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At least 19 records

Understanding the effect of refractory metal chemistry on the stacking fault energy and mechanical property of Cantor-based multi-principal element alloys

Multi-principal-element alloys (MPEAs) based on 3d-transition metals show remarkable mechanical properties. In this study, the stacking fault energy (SFE) in face-centered cubic (fcc) alloys is a critical property that controls underlying deformation mechanisms and mechanical response. Here, we present an exhaustive density-functional theory study on refractory- and copper-reinforced Cantor-based systems to ascertain the effects of refractory metal chemistry on SFE. We find that even a small percent change in refractory metal composition significantly changes SFEs, which correlates favorably with features like electronegativity variance, size effect, and heat of fusion. For fcc MPEAs, we also detail the changes in mechanical properties, such as bulk, Young's, and shear moduli, as well as yield strength. A Labusch-type solute-solution-strengthening model was used to evaluate the temperature-dependent yield strength, which, combined with SFE, provides a design guide for high-performance alloys. We also analyzed the electronic structures of two down-selected alloys to reveal the underlying origin of optimal SFE and strength range in refractory-reinforced fcc MPEAs. These new insights on tuning SFEs and modifying composition-structure-property correlation in refractory- and copper-reinforced MPEAs by chemical disorder, provide a chemical route to tune twinning- and transformation-induced plasticity behavior in fcc MPEAs.

36 MATERIALS SCIENCE

Influence of stacking fault energy and hydrogen on deformation mechanisms in high Mn austenitic steels during in-situ tensile testing

High Mn austenitic steels are considered an economical alloy system for hydrogen storage and transport applications. This study used stacking fault energy (SFE) as a design parameter to achieve hydrogen embrittlement (HE)-resistant high Mn austenitic alloys. The role of hydrogen on the deformation mechanisms of low (29 mJ/m 2 ) and high SFE (49 mJ/m 2 ) alloys was evaluated through in-situ neutron diffraction during tensile loading. Hydrogen-precharging increased yield strength, partly due to hydrogen-induced lattice distortion (i.e., solute strengthening). Hydrogen accelerated the increase in defect density, including dislocations and stacking faults. The formation of planar deformation structures (twins and stacking faults), relative to dislocations, plays a critical role in promoting hydrogen-assisted fracture. The stacking fault frequency parameter obtained from neutron diffraction quantifies planar deformation tendencies, correlated with HE sensitivity. The higher SFE alloy exhibited greater resistance to HE, associated with the reduced propensity to form stacking faults and twins upon deformation in the hydrogen-precharged condition.

High Mn austenitic steel

The impact of nickel concentration and stacking fault energy on deformation mechanisms in high-purity austenitic Fe-Cr-Ni alloys

Understanding how composition affects deformation mechanisms in austenitic stainless steels is essential for developing accurate predictive models of stress-induced failures and stress corrosion cracking. Nickel (Ni), an element classified as a critical element, plays a crucial role in these processes. It is important to examine how Ni concentration influences stacking fault energy (SFE) and, consequently, the deformation mechanisms of austenitic stainless steels. However, in commercial stainless steels, the effects of other alloying elements and impurities can obscure Ni's role, complicating efforts to isolate its impact. Here, in this study, we use two high-purity Fe-Cr-Ni alloys to investigate how Ni concentration and SFE interact to alter deformation mechanisms and induce martensitic transformation. By combining in situ synchrotron X-ray diffraction (XRD) tensile testing and post-mortem electron microscopy with density functional theory simulations, we gain precise insights into these phenomena. We find that the Fe18Cr10Ni (wt%) alloy, with its low SFE, exhibits higher stacking fault probability, deformation-induced martensitic transformation, and a lesser increase in dislocation density with plastic strain. In contrast, the Fe18Cr14Ni (wt%) alloy, with its higher SFE, shows enhanced deformation twinning and greater dislocation density with increasing strain. These findings from high-purity ternary alloys provide valuable insights that can guide the search for alternative elements to replace Ni while achieving similar effects on phase stability and deformation behavior.

36 MATERIALS SCIENCE

Compositional effect on pressure-induced polymorphism in high-entropy alloys

Recently, pressure-induced polymorphic phase transitions were discovered in several fragmented high-entropy alloys (HEAs), offering a valuable opportunity to deepen our understanding of these materials. However, the chemical and physical factors that govern these transitions are still unclear. Here, in this work, we combined in situ high-pressure synchrotron X-ray diffraction, X-ray emission spectroscopy (XES), and high-resolution transmission electron microscopy (HRTEM) to systematically study the evolution of the atomic and electronic structures in the Cantor alloy and its face-centered-cubic ( fcc ) subset alloys (CoCrFeMnNi, CoCrFeNi, CoCrMnNi, CoFeMnNi, CoCrNi, CoFeNi, CoMnNi, CrFeNi, and FeMnNi). Surprisingly, diverse behavior was observed among these closely related alloys during compression and decompression, which includes irreversible, reversible fcc to hexagonal close-packed (hcp) phase transitions, or even no detectable phase transitions up to ∼40 GPa. HRTEM measurements confirmed that the fcc and hcp phases abided by the classic Shoji-Nishiyama orientation relationship during the transitions. XES data indicated that high-pressure suppresses the local magnetic moments in all the studied alloys, suggesting that magnetic states do not significantly influence the polymorphic transitions. By comparing the effects of the atomic size difference, entropy, valence electron concentration, and stacking fault energy across all the compositions studied, only the stacking fault energy shows a strong correlation with the phase transitions, indicating it plays a key role in inducing polymorphism in HEAs.

