Phonon- and phason-dynamics in Al–Cu–Fe quasicrystals

The lattice dynamics of quasicrystals includes local phason jumps as well as phonons. Phason dynamics is important for the understanding of both the structure and atomic motion in quasicrystals, leading to short-ranged atomic motion not involving vacancies in addition to diffusion. We have studied the phason and phonon dynamics of icosahedral i-Al₆₂Cu_25.5Fe_12.5. Quasielastic Mössbauer spectroscopy (QMS) was used to probe the iron phason dynamics. Inelastic nuclear-resonant absorption (INA) of synchrotron radiation and inelastic neutron scattering (INS) were used to study the iron-partial as well as the total vibrational DOS (VDOS). We find from preliminary QMS studies that iron atoms jump on a time scale about two orders of magnitude slower than that found for copper. The EFG shows an abrupt change in slope at ca. 825 K which may be related to a transition from simple (isolated) to more complicated (co-operative) phason jumps. From INA we find that the iron-partial VDOS differs radically from that of the total (neutron-weighted) generalised VDOS measured by INS. Both these properties are related to the specific local environments of Fe and Cu in i-AlCuFe.     

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.     

Characterization of quenched-in vacancies in Fe–Al alloys

Physical and mechanical properties of Fe–Al alloys are strongly influenced by atomic ordering and point defects. In the present work positron lifetime (LT) measurements combined with slow positron implantation spectroscopy (SPIS) were employed for an investigation of quenched-in vacancies in Fe–Al alloys with the Al content ranging from 18 to 49 at.%. The interpretation of positron annihilation data was performed using ab-initio   theoretical calculations of positron parameters. Quenched-in defects were identified as Fe-vacancies. It was found that the lifetime of positrons trapped at quenched-in defects increases with increasing Al content due to an increasing number of Al atoms surrounding the Fe vacancies. The concentration of quenched-in vacancies strongly increases with increasing Al content from ≈10⁻⁵$\approx {10}^{-5}$ in Fe₈₂Al₁₈${\mathrm{Fe}}_{82}{\mathrm{Al}}_{18}$ (i.e. the alloy with the lowest Al content studied) up to ≈10⁻¹$\approx {10}^{-1}$ in Fe₅₁Al₄₉${\mathrm{Fe}}_{51}{\mathrm{Al}}_{49}$ (i.e. the alloy with the highest Al content studied in this work).     

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.     

Microstructural evolution in Al–Mn–Cu–(Be) alloys

This study investigates the effects of alloying elements on the microstructural evolution of Al-rich Al–Mn–Cu–(Be) alloys during solidification, and subsequent heating and annealing. The samples were characterised using scanning electron microscopy, energy dispersive X-ray spectroscopy, synchrotron X-ray diffraction, time-of-flight secondary-ion mass spectroscopy, and differential scanning calorimetry. In the ternary Al₉₄Mn₃Cu₃ (at%) alloy, the phases formed during slower cooling (≈1?K?s^?1) can be predicted by the known Al–Mn–Cu phase diagram. The addition of Be prevented the formation of Al₆Mn, decreased the fraction of τ₁-Al₂₉Mn₆Cu₄, and increased the fraction of Al₄Mn. During faster cooling (≈1000?K?s^?1), Al₄Mn predominantly formed in the ternary alloy, whereas, in the quaternary alloys, the icosahedral quasicrystalline phase dominated. Further heating and annealing of the alloys caused an increase in the volume fractions of τ₁ in all alloys and Be₄Al (Mn,Cu) in quaternary alloys, while fractions of all other intermetallic phases decreased. Solidification with a moderate cooling rate (≈1000?K?s^?1) caused considerable strengthening, which was reduced by annealing for up to 25% in the quaternary alloys, while hardness remained almost the same in the ternary alloy.     

