Al-Mg-Si alloys with total solute contents ranging from 0.8 to 1.4 wt.% were solutionised, quenched and then artificially aged (AA) at 180 °C, after which positron annihilation lifetime spectroscopy was applied to obtain information about precipitation and vacancy evolution during preceding ageing. Hardness and electrical resistivity measurements were carried out to complement these measurements. AA was carried out in four different heating media, which allowed for varying the heating rate from 2.4 K/s to 170 K/s. The main result of the study is that there is a competition between vacancy losses and precipitation. Any precipitation taking place during quenching or during heating to the AA temperature helps to prevent vacancies from going to sinks and allows them to assist in solute clustering. Higher solute content, slower heating to 180 °C and natural pre-ageing before AA were found to have a comparable effect.
The effect of Mg content on the natural ageing of Al-Cu-Li-(Mg) alloys has been investigated on a compositionally graded material made by linear friction welding, allowing to probe Mg contents between 0 and 0.4 at.%. High throughput time-and space-resolved characterization of natural ageing kinetics has been achieved using small-angle X-ray scattering, supplemented by differential scanning calorimetry. Natural ageing results mainly in the formation of Cu-rich clusters whose characteristics strongly depend on the presence of Mg. Larger precipitates of 2 nm size also form to a lesser extent abov…
Ageing mechanisms of the U-7\%wtNb alloy have been investigated on samples exposed to temperatures of 150$^{o}$C for up to 5000\,hours. A variety of surface and bulk analytic techniques have been used to investigate microstructural, chemical and crystallographic changes. Characterisation of the alloy's evolving behaviour was carried out through secondary electron microscopy, energy dispersive x-ray spectroscopy, electron backscatter diffraction, transmission electron microscopy and x-ray diffraction. Vickers hardness testing showed evidence of a strong thermal hardening relationship with agein…
In this study atom probe tomography was used to investigate the microstructure of AA2198 (Al-1.35Cu-3.55Li-0.29Mg-0.08Ag) over a range of ageing conditions to examine the evolution of phases in the alloy, in particular aiming to reveal the nucleation mechanism of the strengthening T1 phase, which has been under debate for decades. T1 precursor phases were observed from early ageing, a significant number of which were connected to solute-enriched dislocations. Ag and Mg segregation to T1 interfaces was convincingly observed when the plates were oriented perpendicular to the probing direction, w…
Ageing mechanisms of the U-5\,\%wtNb system have been investigated on samples exposed to temperatures of 150$\,^{\circ}$C for up to 5000\,hours. A variety of surface and bulk analytic techniques have been used to investigate phase, chemical and crystallographic changes. Characterisation of microstructural evolution was carried out through secondary electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM) and x-ray diffraction (XRD). This investigation suggests crystallographic defects such as twinning…
Room temperature solute clustering in aluminium alloys, or natural ageing, despite its industrial relevance, is still subject to debate, mostly due to its experimentally challenging nature. To better understand the complex multi-constituents' interactions at play, we have studied ternary and quaternary subsystems based on the Al-Cu alloys, namely Al-Cu-Mg, Al-Cu-Li and Al-Cu-Li-Mg. We used a recently introduced correlative technique using small-angle neutrons and X-ray scattering (SANS and SAXS) to extract the chemically resolved kinetics of room temperature clustering in these alloys, which w…
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 \approx 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…
The chemical enrichment/ordering of solute atoms in Mg matrix are crucial to understand the formation mechanism of long-period stacking ordered (LPSO) structures. In this study, three-dimensional distribution of solute elements in an Mg-Zn-Gd alloy during ageing process is quantitatively characterized by three-dimensional atom probe (3DAP) tomography. Based on the radius distribution function, it is found that Zn-Gd solute pairs in Mg matrix appear mainly in two peaks at early stage of ageing and the separation distance between Zn and Gd atoms is well rationalized by the first-principles calcu…
