The most stable crystal structure and the formation processes of an order-disorder (OD) intermetallic phase in the Mg–Al–Gd ternary system

The most stable crystal structure for an 18R-type order-disorder (OD) intermetallic phase in the Mg–Al–Gd ternary system and its formation processes by annealing at 525?°C have been investigated by means of transmission electron microscopy and scanning transmission electron microscopy. The most energetically favourable polytype at 525?°C is found to be the structurally simplest one, a maximum degree of order polytype (monoclinic, 1M, space group: C2/m), described with a single stacking vector in stacking six-layer structural blocks. The formation of this simplest polytype occurs in the sequence of (i) enrichment of Gd and Al in four consecutive close-packed planes while keeping the hexagonal close-packed stacking of the AB-type, (ii) formation of Al₆Gd₈ clusters in the four consecutive atomic planes, introducing a stacking fault in the middle of the four consecutive atomic planes, (iii) thickening by the formation of Gd and Al-enriched four consecutive planes at a distance of two or three close-packed Mg atomic planes from the pre-existing Gd and Al-enriched four consecutive atomic planes so as to form six-layer and, sometimes seven-layer structural blocks, (iv) in-plane ordering of Al₆Gd₈ clusters in the four consecutive atomic planes and the stacking of structural blocks in the preferential stacking positions to form the OD structure, and (v) elimination of different structural blocks (other than six-layer ones) and the long-range ordering in the stacking of structural blocks.     

Approximant crystals of icosahedral Mg–(Ga,Al)–Zn alloys

The zero field cooled (ZFC) and field cooled (FC) low-field magnetic moment m of a dense frozen ferrofluid containing Fe₅₅Co₄₅ particles of size 4.6nm in hexane exhibits irreversibility at temperatures T?T _b≈ 30?K. FC in μ ₀ H ≤ 1?T gives rise to shifted minor hysteresis loops below T _b. At T _c≈ 10?K, sharp peaks of m ^ZFC and of the ac susceptibility χ ′, a kink of the thermoremanent magnetic moment m ^TRM, a sizeable reduction of the coercive field H _c, and the appearance of a spontaneous moment m ^SFM indicate a phase transition with near mean-field critical behaviour of both m ^SFM and χ ′ . These features are explained within a core-shell model of nanoparticles, whose strongly disordered shells gradually become blocked below T _b, while their soft ferromagnetic cores couple dipolarly and become superferromagnetic (SFM) below T _c.     

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.     

Investigation on the microstructure of a τ-Mg32(Al,Zn)49 strengthened Mg–Zn–Al alloy with relatively low Zn content

In the present work different orthogonal tight-binding molecular dynamics methods have been employed for describing small silicon clusters. The cohesive energies calculated using these methods have been compared with those found from the first principles Car-Parrinello method. The comparison shows that the orthogonal tight binding matrix elements and repulsive potentials need to include the radial cutoff up to fourth neighbor distance in diamond structure in order to reproduce ab initio results. The environmental correction is not needed in this orthogonal tight-binding method.     

Effect of Ni on growth kinetics,microstructural evolution and crystal structure in the Cu(Ni)–Sn system

Abstract

The role of Ni addition in Cu on the growth of intermetallic compounds in the Cu–Sn system is studied based on microstructure, crystal structure and quantitative diffusion analysis. The diffraction pattern analysis of intermetallic compounds indicates that the presence of Ni does not change their crystal structure. However, it strongly affects the microstructural evolution and diffusion rates of components. The growth rate of (Cu,Ni)₃Sn decreases without changing the diffusion coefficient because of the increase in growth rate of (Cu,Ni)₆Sn₅. For 3 at.% or higher Ni addition in Cu, only the (Cu,Ni)₆Sn₅ phase grows in the interdiffusion zone. The elongated grains of (Cu,Ni)₆Sn₅ are found when it is grown from (Cu,Ni)₃Sn. This indicates that the newly formed intermetallic compound joins with the existing grains of the phase. On the other hand, smaller grains are found when this phase grows directly from Cu in the absence of (Cu,Ni)₃Sn indicating the ease of repeated nucleation. Grain size of (Cu,Ni)₆Sn₅ decreases with further increase in Ni content, which indicates a further reduction of activation barrier for nucleation. The relations for the estimation of relevant diffusion parameters are established considering the diffusion mechanism in the Cu(Ni)–Sn system, which is otherwise impossible in the phases with narrow homogeneity range in a ternary system. The flux of Sn increases, whereas the flux of Cu decreases drastically with the addition of very small amount of Ni, such as 0.5 at.% Ni, in Cu. Analysis of the atomic mechanism of diffusion indicates the contribution from both lattice and grain boundary for the growth of (Cu,Ni)₆Sn₅ phase.     

