temperature to an underaged condition rather than the fully hardened, T6 temper. This beneficial effect of underageing is manifest in reduced rates of secondary creep. Similar results have been obtained for the commercial alloy 2024. Delays at ambient temperature after underageing and before testing lead to secondary precipitation and a progressive decrease in creep performance that eventually reverts to close to that for the T6 condition. This detrimental effect may be overcome by slow cooling from the underageing temperature, which arrests or impedes subsequent secondary precipitation. Microstructural observations suggest that the enhanced creep resistance in the underaged condition is a consequence of the presence of “free” solute in solid solution that is not yet involved in precipitation.     

Simultaneous improvement of strength and ductility by Mn addition in extruded Mg–Gd–Zn alloy

The influence of Mn content on the microstructure, tensile properties and strain-hardening behaviors of extruded Mg?1Gd?0.5Zn?xMn (x=0, 0.3 and 1, wt.%) alloy sheets was investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), and electron backscatter diffraction (EBSD). The results show that the completely recrystallized grain structure and the extrusion direction (ED)-titling texture are observed in all the extruded sheets. The mean grain size and weakened ED-titling texture of the extruded sheets are gradually reduced with increasing Mn content. This is primarily associated with the formation of new fine α-Mn particles by Mn addition. Tensile properties show that the addition of Mn also leads to the improvement of yield strengths, ultimate tensile strengths and elongations of the extruded Mg?1Gd?0.5Zn?xMn sheets, which is mainly due to the fine grains and α-Mn particles. In addition, the Mg?1Gd?0.5Zn?1Mn sheet has the lowest strain-hardening exponent and the best hardening capacity among all prepared Mg?1Gd?0.5Zn?xMn sheets.     

Atom probe tomography of nanoscale microstructures within precipitate free zones in Al–Zn–Mg(–Ag) alloys

Solute distributions in the vicinity of grain boundaries in Al–Zn–Mg(–Ag) alloys were studied using a three-dimensional atom probe, in order to elucidate the mechanism of formation of precipitate free zones (PFZs) and the fundamental role of Ag in controlling PFZ width. It is shown that nanoscale clusters are formed within the PFZ in Al–Zn–Mg, despite the solute concentration remaining at the levels in the as-quenched state. Such observations have not previously been possible, and show unambiguously that vacancy depletion is the dominant mechanism of formation of PFZs in this alloy. In the Ag-containing alloy, a narrower PFZ is observed, with a reduced solute level, showing that here the dominant mechanism of PFZ formation is solute depletion. The role of Ag in this change of mechanism appears to be due to its favorable interactions not only with Mg and Zn atoms but also with vacancies.     

The 18R and 14H long-period stacking ordered structures in Mg–Y–Zn alloys

The 18R and 14H long-period stacking ordered structures formed in Mg–Y–Zn alloys are examined systematically using electron diffraction and high-angle annular dark-field scanning transmission electron microscopy. In contrast to that reported in previous studies, the 18R structure is demonstrated to have an ordered base-centred monoclinic lattice, with Y and Zn atoms having an ordered arrangement in the closely packed planes. Furthermore, the composition of 18R is suggested to be Mg₁₀Y₁Zn₁, instead of the Mg₁₂Y₁Zn₁ composition that is commonly accepted. The 14H structure is also ordered. It has a hexagonal unit cell; the ordered distribution of Y and Zn atoms in the unit cell is similar to that in the 18R and its composition is Mg₁₂Y₁Zn₁. The 18R unit cell has three ABCA-type building blocks arranged in the same shear direction, while the 14H unit cell has two ABCA-type building blocks arranged in opposite shear directions.     

Study of precipitation in aged binary Mg–Al and ternary Mg–Al–Zn alloys using 27Al NMR spectroscopy

Nuclear magnetic resonance (NMR) spectroscopy of ²⁷Al was used to study the development of precipitation in aged Mg–6 wt%Al, Mg–9 wt%Al and Mg–9 wt%Al–(x) wt%Zn alloys. The ²⁷Al spectra for the aged alloys consist of two peaks; one from the aluminium in solid solution and the other from aluminium in the precipitate phase. The proportion of aluminium atoms in the matrix and precipitate phases was measured, as a function of time at temperature, using the relative intensities of peaks. The nucleation of the continuous precipitates was found to be highly dependent on the initial supersaturation and it is proposed that it is a homogeneous process. The Austin–Rickett relation successfully models the amount of continuous precipitation with aging time; the kinetics is consistent with one-dimensional and interface-controlled growth. Changes in composition of the matrix and precipitate phases were correlated with the ²⁷Al Knight shift characterising these phases. The Knight shift data from a series of ternary Mg–9 wt%Al–(x)wt%Zn alloys indicates that the Zn segregates to the precipitate phase during precipitation.     

Microstructure and microsegregation in Al-rich Al–Cu–Mg alloys

Microstructure and microsegregation in two directionally solidified Al alloys, Al–3.9Cu–0.9Mg and Al–15Cu–1Mg (in wt%), were investigated for cooling rates between 0.78 and 0.039 K/s. Transverse and longitudinal sections were examined to exhibit dendritic microstructures. Fractions of solids formed were determined using quantitative image analysis and solute redistribution in the primary phase was determined using area scans. The model employed to calculate microsegregation is based on the Scheil model but including solid-state diffusion, dendrite arm coarsening and undercooling of the dendrite tip and the formation of eutectic. The model-calculated results were found to be in good agreement with the experimentally determined concentration distributions in the primary α phase and the amounts of phases formed. It was found that the dendrite morphology was best described by a cylindrical arm geometry and that the accuracy of the phase diagram could have a significant influence on the microsegregation predictions. For the alloy with low copper content, two types of embedded droplets were observed.     

Influence of alloy composition and heat treatment on precipitate composition in Al–Zn–Mg–Cu alloys

The composition of precipitates in three alloys of the Al–Zn–Mg–Cu system has been investigated for different heat treatments, including peak-aged and over-aged states as well as near-equilibrium conditions, by combining atom probe tomography and systematic anomalous small-angle X-ray scattering experiments. We show that the concentration of Cu in the precipitates changes during heat treatments and is alloy dependent. At low ageing temperature (120 °C) the Cu content in the precipitates is close to the alloy content. The precipitate Cu content is shown to increase with increasing temperature and Cu alloy content. We show that in near-equilibrium conditions the precipitate compositions are 33 at.% in Mg, about 15 at.% in Al, about 13 at.% in Cu and balance Zn. Our results strongly suggest that the gradual incorporation of Cu in the precipitates during the heat treatment is essentially related to the slower diffusivity of this element in aluminium.     

Correlations among stress corrosion cracking,grain-boundary microchemistry,and Zn content in high Zn-containing Al–Zn–Mg–Cu alloys

The correlations among the corrosion behaviour, grain-boundary microchemistry, and Zn content in Al–Zn–Mg–Cu alloys were studied using stress corrosion cracking (SCC) and intergranular corrosion (IGC) tests, combined with scanning electron microscopy (SEM) and high-angle angular dark field scanning transmission electron microscopy (HAADF-STEM) microstructural examinations. The results showed that the tensile strength enhancement of high Zn-containing Al–Zn–Mg–Cu alloys was mainly attributed to the high density nano-scale matrix precipitates. The SCC plateau velocity for the alloy with 11.0 wt.% Zn was about an order of magnitude greater than that of the alloy with 7.9 wt.% Zn, which was mainly associated with Zn enrichment in grain boundary precipitates and wide precipitates-free zones. The SCC mechanisms of different Zn-containing alloys were discussed based on fracture features, grain-boundary microchemistry, and electrochemical properties.