Complex Concentrated Alloys Research Articles

Insight into the oxidation behavior and excellent internal oxidation and nitridation resistance of Fe71.5-x(Ni, Cr, Ti)28.5Alx complex concentrated alloys by advanced characterization

For precipitate-strengthened alloys, the decomposition of the precipitates at the subsurface during high-temperature oxidation is detrimental to mechanical properties. In this study, we adjusted Al concentrations in Fe71.5-x(Ni, Cr, Ti)28.5Alx (x = 8, 12, and 16 at. %) complex concentrated alloys (CCAs) to precipitate elongated cuboidal L21 with higher density and Al concentration, as well as reduced inter-precipitate spacing. This is more conducive to the rapid diffusion of Al to the matrix and grain boundaries, promoting the formation of a continuous and compact Al2O3 layer with random crystallographic orientation at 800 °C in air. This not only inhibits the further decomposition of the L21 phase but also avoids internal oxidation and nitridation.

Quantifying the atomic neighbourhoods in complex concentrated alloys.

Quantifying the atomic neighbourhoods in complex concentrated alloys.

Improvement in mechanical as well as magnetic properties of a (FeCoNi)90Ti10-xAlx complex concentrated alloy series by tuning the chemical order

There is considerable interest in magnetic materials which also possess good mechanical properties. Hence, the effect of Ti/Al ratio on the microstructure, mechanical and magnetic properties of (FeCoNi)90Ti10-xAlx complex concentrated alloys (CCA) was investigated. An increase in the Ti/Al ratio in these CCA enhanced chemical ordering and substantially improved selected mechanical and magnetic properties. As the Ti/Al ratio changed from 10 to 0, the ductility increased from 7.5 to close to 50 %, the saturation magnetization (Ms) increased from 115.2 to 136.7 emu/g, and the coercivity (Hc) decreased from 17.9 to 4.2 Oe. The Fe30Co30Ni30Ti5Al5 alloy exhibit higher UTS×EL value than available soft magnetic materials and has relatively higher Ms and lower Hc compared with other CCA. These results provide a methodology to modulate the chemical order in the Fe-Co-Ni system by Al and Ti additions and synergistically tune the mechanical and magnetic properties for high performance rotating electrical machine applications.

Lightweight single-phase Al-based complex concentrated alloy with high specific strength

Developing light yet strong aluminum (Al)-based alloys has been attracting unremitting efforts due to the soaring demand for energy-efficient structural materials. However, this endeavor is impeded by the limited solubility of other lighter components in Al. Here, we propose to surmount this challenge by converting multiple brittle phases into a ductile solid solution in Al-based complex concentrated alloys (CCA) by applying high pressure and temperature. We successfully develop a face-centered cubic single-phase Al-based CCA, Al55Mg35Li5Zn5, with a low density of 2.40 g/cm3 and a high specific yield strength of 344×103 N·m/kg (typically ~ 200×103 N·m/kg in conventional Al-based alloys). Our analysis reveals that formation of the single-phase CCA can be attributed to the decreased difference in atomic size and electronegativity between the solute elements and Al under high pressure, as well as the synergistic high entropy effect caused by high temperature and high pressure. The increase in strength originates mainly from high solid solution and nanoscale chemical fluctuations. Our findings could offer a viable route to explore lightweight single-phase CCAs in a vast composition-temperature-pressure space with enhanced mechanical properties.

Tribological behavior of a Ti42Nb42Mo6Fe5Cr5 complex concentrated alloy and prediction through response surface methodology based mathematical modeling