The influence of hydrogen on the structural evolutions of an Al-Mg-Si alloy during natural and artificial ageing was investigated experimentally. The aim of the study was a better understanding of interactions between hydrogen and crystalline defects and especially vacancies. Experimental data demonstrate that during natural ageing in hydrogen environment, the hardening response is delayed. This is attributed to a slower recovery of excess vacancies linked to a lower mobility. To confirm and quantify the influence of hydrogen on the vacancy migration energy, artificial ageing was carried out i…
The Ni-based superalloy Alloy 718 is used in aircraft engines as high-pressure turbine discs and must endure challenging demands on high-temperature yield strength, creep-, and oxidation-resistance. Nanoscale $γ^{\prime}$- and $γ^{\prime \prime}$-precipitates commonly found in duplet and triplet co-precipitate morphologies provide high-temperature strength under these harsh operating conditions. Direct ageing of Alloy 718 is an attractive alternative manufacturing route known to increase the yield strength at 650 $^°$C by at least +10 $\%$, by both retaining high dislocation densities and chan…
We report on a quantitative investigation into the effect of size and distribution of rod-shaped β' precipitates on strength and ductility of a Mg-Zn alloy. Despite precipitation strengthening being crucial for the practical application of magnesium alloys this study represents the first systematic examination of the effect of controlled deformation on the precipitate size distribution and the resulting strength and ductility of a magnesium alloy. Pre-ageing deformation was used to obtain various distributions of rod-shaped β' precipitates through heterogeneous nucleation. Alloys were extruded…
The effects of ageing at 800 $^\circ$C on the properties of the IRIS alloy (Ti$_{49.9}$Al$_{48}$W$_2$B$_{0.1}$) are studied. The initial microstructure of this alloy densified by Spark Plasma Sintering (SPS) is mainly composed of lamellar colonies which are surrounded by $γ$ grains. The evolutions of the alloy strength and creep resistance resulting from this ageing treatment are measured by the related mechanical tests. The microstructural changes are investigated by scanning and transmission electron microscopies and by X-ray diffraction. The main structural evolutions consist in a shrinkage…
The effect of pre-ageing deformation on the size and distribution of beta-prime precipitates and subsequently on the resulting strength and ductility have been measured in a Mg-3.0at.%Zn-0.5at.%Y alloy. The alloy was extruded and then subjected to a T8 heat treatment comprised of a solution-treatment, cold-work and artificial ageing. Extrusion was used to introduce texture, ensuring that deformation occurred via slip rather than twinning. Samples were subjected to controlled uniaxial deformation and then isothermally aged to peak hardness. Precipitate length, diameter and number density were m…
The consequences of hydrogen on the formation and growth of GP zones during natural ageing in an Al-5Cu alloy is investigated experimentally down to the atomic scale and numerically using ab initio calculations. As observed through scanning/transmission electron microscopy, the hardening kinetic is delayed due to a slower growth of GP zones during natural ageing when hydrogen is incorporated. According to ab initio calculations, the delayed hardening results from hydrogen trapped in vacancies that reduce significantly the diffusion coefficient of copper and the self diffusion of aluminium. Thi…
This work presents a detailed investigation into the effect of a low Cu addition (0.01 at.%) on precipitation in an Al-0.80Mg-0.85Si alloy during ageing. The precipitate crystal structures were assessed by scanning transmission electron microscopy combined with a novel scanning precession electron diffraction approach, which includes machine learning. The combination of techniques enabled evaluation of the atomic arrangement within individual precipitates, as well as an improved estimate of precipitate phase fractions at each ageing condition, through analysis of a statistically significant nu…
We apply a combinatorial approach to study the influence of Mg concentration on the precipitation kinetics in an Al-Cu-Li alloy using a diffusion couple made by linear friction welding. The precipitation kinetics is monitored in the composition gradient material using simultaneous space and time-resolved in-situ small-angle X-ray scattering measurements during ageing, and the strengthening of the precipitates is evaluated by micro-hardness profiles. This data provides an evaluation of the amount of Mg necessary to promote precipitation of the T1-Al2CuLi phase.