Modeling the TDFD dissolution of Al–Fe–Mn–Si particles in an Al–4.5Zn–1Mg alloy

Dissolution of large particles in DC-cast 7xxx aluminum alloys is one of the primary objectives of the homogenization process. A mathematical model to describe and predict this complex thermodynamical and kinetical process is of great significance. In this paper, the details of a diffusion-limited dissolution model, based on the thinning, discontinuation and full dissolution (TDFD) mechanism, to predict the dissolution of the Al₁₇(Fe_3.2, Mn_0.8)Si₂ particles is described. The model is capable of predicting the volume fraction and thickness of the particles during homogenization at different temperatures and time intervals. The predicted results are in good agreement with measurements using quantitative X-ray diffraction (QXRD) and quantitative field emission gun-scanning electron microscopy (QSEM). The model predictions of the supersaturation parameter, interface position, interface movement rate of the planar surfaces and the cylindrical edges, and the effect of the occurrence of discontinuities on the dissolution extent are presented.     

First-principles study of the effect of iron on the crystal structure,stability and chemical bonding in the β-based AlCu ordered η2-phase and the pretransition state of a solid solution

First-principles calculations showed that the thermodynamic stability of β-based ordered η₂-AlCu phase doped with Fe is due to iron substitution in the copper sublattice (Fe_Cu), which corresponds to the maximum number of Fe–Al bonds in the first cubic coordination polyhedron. This iron localisation leads to stable ω-like atomic displacements and pentagonal Al-nets in the (010) plane of η₂-AlCu(Fe). This phase with iron substituting copper (e/a?=?1.925) is an energetically preferred η-based non-canonical approximant of the icosahedral phase (e/a?=?1.86). The energy gain for the Fe_Cu position is determined by strong covalent Fe3d–Al3p bonding, while there is a weak Fe3d–Cu4s3d hybridisation for the Fe_Al substitution. Using a composite cluster model, we demonstrate that short-range order in the pretransition state of the β-Al–Cu–Fe solid solution observed prior to the precipitation of η-phase is stabilised due to formation of Fe–Al bonds in the first cubic coordination polyhedron of the composite cluster.     

Effect of Pt on interdiffusion and mechanical properties of the γ and γ′ phases in the Ni–Pt–Al system

The effect of Pt on the growth kinetics of the γ′-[Ni(Pt)]₃Al ordered intermetallic phase and the γ-Ni(Pt, Al) solid solution diffusion rates of the species, hardness and elastic modulus was examined by employing the diffusion couple experimental technique. Experiments were conducted by using the β-Ni(Pt)Al phase and Ni(Pt) alloy couples, each of which had a fixed amount of Pt (5, 10 and 15 at. %) in both the end members so that the Pt content is more or less constant throughout the interdiffusion zone. The results suggest that the growth kinetics of both phases and the average effective interdiffusion coefficients of Ni and Al increase with the increase in Pt content. Nanoindentation studies across the compositional gradients show that the mechanical properties of the intermetallic phase in the superalloy are relatively insensitive to the presence of Pt but are more sensitive to the Ni/Al ratio. In contrast, the marked variation in the hardness of the γ phase were noted, increasing markedly with Al concentration in a given couple and also increasing with increasing Pt content. Possible causes for the observed variations are discussed.     

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.     

Experimental examination of strain field within GP zone in an Al–Zn–Mg–Cu alloy

The strain field of GP zone plays a very important role in strengthening of the precipitation-hardened aluminum alloys by prohibiting movement of dislocations; however, quantitative analysis about the strain field of the GP zone in the aluminum alloys has been seldom reported elsewhere. In this paper, the microstructure of GP zone in an Al–Zn–Mg–Cu alloy was explored by using high-resolution transmission electron microscopy (HRTEM), and the displacement field of lattice planes within the GP zone was experimentally measured by geometric phase analysis (GPA) technique; then, the quantitative results about strains of the distorted lattice planes within the GP zone were also obtained. It is found that the GP zone core is convergence region of the strains, and the maximum value of the compressive strains within the GP zone is about 7.6%.     