In the present work, a novel Ti42Nb42Mo6Fe5Cr5 complex concentrated alloy (CCA) was developed using the vacuum arc melting technique. The as-cast CCA underwent a two-stage heat treatment process. In the first stage of heat treatment (HT 1), the alloy was heated to 900˚C. Subsequently, in the second stage of heat treatment (HT 2), the HT 1 samples were annealed at various temperatures, including 700˚C, 900˚C, and 1100˚C, for 20 h. The microstructure and mechanical response of the as-cast, HT 1 and HT 2 (annealed) samples were thoroughly investigated. The phase evolution, microstructure, and chemical composition were analyzed using XRD and SEM-EDS. The XRD analysis revealed major solid solution BCC phases (BCC 1 and BCC 2) with a small amount of Laves phase; however, the amount of Laves phase increased with increase in annealing temperature. The microhardness and elastic modulus of the CCA specimens were evaluated using instrumented micro-indentation. The CCA annealed at 1100˚C exhibits the highest microhardness and elastic modulus, with values of 5.94 ± 0.38 GPa and 124.40 ± 7.17 GPa, respectively. Response surface methodology (RSM) was used to develop a mathematical model aimed at predicting tribological characteristics, specifically the specific wear rate (SWR) and coefficient of friction (COF). RSM proposes a quadratic model to represent the mathematical relationship between input parameters for evaluating SWR and COF. The desirability function approach is employed to optimize input parameters to minimize both SWR and COF. The optimized values of SWR and COF are 6.87 × 10−4 mm3/N.m and 0.30 under a 27.52 N load, 2.86 Hz oscillation frequency, and 1100˚C annealing temperature. Surface topography analysis of the worn surface was evaluated using SEM and a profilometer to understand the wear mechanism and surface characteristics.

In-situ N-doping to improve wear and corrosion resistance of a complex-concentrated alloy manufactured by directed energy deposition

In this study, the effects of in-situ N-doping on wear and corrosion resistance of a complex-concentrated alloy (CCA) prepared by directed energy deposition have been studied. After the addition of N, the wear resistance of the CCA is significantly improved (wear rate: decreasing from ∼2.92 × 10−4 mm3/N•m to ∼0.68 × 10−4 mm3/N•m). Attributed to grain refinement and solution strengthening brought by N-doping, the resistance of the matrix to plastic deformation and delamination is enhanced effectively. Besides, the in-situ N-doping helps to reduce corrosion sites and promote the formation of protective films to improve electrochemical corrosion resistance. Therefore, in-situ N-doping is an effective method to improve the wear resistance and corrosion resistance of superalloy.

Microalloying design in directed energy deposition of complex-concentrated alloy: Pre-nitriding to inhibit hot cracking and promote mechanical properties

With the development of ultra-supercritical (USC) power generation technology, the increase of steam temperature puts higher requirements for high-temperature performance and processing reliability of superalloys. Here, a new complex-concentrated alloy (CCA) is developed for manufacturing the devices in USC circumstances. For the laser additive manufacturing of CCA, avoiding the hot cracking is crucial to guarantee reliable printability and favorable service performance. In this work, the nitrogen (N) is introduced innovatively by pre-nitriding powder to ensure sufficient N to combine with the matrix during the directed energy deposition process. The solidification temperature range can be narrowed to inhibit the hot cracking with the N-doping effectively. As a result, the sample with N-doping exhibited an extraordinary performance of strength (1083.51 MPa) and plasticity (20.83 %). The strengthening mechanisms mainly include solid solution strengthening, grain refinement strengthening, and dislocation strengthening. The elimination of defects leads to an increase in ductility in the meantime. In addition, the dynamic oscillation of the molten pool caused by pre-nitriding powder also has a nonnegligible impact on the breakdown of grain epitaxy growth and the initiation of grain refinement. These findings shed new light on the alloy design concept to inhibit hot cracking and promote mechanical properties.

A machine learning framework for the prediction of grain boundary segregation in chemically complex environments