The precipitation microstructure of the γ' (AlAg2) intermetallic phase has been examined in aluminium-silver-copper alloys. The microstructure developed in an Al-0.90at.%Ag-0.90at.%Cu alloy was significantly different from that reported for binary Al-Ag alloys. The orientation relationship between the matrix and precipitate was unchanged; however, the γ' phase formed as aggregates with a two-dimensional open assemblies. Each such assembly contained two variants of the γ' phase alternately arranged to form a faceted elliptical unit. The θ' (Al2Cu) phase formed on these assemblies after further …
The close-range interaction of dislocations and solute clusters in the Al-Mg binary system is studied by means of atomistic simulations. We evaluate the binding energy of dislocations to the thermodynamically stable solute atmospheres that form around their cores, at various temperatures and average solid solution concentrations. A measure of the cluster size that renders linear the relationship between the binding energy and the cluster size is identified. It is shown that as the temperature increases the representative cluster dissolves following an Arrhenius law. The corresponding activatio…
We have studied the effect of ageing within the miscibility gap on the electric, magnetic and thermodynamic properties of a non-stoichiometric Heusler Cu-Al-Mn shape-memory alloy, which undergoes a martensitic transition from a $bcc$-based ($β$-phase) towards a close-packed structure ($M$-phase). Negative magnetoresistance which shows an almost linear dependence on the square of magnetization with different slopes in the $M$- and $β$-phases, was observed. This magnetoresistive effect has been associated with the existence of Mn-rich clusters with the Cu$_2$AlMn-structure. The effect of an appl…
While producing comparable efficiencies and showing similar properties when probed by conventional techniques, such as Raman, photoluminescence and X-ray diffraction, two thin film solar cell materials with complex structures, such as quaternary compound CZTSe, may in fact differ significantly in their microscopic structures. In this work, laser induced modification Raman spectroscopy, coupled with high spatial resolution and high temperature capability, is demonstrated as an effective tool to obtain important structure information beyond that the conventional characterization techniques can o…
The harmonic Kanzaki-Krivoglaz-Khachaturyan model of strain-induced interaction is generalized to concentrated size-mismatched alloys and adapted to first-principles calculations. The configuration dependence of both Kanzaki forces and force constants is represented by real-space cluster expansions that can be constructed based on the calculated forces. The model is implemented for the fcc lattice and applied to Cu$_{1-x}$Au$_x$ and Fe$_{1-x}$Pt$_x$ alloys for concentrations $x=0.25$, 0.5, and 0.75. The asymmetry between the $3d$ and $5d$ elements leads to large quadratic terms in the occupati…
We provide a fundamental insight into the microscopic mechanisms of the ageing processes. Using large scale molecular dynamics simulations of the prototypical ferroelectric material PbTiO3, we demonstrate that the experimentally observed ageing phenomena can be reproduced from intrinsic interactions of defect-dipoles related to dopant-vacancy associates, even in the absence of extrinsic effects. We show that variation of the dopant concentration modifies the material's hysteretic response. We identify a universal method to reduce loss and tune the electromechanical properties of inexpensive ce…
Microscopic description in the study of immiscibility and segregating properties of liquid metallic binary alloys has gained a renewed scientific and technological interests during the last eight years for the physicists, metallurgists and chemists. Especially, in understanding the basic mechanisms, from the point of interionic interaction, and how and why segregation in some metallic alloys takes place at and under certain thermodynamic state specified by temperature and pressure. An overview of the theoretical and experimental works done by different authors or groups in the area of segregat…
We study the structural properties and the collective microscopic dynamics of atoms in the amorphous metallic alloy $Ni_{33}Zr_{67}$ at the temperature $T=300K$ by molecular dynamics simulations. The calculated equilibrium structural and dynamical characteristics are compared with the experimental data on neutron diffraction and on inelastic X-ray scattering. We present the interpretation of observed structural relaxation of the microscopic density fluctuations of particles for amorphous metallic alloy in the framework of the recurrent relation approach. The results of theoretical calculations…
