Solute Atom Clusters Research Articles

A Concept of Local Coordination Number for the Characterization of Solute Clusters within Atom Probe Tomography Data.

Identifying clusters of solute atoms in a matrix of solvent atoms helps to understand precipitation phenomena in alloys, for example, during the age hardening of certain aluminum alloys. Atom probe tomography datasets can deliver such information, provided that appropriate cluster identification routines are available. We investigate algorithms based on the local composition of the neighborhood of solute atoms and compare them with traditional approaches based on the local solute number density, such as the maximum separation distance method. For an ideal solid solution, the pair correlation functions of the kth nearest solute atom in the coordination number representation are derived, and the percolation threshold and the size distribution of clusters are studied. A criterion for selecting optimal control parameters based on maximizing the phase separation by the degree of clustering is proposed for a two-phase system. A map of phase compositions accessible for cluster analysis is constructed. The coordination number approach reduces the influence of density variations commonly observed in atom probe tomography data. Finally, a practical cluster analysis technique applied to the early stages of aluminum alloy aging is described.

Approaching 1 GPa Ultra‐High Tensile Strength in a Nanostructured Al–Zn–Mg–Cu–Zr–Sc Alloy Prepared by Severe Plastic Deformation

Alloy composition and heat treatment processes have limited possibility to enhance ultra‐high strength of aluminum alloys, which restricts their widespread application in lightweight equipment. Consequently, high‐density dislocations and grain refinement are suggested to strengthen ultra‐high strength aluminum alloys. Herein, a novel nanostructured Al–Zn–Mg–Cu–Zr–Sc (AZMCZS) alloy with homogeneous microstructure is prepared through the synergistic processing of hot extrusion and high‐pressure torsion. Additionally, the microstructures and strengthening mechanisms of the nanostructured Al alloy are analyzed. It is observed that the ultimate tensile strength of the nanostructured Al alloy reaches nearly 1 GPa, and the elongation of the alloy is 1.9%. The nanostructured Al alloy mainly consists of nanoscale grains (≈117.7 nm), high‐density dislocations (2.4 × 1015 m−2), nano‐sized precipitates (the size of 20–51 nm), and solute atom clusters (≈3 nm). The multiple strengthening mechanisms of the nanostructured Al alloy are revealed in terms of grain refinement, dislocations, precipitates, and solute atom clusters. Grain refinement and dislocation strengthening show superior outcomes and are considered to be the predominant strengthening mechanisms. These findings demonstrate that this nanostructural architecture offers a new way to design super‐strength metals and alloys by effectively controlling the processing regime of severe plastic deformation.

Solute clustering and its role in a titanium alloy made by laser powder bed fusion

In recent years, atomic clusters and composition undulation have been observed in a number of concentrated solid-solution alloys and were found to be beneficial for strength-ductility synergy. Some reports are also available on the observation of atomic clusters in body-centred cubic metastable β titanium alloys but the role of these atomic clusters in mechanical property development is unclear. In this study, we report the formation of solute atomic clusters in an additively manufactured and solution-treated metastable titanium alloy and investigate their role in deformation and strengthening mechanisms. It was found that the atomic clusters together with ultrafine ω precipitates present in the material effectively pin dislocation motion and contribute to an ultrahigh yield strength. The interaction between dislocations and solute atomic clusters leads to an increased shear stress necessary for dislocation motion. The atomic clusters and the resulting chemical undulation generate pronounced atomic strain fluctuations and distortions with alternating tensile and compressive strain fields, which lead to large local internal stresses and thus resistance to dislocation glide. Cross slip has also been frequently observed in the additively manufactured and solution-treated metastable titanium alloys, which is beneficial for strain hardening and ductility. We also reveal that thermal cycling in the alloy can lead to a significant influence on the microstructural evolution. During solidification and cooling upon laser powder bed fusion, only β and athermal ω precipitates form. With repetitive thermal cycling, the microstructure transforms into α + β grains together with isothermal ω particles. The present findings suggest that solute atom clustering can be introduced through proper selection of solute elements, providing a new strengthening mechanism for titanium alloys.