The discovery of complex concentrated alloys (CCA) has unveiled materials with diverse atomic environments, prompting the exploration of solute segregation beyond dilute alloys. However, the vast number of possible elemental interactions means a computationally prohibitive number of simulations are needed for comprehensive segregation energy spectrum analysis. Data-driven methods offer promising solutions for overcoming such limitations for modeling segregation in such chemically complex environments (CCEs), and are employed in this study to understand segregation behavior of a refractory CCA, NbMoTaW. A flexible methodology is developed that uses composable computational modules, with different arrangements of these modules employed to obtain site availabilities at absolute zero and the corresponding density of states beyond the dilute limit, resulting in an extremely large dataset containing 10 million data points. The artificial neural network developed here can rely solely on descriptions of local atomic environments to predict behavior at the dilute limit with very small errors, while the addition of negative segregation instance classification allows any solute concentration from zero up to the equiatomic concentration for ternary or quaternary alloys to be modeled at room temperature. The machine learning model thus achieves a significant speed advantage over traditional atomistic simulations, being four orders of magnitude faster, while only experiencing a minimal reduction in accuracy. This efficiency presents a powerful tool for rapid microstructural and interfacial design in unseen domains. Scientifically, our approach reveals a transition in the segregation behavior of Mo from unfavorable in simple systems to favorable in complex environments. Additionally, increasing solute concentration was observed to cause anti-segregation sites to begin to fill, challenging conventional understanding and highlighting the complexity of segregation dynamics in CCEs.

Effect of Fe and Mn on structure, mechanical properties, and oxidation resistance of lightweight intermetallic Al55Cr23Ti22 complex concentrated alloy

In this study, we analysed the effect of Fe, Mn, or Fe and Mn additions (5 or 10 at%) on the structure, mechanical properties, deformation behaviour, including microstructure evolution, and oxidation resistance of a lightweight (density of 3.92 g/cm3) intermetallic Al55Cr23Ti22 complex concentrated alloy (CCA) with a L12 + C11b structure. The additions of Fe, Mn, or Fe and Mn (at the expense of Cr) retained the density below 4 g/cm3 and resulted in forming a D8a phase (Th6Mn23-prototype; cF120; Fm-3m) in all the alloys, except for the Al55Cr18Ti22Mn5 alloy. The D8a phase nucleated with a different morphology within or adjacent to the C11b phase, and adopted an orientation relationship of (110)C11b || (4‾4‾ 0)D8a, [3 3‾ 1]C11b || [1‾ 11‾]D8a, which provided coherent C11b/D8a interfaces. Alloying with Mn or Fe and Mn had either neutral or negative effect on the mechanical properties, while the Fe additions boosted the strength along with some decrease in the compressive plasticity at room temperature. Specifically, the Al55Cr13Ti22Fe10 alloy showed a yield strength of 250 MPa at 1000°С, which was 60 % higher compared to the Al55Cr23Ti22 alloy. During plastic deformation, all the alloys demonstrated pronounced strain hardening at T ≤ 800 °C and steady state flow at 1000 °C. Post-deformation observation of the microstructure of the Al55Cr13Ti22Fe10 alloy showed the inhomogeneous distribution of the strain-induced defects between the L12 matrix and (C11b + D8a) regions at 800 °C and partial recrystallisation of these phases at 1000 °C. All the alloys exhibited complex oxidation behaviour with multistage oxidation kinetics. The addition of 5 at% of Fe or Mn was beneficial for the oxidation resistance, while the further increase in their contents intensified the mass gain after a certain time. The latter effect was more pronounced in the Al55Cr13Ti22Mn10 alloy than in the Al55Cr13Ti22Fe10 alloy, because of forming a loose Al2O3 oxide layer. All the alloys investigated exhibited a superior synergy of 1000°C-specific yield strength and compressive plasticity at room temperature, as well as a lower mass gain after 100 h at 1000 °C, compared to both lightweight and the most oxidation-resistant refractory CCAs.

Designing complex concentrated alloys with quantum machine learning and language modeling

Designing complex concentrated alloys with quantum machine learning and language modeling

Study on the strain partitioning behavior in heterostructured complex-concentrated alloy via high-resolution digital image correlation

Here, we investigate the tensile deformation behavior in a Ni42Fe30Cr12Mn8Al5Ti3 complex-concentrated alloy with heterogeneously-grained structure consisting of fine and ultrafine grains containing nano-sized L12 precipitates. It is found that Lüders band initiation and propagation account for the early stage of deformation. High-resolution digital image correlation investigation reveals that there is strong strain partitioning between fine and ultrafine-grained domains upon plastic deformation. Significant strain gradient across the domain-interfaces is thus established. Strain partitioning promoted dense microshear bands are observed in the deformed alloy. They are uniformly distributed and interacted with each other, resulting in the formation of strain concentration zones, which are mostly evolved in fine-grained domains and some of them extend into ultrafine-grained domains at high strain levels. Thus, the global plastic deformation of the alloy is synergistically accommodated. Finally, local high stress in strain concentration zones in ultrafine-grained domains promotes the formation of voids at triple junctions of grain boundaries.