Short-range ordering (SRO) tendency for disordered alloys is considered as competition between chemical ordering and geometric (mainly, difference in atomic radius for constituents) effects. Especially for multicomponent (including the so-called high entropy alloys (HEAs) near equiatomic composition), it has been considered as difficult to systematically characterize the SRO tendency only by geometric effects, due mainly to the fact that (i) chemical effects typically plays significant role, (ii) near equiatomic composition, we cannnot classify which elements belong to solute or solvent, and (…
Short-range order (SRO) in disordered alloys is typically interpreted as competition between chemical effect of negative (or positive) energy gain by mixing constituent elements and geometric effects comes from difference in effective atomic radius. Although we have a number of theoretical approaches to quantitatively estimate SRO at given temperatures, it is still unclear to systematically understand trends in SRO for binary alloys in terms of geometric character, e.g., effective atomic radius for constituents. Since chemical effect plays significant role on SRO, it has been believed that pur…
Near-atomic investigation on the elemental redistribution during co-precipitation of nano-sized kappa phase and B2 phase in an Al-alloyed lightweight steel
University of Kassel（卡塞尔大学）；RWTH Aachen University（亚琛工业大学）
"Micro-alloying", referring to the addition of small concentration of a foreign metal to a given metallic glass, was used extensively in recent years to attempt to improve the mechanical properties of the latter. The results are haphazard and nonsystematic. In this paper we provide a microscopic theory of the effect of micro-alloying, exposing the delicate consequences of this procedure and the large parameter space which needs to be controlled. In particular we consider two very similar models which exhibit opposite trends for the change of the shear modulus, and explain the origins of the di…
Zn-Al alloys have become one of the major engineering alloys among commercially available alloys. This study was conducted on eutectoid composition of Zn-Al alloy with an observation of the effect of copper addition. For this purpose, one eutectoid (Zn-22wt%Al) and three other alloys, adding 1wt%, 3wt% and 5wt% copper with this eutectoid composition, were molded in permanent metal mould. Microscopic studies exhibited varied grains which confirmed the formation of different phases. Moreover, the formation of different phases in micro study was supported by XRD analysis. Hardness of the samples …
Both continuous and discontinuous precipitation is known to occur in CuAg alloys. The precipitation of Ag-rich phase has been experimentally investigated by atom probe tomography and transmission electron microscopy after ageing treatment of Cu-5%wtAg at 440$^\circ$C during 30'. Both continuously and discontinuously formed precipitates have been observed. The precipitates located inside the grains exhibit two different faceted shapes: tetrahedral and platelet-shaped precipitates. Dislocations accommodating the high misfit at the interface between the two phases have also been evidenced. Based …
The earlier-developed master equation approach and kinetic cluster methods are applied to study kinetics of L1_0 type orderings in alloys, including the formation of twinned structures characteristic of cubic-tetragonal-type phase transitions. A microscopical model of interatomic deformational interactions is suggested which generalizes a similar model of Khachaturyan for dilute alloys to the physically interesting case of concentrated alloys. The model is used to simulate A1->L1_0 transformations after a quench of an alloy from the disordered A1 phase to the single-phase L1_0 state for a numb…
The kinetics of coherent Cu rich precipitation in Fe-Cu and Fe-Cu-Ni alloys during thermal ageing have been modeled by Atomic Kinetic Monte Carlo method (AKMC). The AKMC is parameterized by existing ab-inito data to treat vacancy mediated diffusion which is depend on local atomic environment. A nonlinear semi-empirical time adjusting method is proposed to rescaled the MC time. The combining AKMC and time adjusting method give a good agreement with experiments and other simulations, including advancement factor and the Cu cluster mobility. Simulations of ternary alloys reveal Ni has a temporal …
The earlier-suggested master equation approach is used to develop the consistent statistical theory of diffusion in alloys using the five-frequency model of FCC alloys as an example. Expressions for the Onsager coefficients in terms of microscopic interatomic interactions and some statistical averages are presented. We discuss methods of calculations of these averages using both the mean-field and the pair-cluster approximation to describe influence of vacancy-solute and solute-solute interactions, and both the nearest-neighbor and the second-shell approximation to describe vacancy correlation…