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.     

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     

Frequency dependence of the spin glass freezing temperatures in icosahedral R–Mg–Zn (R = rare earth) quasicrystals

We present ac susceptibility measurements with the frequency spanning three orders of magnitude on single grain, icosahedral R–Mg–Zn (R = rare earth) quasicrystals. The freezing temperature in Gd-based, Heisenberg spin glasses in this family increases by ～2% with a frequency increase from 10?Hz to 10?kHz, whereas the freezing temperature in the non-Heisenberg members of the family is significantly more responsive to the frequency change (by 16–22%), suggesting that an additional magnetic anisotropy distribution in the non-Heisenberg spin glasses causes changes in the low frequency magnetic dynamics.     

Structure of dislocations and stacking faults in the complex intermetallic ξ′-(Al–Pd–Mn) phase

We present the results of an electron microscopy study of defects in plastically deformed single crystals of the intermetallic ξ^′-(Al–Pd–Mn) phase. Pure edge dislocations with two different Burgers vector directions and four different Burgers vector magnitudes were found. All Burgers vector magnitudes observed can be described in terms of irrational fractions of the unit-cell parameters, and we have observed Burgers vector directions that can be indexed using irrational indices. The stacking faults observed have displacement vectors whose magnitudes and directions are incompatible with the unit cell of the ξ^′ phase. A comparison of the Burgers vectors observed in this study with those reported for the corresponding icosahedral quasicrystal shows that they are equivalent with respect to their directions and lengths. This leads to the conclusion that local order rather than long-range periodic (or quasiperiodic) order governs the structure of defects in these materials.     

Observations of the stress developed in Si inclusions following plastic flow in the matrix of an Al–Si–Mg alloy

Abstract

Measurements are made of the stress developed in near-spherical elastic inclusions in an elastic plastic matrix under both tension and compression loading. Two experimental conditions are reported. The first case is where no thermal mismatch exists between the inclusions and the matrix, so that the stress in the inclusion is purely a result of the misfit in the elastic moduli and of the distortion of the plastic slip-line field around the inclusion. The observations are believed to be the first such and are in qualitative agreement with finite-element modelling for idealised inclusion distributions. The second case is the more usual one where a thermal misfit stress exists and observations are reported of the stress relief effects caused by the interaction of the plasticity-induced stress with the thermal and elastic misfit stresses.     

The structure of a long-period stacking phase in an Mg–Al–Y alloy studied by electron microscopy

A new phase with a 10H-type long-period stacking (LPS) structure was found in an Mg₇₅Al₁₀Y₁₅ alloy annealed at 823?K. The LPS structure in the Mg₇₅Al₁₀Y₁₅ alloy annealed at 823?K for 2?h has an ordered arrangement of L1₂-type structural Al₆Y₈ clusters on the two-dimensional plane parallel to the c-plane of hexagonal Mg lattice and a disordered arrangement along the c-axis, whereas a perfectly ordered structure along the c-axis, which has a period with two times of that of the 10H-type LPS structure, was established by annealing at 823?K for 24?h. The structural model of the ordered LPS phase is proposed by high-resolution images taken with a Cs-corrected scanning transmission electron microscope and also electron diffraction patterns.     

Photodynamics of Ga_(Zn)–V_(Zn) complex defect in Ga-doped ZnO

The wide-band-gap II–VI compound semiconductor ZnO is regarded as a promising single-photon emission(SPE)host material. In this work, we demonstrate that a(GaZn–VZn)-complex defect can readily be obtained and the density can be controlled in a certain range. In analogy to nitrogen vacancy centers, such a defect in ZnO is expected to be a new single photon source. The optical properties of the(GaZn–VZn)-complex defect are further studied by photoluminescence and time-resolved photoluminescence spectra measurements. The electron transitions between the defect levels emit light at ～ 650 nm with a lifetime of 10–20 nanoseconds, indicating a good coherent length for SPE. Finally, a two-level emitter structure is proposed to explain the carrier dynamics. We believe that the photodynamics study of the(GaZn–VZn)-complex defect in this work is important for ZnO-based quantum emitters.