Cr content dependent lattice distortion and solid solution strengthening in additively manufactured CoFeNiCrx complex concentrated alloys – a first principles approach

In the previous study, the authors reported that multicomponent CoFeNiCrx (x = 0, 12, 18, 24 at%) complex concentrated alloys fabricated through laser directed energy deposition experienced a substantial reduction in the saturation magnetization (Ms) and the Curie transition temperature (Tc) with the increase in Cr content. The present investigation additionally explores the effect of Cr concentration on the structural and strengthening behavior in laser directed energy deposition processed CoFeNiCrx alloy system. The novel approach adopted in the present work included the integration of experimental and computational efforts involving laser direct energy deposition (L-DED) based synthesis/fabrication of a series of new CoFeNiCrx alloys through in-situ compositional tuning which is often difficult using conventional techniques and prediction of mechanical properties of these compositionally tuned alloys using a computational methodology based on the density functional theory (DFT). X-ray diffraction and nanoindentation studies revealed that while there was a slight reduction in lattice parameters, the elastic modulus increased by approximately 30 % and the yield strength increased by 25 % with increasing Cr content. The density functional theory framework was employed to interpret the influence of Cr atoms on local lattice distortions and observed yield strength. The calculated local lattice distortion, in terms of first nearest neighbors, significantly increased with Cr concentration, which is attributed to the enlargement of Cr atomic radius in the alloyed multielement environment in comparison to its radius in the elemental form. This distortion at the local level caused solid solution strengthening. The theoretically predicted solid solution strengthening values using the Varvenne model are consistent with experimental results.

New strategy in light-weight and ultrastrong Ti40Nb15Mo30(NbC)15 refractory complex concentrated alloy

Traditional refractory high-entropy alloys (RHEAs) generally exhibit a trade-off between high-temperature strength and light weight. In present work, a novel design strategy based on tailoring element distribution is proposed to achieve excellent high-temperature strength at a density lower than 7 g·cm-3. Specifically, a Ti40Nb15Mo30(NbC)15 composite was designed and prepared by powder metallurgy. The composite is found to be composed of two ultrafine-grained (UFG) phases including a body-centered cubic (bcc) solid-solution phase and a face-centered cubic (fcc) ceramic reinforcement phase (Ti, Nb)C. The as-sintered composite shows a uniform and UFG microstructure where two phases are interconnected. Due to this unique microstructure, the Ti40Nb15Mo30(NbC)15 composite displays superb specific yield strengths among surveyed RHEAs, complex concentrated alloys, and metal-matrix composites from 800°C (243 MPa·g-1·cm3) to 1000°C (127 MPa·g-1·cm3). The outstanding high-temperature compressive strength was found to be associated with high resistance to dislocation motion and strong dislocation interactions in both the bcc and fcc phases. The phase interface after hot compression remained semi-coherent, vindicating its high stability. The high-density of stable phase interfaces not only retards the dislocation motion due to the large image force near the phase boundary but also induces a high value of activation energy for diffusion. The high activation energy can further achieve significant microstructure stability even after a long-term annealing (36 h) at 1000°C. This work provides new perspectives for the design and application of light and ultrastrong refractory complex concentrated alloys (RCCAs) by comparison to the insufficient strength of many traditional and light RCCAs.

Microstructural Characterization of AlCrCuFeMnNi Complex Concentrated Alloy Prepared by Pressureless Sintering.