Microstructure-Informed Prediction of Hardening in Ion-Irradiated Reactor Pressure Vessel Steels

Ion irradiation combined with nanoindentation is a promising tool for studying irradiation-induced hardening of nuclear materials, including reactor pressure vessel (RPV) steels. For RPV steels, the major sources of hardening are nm-sized irradiation-induced dislocation loops and solute atom clusters, both representing barriers for dislocation glide. The dispersed barrier hardening (DBH) model provides a link between the irradiation-induced nanofeatures and hardening. However, a number of details of the DBH model still require consideration. These include the role of the unirradiated microstructure, the proper treatment of the indentation size effect (ISE), and the appropriate superposition rule of individual hardening contributions. In the present study, two well-characterized RPV steels, each ion-irradiated up to two different levels of displacement damage, were investigated. Dislocation loops and solute atom clusters were characterized by transmission electron microscopy and atom probe tomography, respectively. Nanoindentation with a Berkovich indenter was used to measure indentation hardness as a function of the contact depth. In the present paper, the measured hardening profiles are compared with predictions based on different DBH models. Conclusions about the appropriate superposition rule and the consideration of the ISE (in terms of geometrically necessary dislocations) are drawn.

Natural aging and vacancy trapping in Al-6xxx

Undesirable natural aging (NA) in Al-6xxx delays subsequent artificial aging (AA) but the size, composition, and evolution of clustering are challenging to measure. Here, atomistic details of early-stage clustering in Al–1%Mg–0.6%Si during NA are studied computationally using a chemically-accurate neural-network potential. Feasible growth paths for the preferred beta '' precipitates identify: dominant clusters differing from beta '' motifs; spontaneous vacancy-interstitial formation creating 14–18 solute atom beta ''-like motifs; and lower-energy clusters requiring chemical re-arrangement to form beta '' nuclei. Quasi-on-lattice kinetic Monte Carlo simulations reveal that 8–14 solute atom clusters form within 1000 s but that growth slows considerably due to vacancy trapping inside clusters, with trapping energies of 0.3-0.5 eV. These findings rationalize why cluster growth and alloy hardness saturate during NA, confirm the concept of “vacancy prisons”, and suggest why clusters must be dissolved during AA before formation of beta ''. This atomistic understanding of NA may enable design of strategies to mitigate negative effects of NA.Graphical abstractEnergy and RMS vacancy displacement vs simulation time for three different kMC simulations of Al matrix containing Mg (green) and Si atoms(orange), and 1 vacancy (pink). Geometries extracted from the third trajectory at four different times show solute clustering and vacancy trapping.

Modelling the spatial evolution of excess vacancies and its influence on age hardening behaviors in multicomponent aluminium alloys

Excess vacancies play crucial roles in the precipitation of age-hardening precipitates in aluminium alloys, but their spatial evolution across grains during heat treatments is less known. In this work, a numerical model is developed to predict the spatial evolution of non-equilibrium excess vacancies during cooling from solution treatment and during ageing heat treatments of multicomponent aluminium alloys. A finite volume scheme is applied to derive the spatial distribution of vacancy site fraction across grains by solving the diffusion equations of vacancies under the influence of solute elements. Binding energies between solute atoms and vacancies predicted by first-principles calculations has been used to handle the trapping of excess vacancies by solute atoms and atom clusters. The annihilation rates of excess vacancies at grain boundaries and at dislocation jogs have been derived based on a rigorous description of the annihilation mechanisms of vacancies. The evolution of the density of dislocation jogs due to vacancy annihilation has been taken into account. The model is successfully applied to interpret the age hardening behaviors of experimental alloys subjected to different thermomechanical processing conditions. This model will help to reach a deeper understanding of the roles of excess vacancies in precipitation kinetics and therefore is important to further optimize thermomechanical processing parameters and alloy composition to improve the macroscopic mechanical properties of age hardening aluminium alloys.