The long wavelength limit of a recent microscopic phase field crystal (PFC) theory of a binary alloy mix- ture is used to derive an analytical approximation for the segregation coefficient as a function of the interface velocity, and relate it to the two-point correlation function of the liquid and the thermodynamic properties of solid and liquid phases. Our results offer the first analytic derivation of solute segregation and solute drag de- rived from a microscopic model, and analytically support recent molecular dynamics and fully numerical PFC simulations. Our analytical result also provid…
Impurity diffusion coefficients are entirely obtained from a low cost classical molecular statics technique (CMST). In particular, we show how the CMST is appropriate in order to describe the impurity diffusion behavior mediated by a vacancy mechanism. In the context of the five-frequency model, CMST allows to calculate all the microscopic parameters, namely: the free energy of vacancy formation, the vacancy-solute binding energy and the involved jump frequencies, from them, we obtain the macroscopic transport magnitudes such as: correlation factor, solvent-enhancement factor, Onsager and diff…
Impurity diffusion coefficients are entirely obtained from a low cost classical molecular statics technique (CMST). In particular, we show how CMST is appropriate in order to describe the impurity diffusion behavior mediated by a vacancy mechanism. In the context of the five-frequency model, CMST allows to calculate all the microscopic parameters, namely: the free energy of vacancy formation, the vacancy-solute binding energy and the involved jump frequencies, from them, we obtain the macroscopic transport magnitudes such as: correlation factor, solvent-enhancement factor, Onsager and diffusio…
Composite quantum materials are the ideal examples of multifunctional systems which simultaneously host more than one novel quantum phenomenon in physics. Here, we present a combined theoretical and experimental study to demonstrate the presence of an extremely large exchange bias in the range 0.8 T - 2.7 T and a fully compensated magnetic state (FCF) in a special type of Pt and Ni doped Mn$_3$In cubic alloy. Here, oppositely aligned uncompensated moments in two different atomic clusters sum up to zero which are responsible for the FCF state. Our Density functional theory (DFT) calculations sh…
We present the results of a systematic study using the density functional theory (within the local density approximation) of the effects of biaxial strain and composition on the self-diffusion of Si and Ge in SiGe alloys diffusing by a vacancy mechanism. The biaxial strain dependence of the vacancy formation energy was reconfirmed with previous calculations. The effect of biaxial strain on the interaction potential energy between a substitutional Ge atom and a vacancy was calculated. These calculations were used to estimate the change in the activation energy (due to biaxial strain) for the se…
Insights into hydrogen-induced vacancy stability and creep in chemically complex alloys
Ames National Laboratory, US Department of Energy, Iowa State University（艾姆斯国家实验室，美国能源部，爱荷华州立大学）；Los Alamos National Laboratory（洛斯阿拉莫斯国家实验室）；Department of Materials Science & Engineering, Iowa State University（爱荷华州立大学材料科学与工程系）
A classical molecular static technique (CMST) and DFT calculations using SIESTA, are employed here to characterize the self diffusion and the tracer solute diffusion in the bulk of BCC diluted $FeCr$ alloy driven by both vacancy and interstitial migration. For the first time in the literature, a six-frequency model (developed by Okamura and Allnatt) involved in a second nearest neighbor binding approach is adapted for calculations in a real system. We obtain microscopic parameters, namely: i) the free energy of vacancy formation and the vacancy-solute binding energy, ii) the involved jump freq…
Sustained external forces acting on a material provide additional mechanisms to evolve the state of the system, and these mechanisms do not necessarily obey the microscopic detailed balance. Therefore, standard methods to compute the thermodynamic and kinetic properties do not apply in such driven systems. The competition between these mechanisms and the standard thermally activated jumps leads to non-equilibrium steady states. We extend the Self-Consistent Mean Field theory to take into account forced atomic relocations (FARs) as a model of these additional kinetic mechanisms. The theory is a…
Understanding the mechanisms which relate properties of liquid and solid phases is crucial for fabricating new advanced solid materials, such as glasses, quasicrystals and high-entropy alloys. Here we address this issue for quasicrystal-forming Al-Cu-Fe alloys which can serve as a model for studying microscopic mechanisms of quasicrystal formation. We study experimentally two structural-sensitive properties of the liquid -- viscosity and undercoolability -- and compare results with \textit{ab initio} investigations of short-range order (SRO). We observe that SRO in Al-Cu-Fe melts is polytetrah…