A significant and increasing number of studies have been dedicated to complex concentrated alloys (CCAs) due to the improved properties that these metallic materials can exhibit. However, while most of these studies employ melting techniques, only a few explore powder metallurgy and pressureless sintering as production methods. In this work, a microstructural characterization of AlCrCuFeMnNi CCA samples obtained by powder metallurgy and pressureless sintering using mixtures of powders with different compositions was carried out. One batch of samples (B1) was prepared using commercial powders of Al, Cr, Cu, Fe, Mn, and Ni. Another batch (B2) used mixtures of CrFeMn, AlNi, and Cu powders. A third set of samples (B3) was obtained by adding 1% at. of Mg to the B2 powder. The samples were characterized by X-ray diffraction, scanning and transmission electron microscopy, energy dispersive spectroscopy, density measurements, and hardness tests. Thermodynamic calculations were also used to complement the microstructural characterization. All the obtained samples exhibited high relative density and hardness values. However, B3 samples showed a higher hardness, attributed to the finer distribution of oxide particles, which was promoted by the presence of Mg during sintering. These last samples presented a hardness/density ratio of 62 HV/(g cm-3), surpassing that of some martensitic stainless steels and nickel-titanium alloys.

Strengthening complex concentrated alloy without ductility loss by 3D printed high-density coherent nanoparticles

Metallic 3D printing enables fast fabrication of net-shaped components for broad engineering applications, yet it restrains the use of most mechanical processing methods for strengthening alloys, e.g. forging, rolling, etc. Here, we proposed a new strategy for enhancing the strength of 3D printed complex concentrated alloys without losing ductility. This strategy relies on the rapid cooling of 3D printing to achieve a supersaturation state that is beyond conventional casting. Then, spinodal decomposition via aging is exploited to introduce high-density coherent nanoparticles for strengthening. The proposed strategy is demonstrated in a 3D printed Cu-based complex concentrated alloy. The rapid solidification during printing strongly inhibits elemental diffusion, leading to a high supersaturation state. High-density nanoparticles with coherent interface and size of ∼7 nm are introduced into the 3D printed samples through spinodal decomposition via simple aging treatment. The strength of the 3D printed alloy is increased by 30 % after aging with no ductility loss, leading to a strength-ductility combination superior to other Cu alloys. This strategy is readily applicable to other spinodal alloys fabricated by 3D printing for circumventing the strength-ductility trade-off dilemma.

Excellent specific strength-ductility synergy in novel complex concentrated alloy after suction casting

Lightweight alloys are known to improve the fuel efficiency of the structural components due to high strength-to-weight ratio, however, they lack formability at room temperature. This major limitation of poor formability is most of the time overcome by post-fabrication processing and treatments thereby increasing their cost exponentially. We present a novel Ti50V16Zr16Nb10Al5Mo3 (all in at. %) complex concentrated alloy (Ti-CCA) designed based on the combination of valence electron concentration theory and the high entropy approach. The optimal selection of constituent elements has led to a density of 5.63 gm/cc for Ti-CCA after suction casting (SC). SC Ti-CCA displayed exceptional room temperature strength (UTS ∼ 1.25 GPa) and ductility (ε ∼ 35 %) with a yield strength (YS) of ∼ 1.1 GPa (Specific YS = 191 MPa/gm/cc) without any post-processing treatments. The exceptional YS in Ti-CCA is attributed to hetero grain size microstructure, whereas enormous strength-ductility synergy is due to the concurrent occurrence of slip and deformation band formation in the early stages of deformation followed by prolonged necking event due to delayed void nucleation and growth. The proposed philosophy of Ti-CCA design overcomes the conventional notion of strength-ductility trade-off in such alloy systems by retaining their inherent characteristics.