First-principles study of elastic and slip properties of non-canonical β-based Al–Cu–Fe approximants

Ab initio calculations were carried out to compare the mechanical properties of β-based non-canonical Al–Cu–Fe approximants of quasicrystals with cubic (β), monoclinic (η) and orthorhombic (ξ1, ξ2) structures, which all demonstrate high strengthening. The aim was to elucidate the competitive effects of the η- and ξ-ordering and iron content on deformation behaviour of these phases. We found that the Young’s modulus, polycrystalline shear modulus, mechanical stability and shear elastic modulus G(n,m) for different slip planes decrease for β-Al₅₀Cu_1-xFe_x with lowering iron content, but they grow from β-Al₅₀Cu_31.25Fe_18.75 to the ordered η-Al₅₀Cu₄₅Fe₅, and ξ2-Al_45.5Cu₅₀Fe_4.5 that indicates a growing resistance to plastic deformation due to ordering and agrees well with our experimental finding. The preferable slip systems were predicted based on the calculated generalised stacking fault (GSF) energies in β-(Cu,Fe)Al and η-(Cu,Fe)Al with similar Fe concentration. The GSF energies confirmed also that the strengthening observed in η-phase is related to ordering rather than the Fe effect in consistence with a stronger covalent bonding in η-phase.     

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°.     

Defect structure near grain boundaries in deformed polycrystalline Cu–Al alloys

The evolution of defect structure upon the deformation of Cu–Al polycrystalline solid solutions with grain sizes of 10, 100, and 200 μm is studied by means of transmission diffraction electron microscopy. Alloys are deformed by tension at a rate of 10^?2 s^?1 at room temperature. Different parameters that characterize defect structure are measured. Patterns of changes in them are revealed upon moving away from grain boundaries. Analysis of the results testifies to the presence of a reinforced zone near the grain boundaries.     

Formation and ordering of local magnetic moments in Fe–Al alloys

The density functional theory is used to study the local magnetic moments in Fe–Al alloys depending on concentration (from 29 to 44 at% Al) and the Fe nearest environment. We have found three different solutions for the system: a spin-spiral wave (SSW) which has a minimum energy and two collinear states, a ferromagnetic one and a state with both positive and negative Fe magnetic moments (the Fe atoms with many neighboring Al atoms around them have negative magnetic moments, while the other Fe atoms—positive). Both the SSW and the negative Fe moments agree with the experiments. Magnetization curves taken from the literature are analyzed. The assumption of percolation character of the size distribution of magnetic clusters describes well the experimental superparamagnetic behavior above 150 K.     

Disorder in liquid Cu–Pd alloys

The disorder in thermodynamic and microscopic structure of liquid Cu–Pd alloy at 1350?K has been studied using regular associated solution model. For this, we have calculated free energy of mixing (G_M ), activity (a), concentration fluctuation in long wavelength limit [S_CC (0)] and chemical short-range order parameter (α ₁) of liquid Cu–Pd alloy at 1350?K. The energetic and structural asymmetry of liquid Cu–Pd alloys has been successfully explained on the basis of regular associated solution model.     

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.     

Effects of damage rate on Cu precipitation in Fe–Cu model alloys under neutron irradiation

The formation of Cu precipitates and point defect clusters was investigated in two Fe–Cu binary model alloys, Fe–0.3Cu and Fe–0.6Cu, irradiated at 573?K at three different damage rates, namely 3.8?×?10^?10, 1.5?×?10^?8 and 5?×?10^?8?dpa (displacements per atom)/s, up to about 1.6?×?10^?2?dpa. Results of positron annihilation experiments indicated that Cu precipitates were formed in these irradiations with different damage rates. The growth of Cu precipitates does not increase monotonously with increasing irradiation dose, but it rather depends on the nucleation and growth of microvoids. It is also clear that the nucleation and growth of microvoids are influenced by the irradiation dose rate.     