Effect of Hf on the microstructure and martensitic transformation behavior in Ti–Pd–Hf alloy

We investigated the microstructure and the crystallography of martensite variants in Ti–Pd–Hf alloy using electron microscopy. The martensitic transformation temperature decreased with increasing amount of Hf substituted into the Ti50−xPd50Hfx alloy. No indication of a martensitic transformation was observed in the as-quenched Ti25Pd50Hf25 and Ti10Pd50Hf40 alloys, even when the samples were cooled to 150 K. The Ti40Pd50Hf10, Ti35Pd50Hf15, and Ti30Pd50Hf20 alloys were composed of a B19 orthorhombic phase having plate-like habit-plane variants consisting of both major and minor correspondence variants several hundred nanometers in width and several tens of micrometers in length at room temperature. Lattice-invariant shear of these alloys was a {111}B19 Type I twin. A solution-treated sample of the Ti25Pd50Hf25 alloy consisted of a B2 cubic matrix with local atomic displacement and lattice distortions, and rounded H-phase particles several tens of nanometers in diameter were precipitated inside the B2 matrix upon aging of the specimen at 823 K for 10.8 ks. The as-quenched Ti10Pd50Hf40 alloy contained rounded H-phase particles several tens of nanometers in diameter embedded in a B2 matrix at room temperature. The martensitic transformation temperature in the Ti50−xPd50Hfx alloy was drastically decreased by both the fully coherent nanosized H-phase particles and the short-range order originating from clustering of solute atoms.

Abnormal chemical composition fluctuations in multi-principal-element alloys induced by simple cyclic deformation

• We report for the first time that the amplitude of the concentration wave (i.e., the unique composition fluctuations) can be mechanically tailored under cyclic deformation in a well-known Cantor alloy. • Atomic-scale EDS mapping reveals that cyclic deformation may dynamically induce the clustering of solute atoms with a size of 1–3 nm, thus resulting in a higher concentration wave amplitude. • The concentration wave promotes strong interactions between dislocations and local solute clusters. The strength enhancement from the mechanically induced composition fluctuations was quantified to be as high as ∼70 MPa, about one-third of the yield strength of the alloy without pre-deformation. High entropy alloys exhibit excellent combination of mechanical properties because of the unique composition fluctuations, termed as ‘concentration wave’. The concentration wave was closely related to multiple aspects, including the fluctuation of local strain energy, local atomic environment, electronegativity, etc. Here we report for the first time that the amplitude of the concentration wave can be mechanically tailored under cyclic deformation in a well-known Cantor alloy. Atomic-scale energy-dispersive X-ray spectroscopy (EDS) mapping reveals that cyclic deformation may dynamically induce the clustering of solute atoms with a size of 1–3 nm, thus resulting in a higher concentration wave amplitude. The concentration wave promotes strong interactions between dislocations and local solute clusters. Aside from the typical Taylor strengthening contribution due to the presence of isolated dislocations, the strength enhancement from the mechanically induced composition fluctuations was quantified to be as high as ∼70 MPa, about one-third of the yield strength of the alloy without pre-deformation. This opens up a novel strategy of designing high strength alloys by tailoring solute configurations.

Dynamic Interaction between Dislocation and Irradiation-Induced Defects in Stainless Steels during Tensile Deformation

A series of in-situ transmission electron microscopy (TEM) observations during tensile deformation were conducted on the ion-irradiated stainless steel. The jerky motion of dislocations appeared, and dislocations were pinned and depinned at the defects through the in-situ TEM observation. The jump distance traveled by dislocation was measured and discussed as the mean interval of defects interacting with the dislocation motion. Microstructural information of irradiation defects such as obstacle interval was obtained by TEM and atom probe tomography (APT), and the type of pinning site was identified. It was found that Frank loops and black dots were irradiation defects that strongly interacted with dislocations. It was suggested that solute atom clusters act as weak obstacles for dislocations in the dynamic interaction behavior with dislocation motion.

Mechanical performance improvement of Al–Cu–Mg using various thermomechanical treatments

A thermomechanical treatment (TMT) geared to stimulate solute atom clustering was devised to achieve a comprehensive balance of engineering properties in an Al–Cu–Mg alloy. The effect of the TMT on the microstructure and properties of an AA2524 like Al–Cu–Mg alloy were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and atom probe tomography (APT) along with tensile testing and fatigue crack growth testing. Our goal was to exceed threshold levels for fatigue crack growth (FCG) resistance, ductility and strength, using the T3 condition as a benchmark. During the TMT, dislocations and vacancies were introduced by solution treatment, quenching and pre-ageing, followed by asymmetric rolling. This enables short-circuit diffusive pathways that facilitate the formation of Mg–Cu co-clusters that effectively regulate the subsequent precipitation and influence mechanical properties. The contribution to critically resolved shear stress (CRSS) of these clusters of TMT alloys was significantly higher than the T3 state. It is proposed that Goss-grain orientations and shear textures introduced by the asymmetric rolling are also partly responsible for the enhancement of FCG resistance. The potential for solute clusters to contribute to fatigue properties is discussed in terms of the cyclic deformation shearing them, thus liberating their solute which can then bind with vacancies that would otherwise condense at the crack tip.