Modeling the improved hydrogen embrittlement tolerance of twin boundaries in face-centered cubic complex concentrated alloys

With increasing interest in hydrogen as an alternative fuel, there is a need to develop structural alloys with improved resistance to hydrogen embrittlement (HE) for application in the new hydrogen economy. Complex concentrated alloys (CCAs), which include high entropy alloys and their derivatives, medium entropy alloys, are a new class of structural materials, some of which have reported improved HE resistance. While some studies have suggested that the improved HE resistance in CCAs with the face-centered cubic (fcc) crystal structure may be due to the high density of nanotwins within them, a detailed mechanistic understanding is yet to be developed. Towards that end, following the approach of Zhou, Tehranchi and Curtin, we employ a density functional theory-informed Griffith–Rice model22This type of model has also been referred to in the literature as the Rice–Thomson model. In this work, we refer to it as the Griffith–Rice model to reflect that the concept of unstable stacking fault energy was introduced into the model due to Rice (1992). to predict the ductile or brittle response of a crack tip interacting with twin boundaries (TBs) in a model fcc CCA, CrCoNi, both in the absence of and presence of hydrogen. Both the model and molecular dynamics simulations predict that TBs in fcc alloys are not inherently more susceptible to HE than the bulk matrix, and could in fact improve HE resistance by retarding cracks while promoting dislocation emission along the TB. Thus, designing fcc CCAs with a high density of nanotwins or utilizing gradient nanotwinned structures could be a way forward for realizing alloys with high HE resistance.

Frustrated metastable-to-equilibrium grain boundary structural transition in NbMoTaW due to segregation and chemical complexity

Grain boundary structural transitions can lead to significant changes in the properties and performance of materials. In multi-principal element alloys, understanding these transitions becomes complex due to phenomena such as local chemical ordering and multi-component segregation. Using atomistic simulations, we explore a metastable-to-equilibrium grain boundary structural transition in NbMoTaW. The transition, characterized by structural disordering and reduced free volume, shows high sensitivity to its local chemical environment. Most notably, the transition temperature range of the alloy is more than twice that of a pure metal. Differences in composition between coexisting metastable and equilibrium structures highlight the change in local site availability due to structural relaxation. Further examination of grain boundaries with fixed chemical states at varying temperatures reveals that the amount of segregation significantly influences the onset temperature yet has minimal effect on the transition width. These insights underscore the profound effect of chemical complexity and ordering on grain boundary transitions in complex concentrated alloys, marking a meaningful advancement in our understanding of grain boundary behavior at the atomic level.

Serrated plastic flow in deforming complex concentrated alloys: universal signatures of dislocation avalanches

Under plastic flow, multi-element high/medium-entropy alloys (HEAs/MEAs) commonly exhibit complex intermittent and collective dislocation dynamics owing to inherent lattice distortion and atomic-level chemical complexities. Using atomistic simulations, we report on an avalanche study of model face-centered cubic (fcc) NiCoCrFeMn and NiCoCr chemically complex alloys aiming for microstructural/topological characterization of associated dislocation avalanches. The results of our avalanche simulations reveal a close correspondence between the observed serration features in the stress response of the deforming HEA/MEA and the incurred slip patterns within the bulk crystal. We show that such correlations become quite pronounced within the rate-independent (quasi-static) regime exhibiting scale-free statistics and critical scaling features as universal signatures of dislocation avalanches.

The effects of interstitial oxygen on mechanical properties of TiZrNb medium-entropy alloy over a wide temperature range

Interstitial oxygen plays an important role in the microstructure and mechanical properties of recently developed refractory high-entropy or complex concentrated alloys. However, the mechanical properties of the oxygen-doped complex concentrated refractory alloy over a wide temperature range remain unclear. In this work, the effect of interstitial oxygen on the mechanical behavior of TiZrNb medium-entropy alloys (MEAs) has been investigated. At room temperature (RT), the interstitial oxygen improves the yield strength and tensile ductility owing to interstitial solid-solution strengthening and strain-hardening enhancement. However, simultaneous improvement of the RT strength-ductility by adding interstitial oxygen comes at the expense of increasing the ductile-brittle transition temperature (DBTT). Furthermore, the high-temperature yield strength of TiZrNb alloy can be improved up to 800 °C with the addition of 2 at% oxygen. The results above provide valuable insight into the mechanical properties of TiZrNb MEA, which would contribute to optimizing the high-performance refractory complex concentrated alloys in various applications.