Monte Carlo simulations of copper clustering in Fe–Cu alloys under irradiation

We present the computational approach for studying the microstructures of Cu clusters in Fe–Cu alloys by combining the molecular dynamics (MD) simulation and Monte Carlo methods. The MD simulation is used to characterize the primary damage resulting from the displacement cascade in Fe. Then, using the Metropolis Monte Carlo methods, the microstructure of the Cu clusters is predicted under the assumption that the system will evolve towards the equilibrium state. The formation of the Cu clusters is apparent for Fe–Cu alloys of a higher Cu content (1.0 w/o), whereas the degree of Cu clustering is not significant for the lower Cu content (0.1 w/o) alloys. The atomic configuration of the Cu–vacancy complex under irradiation, produced by this simulation, is in a fair agreement with the experiments. The simulation is expected to provide important information on the Cu-cluster morphology, which is useful for experimental data analysis.     

Precipitation and fracture behaviour of Fe–Mn–Ni–Al alloys

The effects of Al addition on the precipitation and fracture behaviour of Fe–Mn–Ni alloys were investigated. With the increasing of Al concentration, the matrix and grain boundary precipitates changed from L1₀ θ-MnNi to B2 Ni₂MnAl phase, which is coherent and in cube-to-cube orientation relationship with the α′-matrix. Due to the suppression of the θ-MnNi precipitates at prior austenite grain boundaries (PAGBs), the fracture mode changed from intergranular to transgranular cleavage fracture. Further addition of Al resulted in the discontinuous growth of Ni₂MnAl precipitates in the alloy containing 4.2?wt.% Al and fracture occurred by void growth and coalescence, i.e. by ductile dimple rupture. The transition of the fracture behaviour of the Fe–Mn–Ni–Al alloys is discussed in relation to the conversion of the precipitates and their discontinuous precipitation behaviour at PAGBs.     

The influence of microstructure on the martensitic transformation in Cu–Zn–Al melt-spun ribbons

The martensitic transformation was investigated in a set of twin roller melt-spun Cu–Zn–Al shape memory alloys, solidified at tangential wheel speeds between 20 and 40 m/s. The resulting microstructures were analyzed using X-ray diffraction, optical and transmission electron microscopy techniques. The characteristic martensitic transformation temperature, M _S, was determined for each condition by conventional resistometric methods. The ribbons are homogeneous in shape and for each quenching rate they exhibit a quite uniform M _S temperature. By proper thermal treatments, the different factors affecting M _S could be separately examined and from temperature measurements, the contribution of L2₁ antiphase boundaries evaluated. A calculation of this contribution using pair interchange energies is in good agreement with the experimental results.     

Nucleation of the Al6(Fe,Mn)-to-α-Al–(Fe,Mn)–Si transformation in 3XXX aluminium alloys. II. Transformation in cast aluminium alloys

The nucleation behaviour of the homogenization-induced Al₆(Fe,?Mn)-to-α-Al–(Fe,?Mn)–Si transformation is investigated in a companion paper to part I (a study with roll-bonded diffusion couples). Diffusion experiments using silicon-coated Al–0.53?wt%?Fe–1.02?wt%?Mn alloy blocks allow control of the thermodynamic driving force for transformation within a microstructure typical of a cast ingot. As expected, this microstructure appears to give ready and yet stochastic nucleation as silicon diffuses into the alloy sections. In addition, transmission electron microscopy is used to analyse partially transformed particles in heat-treated alloy samples of fixed silicon content. This confirms the suggestion made in part I that the transformation preferentially nucleates at matrix grain/cell boundaries. Nucleation theory suggests this results from the ability of the boundaries to relieve volume changes associated with the nucleation event.     

Structural asymmetry in liquid Fe–Si alloys

The thermodynamic properties and microscopic structure of liquid Fe–Si alloys at 1873 K were studied by using the regular associated solution model. The model was utilized to determine the complex concentration in a regular associated solution of Fe, Si and Fe₂Si. The complex concentration was then used to calculate the integral excess free energy of mixing, activity, concentration fluctuations in the long-wavelength limit, S_CC (0), and the Warren–Cowley short-range parameter α ₁. The analysis suggests that heterocoordination leading to the formation of complex Fe₂Si is likely to exist in the liquid and is of a strongly interacting nature. The theoretical analysis reveals that the alloy is more ordered towards the Fe-rich region. The observed asymmetry in the properties of mixing of Fe–Si alloys in the molten state is successfully explained on the basis of the regular associated solution model.