Effect of Neutron Flux on an Irradiation-Induced Microstructure and Hardening of Reactor Pressure Vessel Steels

The existing knowledge about the effect of neutron irradiation on the mechanical properties of reactor pressure vessel steels under reactor service conditions relies to a large extent on accelerated irradiations realized by exposing steel samples to a higher neutron flux. A deep understanding of flux effects is, therefore, vital for gaining service-relevant insight into the mechanical property degradation. The existing studies on flux effects often suffer from incomplete descriptions of the irradiation-induced microstructure. Our study aims to give a detailed picture of irradiation-induced nanofeatures by applying complementary methods using atom probe tomography, positron annihilation, small-angle neutron scattering and transmission electron microscopy. The characteristics of the irradiation-induced nanofeatures and the dominant factors responsible for the observed increase of Vickers hardness are identified. Microstructural changes due to high flux conditions are smaller nm-sized solute atom clusters with almost the same volume fraction and a higher concentration of vacancies and sub-nm vacancy clusters compared to low flux conditions. The results rationalize why pronounced flux effects on the nanofeatures, in particular on solute atom clusters, only give rise to small or moderate flux effects on hardening.

Extreme shear deformation enables ultra-fast riveting of high strength aluminum alloys

Dispersed nano-precipitates strengthen high-strength aluminum (Al) alloys but reduce ductility and formability. Joining these alloys with conventional impact (or driven) riveting has long been a challenge because the rivets may crack in ambient conditions. Rotating hammer riveting (RHR) was developed to rivet fully hardened high-strength Al alloys 2024-T351 and 7075-T6. RHR eliminates the need to soften 7075 rivets by preheating or to store 2024 rivets at low temperature to preserve the annealed condition. Avoiding cracked rivet heads and shanks during RHR is attributed to high-strain-rate plastic deformation, which promotes dynamic recrystallization of grains and amorphization of second phases; this mitigates stress concentration and prevents microvoids. Meanwhile, the coherent solute atom clusters in the Al matrix are sheared by dislocation movement, not coarsened, because the thermal cycle is short (10−1 s). RHR obviates time- and cost-intensive prior and post-processing heat treatments, achieving high integrity between riveted and assembled components.

Characterization of hardening behavior of carbon steels at low temperature irradiations

• Embrittlement factors of carbon steels irradiated at low temperature were fine dislocation loops and solute clusters of Mn-Si-Cu atoms. • Carbon steels and their weld metals containing high concentrations of Cu, Mn and Si had relatively high radiation hardening due to promotion of solute atom clustering. • Low temperature irradiation resulted in higher radiation hardening due to the higher number density of dislocation loops, despite the lower number density of solute clusters. • Low dose rate irradiation (electron irradiation) resulted in greater radiation hardening due to the higher number density of solute clusters than high dose rate irradiation (ion irradiation) did. Overpacks used for geological disposal of high-level radioactive waste will be irradiated by neutrons and γ rays with very low dose rate for a long time. A possible way to predict effects of such radiations is that microstructure changes under the expected irradiation conditions are estimated by both experiments and analytical modeling and then the changes in hardness and fracture toughness from the microstructure changes are estimated. In the present study, carbon steels, which are one of the candidate materials for overpacks, model alloys and a weld of carbon steel were irradiated with either Fe ions or electrons at 90 or 290 °C, and then the microstructure and hardness were investigated to gain an understanding about embrittlement factors of carbon steels and effects of both material composition and irradiation conditions (temperature, dose rate) on radiation-induced changes in microstructure and hardness. Formations of fine dislocation loops and solute clusters containing Mn, Si and Cu atoms were confirmed by microstructure analysis using transmission electron microscopy and atom probe tomography. Hardness increase was well correlated with the evolution of dislocation loops and solute clusters, indicating that these defects are embrittlement factors of carbon steels. Higher radiation hardening was confirmed for the materials containing a high density of Mn, Si and Cu, and the irradiation conditions of low temperature and low dose rate.

The role of silicon on solute clustering and embrittlement in highly neutron-irradiated pressurized water reactor surveillance test specimens

• The role of Si content on irradiation embrittlement was clarified. • Solute atom clusters of highly neutron-irradiated Japanese pressurized water reactor surveillance test specimens were analyzed by atom probe tomography. • The cluster radius and number density decreased and increased, respectively, with increasing Si content, resulting in a constant volume fraction of SCs. • Increase in Si reduces the degree of irradiation embrittlement. This is consistent with the results of our previous study based on Bayesian statistical analysis. Solute clusters (SCs) formed in pressurized water reactor surveillance test specimens neutron-irradiated to a fluence of 1 × 10 20 n/cm 2 were analyzed via atom probe tomography to understand the effect of silicon on solute clustering and irradiation embrittlement of reactor pressure vessel steels. In high-Cu bearing materials, Cu atoms were aggregated at the center of cluster surrounded by the Mn, Ni, and Si atoms like a core-shell structure. In low-Cu bearing materials, Mn, Ni, and Si atoms formed cluster and these solutes were not comprised core-shell structure in SCs. While the number of Cu atoms in clusters was decreased with decreasing nominal Cu content, the number of Si atoms had clearly increased. The cluster radius ( r ) and number density ( N d ) decreased and increased with increasing nominal Si content, respectively. The shift in the reference temperature for nil-ductility transition ( ΔRT NDT ) showed a good correlation with the square root of volume fraction ( V f ) multiplied by ( V f × r ) . The negative relation between the nominal Si content and ΔRT NDT indicated that increasing of nominal Si content reduces the degree of embrittlement.

Irradiation hardening of stainless steel model alloy after Fe-ion irradiation and post-irradiation annealing treatment

Microstructural observation with atom probe tomography, transmission electron microscopy, and mechanical examination with a nano-indenter were performed on stainless steel model alloy that had been irradiated with Fe ions and subjected to post-irradiation annealing treatment (PIA). Significant irradiation hardening occurred in the as-irradiated specimen and irradiation hardening recovery occurred at 400 °C of cumulative PIA, Tiny black dots, Frank loops and Ni-Si clusters formed in the as-irradiated specimen and their recovery was observed with the cumulative PIA. A classic dispersed-barrier hardening model was used to evaluate irradiation hardening connected to microstructural information by applying the density and size of defect variants. Ni-Si clusters and Frank loops contributed substantially to the increase of irradiation hardening, whereas the black dots contributed little for the stainless steel model alloy. The barrier strength factor of Ni-Si clusters, αSC, was obtained as 0.029 and 0.015 for two different obstacle strength model, which suggests that an individual Ni-Si cluster is a weak barrier obstacle to mobile dislocation on the dispersed-barrier hardening model, but that the dense formation of Ni-Si clusters controls irradiation hardening behavior. A quantitative analysis was performed of the increase in strength from the Ni-Si clusters that was caused by coherency strains, and an irradiation hardening mechanism for the stainless steel, including the solute atom clusters, is discussed.

Aluminum Alloys: Solute Atom Clusters and Their Strengthening

Aluminum Alloys: Solute Atom Clusters and Their Strengthening

Natural Aging Effect of Al-20Zn-3Cu Alloy on Mechanical Properties and Its Relation to Microstructural Change

We investigate the effect of the natural age-hardening response of the Al-20Zn-3Cu alloy with natural aging times up to 12 months. The ultimate tensile strength of the Al-20Zn-3Cu alloy is drastically enhanced from 308 to 320 MPa after 2 months and from 320 to 346 MPa after 9 months. Then, natural age hardening becomes saturated after 9 months. A microstructural investigation reveals that the natural age-hardening mechanism is mainly induced by the diffusion of the Zn element. First, a rapid decrease in the volume fraction of the eutectoid lamellae (α-Al+η-Zn) is observed at the early stage of natural aging, leading to an increase in the tensile strength. This originates from the relatively high diffusivity of Zn due to its low melting temperature. Then, the diffusion of Zn into the Al matrix induces clusters of solute atoms that enhance the growth rate of the nanoprecipitates formed in the Al matrix. As a consequence, the tensile strength of the natural-aged Al-20Zn-3Cu alloy increases drastically after 9 months, whereas the ductility is significantly degraded.

Fatigue and dynamic aging behavior of a high strength Al-5024 alloy fabricated by laser powder bed fusion additive manufacturing

A high strength Al-5024 alloy containing Sc and Zr with a bi-modal microstructure consisting of fine equiaxed and coarse columnar grains was successfully fabricated by laser powder bed fusion (LPBF) additive manufacturing. The formation of the bi-modal microstructure was mainly due to both the formation of primary Al3Sc precipitates that act as nucleation sites and the steep temperature gradient during LPBF. By simulating the thermal field of a single melt pool, the formation mechanism of the bi-modal microstructure was explained. It was found by simulation that a solidification interface velocity less than 110 mm/s was beneficial to the nucleation of Al3Sc precipitates and, hence, facilitated the formation of a fine grain microstructure. Applying different heat treatments revealed a trade-off trend between yield strength and ductility as a function of the heat treatment time, and a correlation in fatigue life and yield strength was observed, both of which were closely related to the status of the secondary Al3Sc precipitates. The highest ultimate tensile strength of 450 MPa and corresponding 107 cycle fatigue strength of 105 MPa were achieved after hot isostatic pressing for 4 h at 325 °C with 100 MPa pressure. Dynamic strain aging was found to occur in both as-built and some heat treated samples, which was related to magnesium (Mg) solute atom clustering attributed to: (i) the formation of a diffuse “Mg wall” due to the repetitive melting and rapid cooling in LPBF, and (ii) the growth of intragranular (Al3Sc) and intergranular precipitates (Fe-, Mn-rich) during subsequent heat treatment, thereby leading to an increasing number of misfit dislocations that promote the formation of Mg atom clusters.

A Mechanistic Study of Clustering and Diffusion of Molybdenum and Rhenium Atoms in Liquid Sodium

Liquid Na is widely used as the heat transfer medium in high-temperature heat pipes based on Mo-Re alloys. In this study, ab initio molecular dynamics are employed in order to understand the interactions between the Na solvent and Mo or Re solute in the liquid phase. Both the temperature and concentration effects on the clustering and diffusion behaviors of solute atoms are investigated. It is found that Mo2 and Re2 dimers can be stabilized in liquid Na, and the higher temperature leads to a stronger binding force. Pure Re and Mo-Re mixed solutes can form tetramers at the highest concentration. However, for the pure Mo solute, Mo4 is not observed. The diffusivities of a single solute atom and clusters are calculated. It is found that the Mo species diffuse faster than the Re species, and the diffusivity decreases as the cluster size increases.

Flow behaviors and deformation mechanism of WQ-tempered Al–Li alloy at cryogenic temperatures

Abstract Cryogenic forming is a promising technique for fabricating complex components using high-strength aluminum alloys. In this work, the flow behaviors and microstructure evolution of a WQ-tempered (solution treatment followed by water quenching) 2195 Al–Li alloy was studied by uniaxial tension tests from −196 to 25 °C and strain rates from 2.5 × 10−4 to 1 × 10−2 s−1. The results showed that the ductility gradually increased after decreasing the deformation temperature, while the strain rate had a limited effect on the ductility. Serrated flow caused by dynamic strain aging occurred from −60 to 25 °C, which increased the flow stress due to additional pinning of mobile dislocations by solute atom clusters. Smooth flow curves were obtained from −196 to −90 °C due to the suppression of dynamic strain aging. The microstructure observations indicated that more homogeneous plastic strain and grain rotation occurred in the cryogenically-deformed sample, leading to the formation of weaker fiber texture compared with the sample deformed at room temperature. A higher work hardening rate was achieved at cryogenic temperature, which delayed local necking. The suppression of serrated flow and homogeneous plastic deformation significantly improved the ductility at −196 °C, with a uniform elongation of 35.2%, which was 84.3% higher than that at 25 °C.