36 MATERIALS SCIENCE

On the distribution of stacking faults at dissociated medium-angle grain boundaries: Crystallographic geometry and metastability

Grain boundaries in FCC metals with low stacking-fault energy can form in dissociated configurations of stacking faults. Perhaps the most studied example is 9R stacking at boundaries near Σ3{112}, where the distribution of stacking faults is related to the emission of Shockley partial dislocations. Here, we combine atomic-resolution electron microscopy, atomistic simulations, and dislocation theory to demonstrate that boundaries vicinal to Σ33a support the stabilization of dissociated 9R stacking within a narrow range of inclinations. This boundary is interesting since its misorientation (20.05°) lies in the medium-angle regime, just past the upper misorientation limit for low-angle boundaries, motivating questions for how best to describe it in terms of dislocations. Our HAADF-STEM observations of thin film bicrystals, supported by atomistic modeling, reveal that this inclination dependence arises from specific geometric constraints on the arrangement of Shockley partial dislocations at the interface. Quantification of stacking-fault distributions across multiple boundaries indicates that the density and spacing of faults closely follow the ideal 9R motif, with subtle variations reflecting the complex energy landscape of these boundaries. Through energetic analysis, we establish the presence of competing metastable states enabled by variations in stacking sequences, emphasizing the significant role of crystallographic geometry. We generalize our analysis as a function of misorientation, showing how 9R at the Σ33a boundary is related to previous observations and calculations of HCP at a 29.7° boundary. This study provides a crystallographically grounded framework connecting dislocation structures, stacking-fault distributions, and metastability at grain boundaries in FCC metals.

Atomistic modeling

Doping Effects on the Ductility of a Lightweight Refractory High-Entropy Alloy: Grain Boundary and Bulk Lattice Aspects

Doping elements in small amounts often segregate to grain boundaries (GBs) in alloys and can significantly impact mechanical properties and performance. Refractory high-entropy alloys (RHEAs) are known for their poor ductility, especially at low temperatures. Promoting GB cohesion through segregation can be an effective approach to mitigate embrittlement. Here, in this study, first-principles density functional theory (DFT) calculations were performed to examine the effects of important interstitial dopants (O, B, C, and N) and substitutional dopants (Cr, Y, La, and Ce) on the Σ5(310) [001] tilt GB of a lightweight RHEA Nb 32.5 Ti 27.5 Mo 22.5 Ta 12.5 Hf 2.5 Zr 2.5 . The DFT calculations reveal that certain dopants, such as B, C, Cr, N, and Y, exhibit favorable GB strengthening effects by improving bonding interactions with the bulk alloy. The impact of doping on the ductility parameter of the bulk lattice, defined as the ratio of surface energy to unstable stacking fault energy for the {110} <111> slip system, was also studied; and the results show that doping reduces the intrinsic ductility of the alloy, decreasing the D-parameter from 2.90 to 2.55, depending on the specific dopant. The present findings provide a foundational understanding at atomic level of the effect of representative dopants on mechanical properties of RHEAs and can be used to guide future alloy design for improved mechanical properties.

deformation charge density

Understanding Twinning and Deformation in High Entropy Alloys

A combination of high strength and high ductility has been observed in multi-principal element alloys due to twin formation attributed to low stacking fault energy (SFE). In the pursuit of low SFE alloys, a key bottleneck is the lack of understanding of the composition–SFE cor- relations that would guide tailoring SFE via alloy composition. Using density functional theory (DFT), we show that dopant radius, which have been postulated as a key descriptor for SFE in dilute alloys, does not fully explain SFE trends across different host metals. Instead, charge density is a much more central descriptor. It allows us to (1) explain contrasting SFE trends in Ni and Cu host metals due to various dopants in dilute concentrations, (2) explain the large SFE variations observed in the literature even within a given alloy composition due to the nearest neighbor environments in “model” concentrated alloys, and (3) develop a machine learning model that can be used to predict SFEs in multi-elemental alloys. This model opens a possibility to use charge density as a descriptor for predicting SFE in alloys. Furthermore, a descriptor-less machine learning (ML) model based only on charge density images extracted from density functional theory (DFT) is developed to predict stacking fault energies (SFE) in concentrated alloys. The model is based on convolutional neural networks (CNNs) as one of the promising ML techniques for dealing with complex images and data. Identification of correct descriptors is a key bottleneck to develop ML models for predicting materials properties. Often, in most ML models, textbook physical descriptors such as atomic radius, valence charge and electronegativity are used as descriptors which have limitations because these properties change in concentrated alloys when multiple elements are mixed to form a solid solution. We illustrate that, within the scope of DFT, the search for descriptors can be circumvented by electronic charge density, which is the backbone of the Kohn-Sham DFT and describes the system completely. The performance of our model is demonstrated by predicting SFE of concentrated alloys with an RMSE and R2 of 6.18 mJ/m2 and 0.87, respectively, validating the accuracy of the proposed approach.

36 MATERIALS SCIENCE

Deformation mechanisms of nanotwinned Al and binary Al alloys

The objective of this proposal is to investigate, at a fundamental level, the deformation mechanisms of nanotwinned (NT) Al alloys with high density twin boundaries (TBs) and stacking faults (SFs). Nanotwinned metals with low stacking fault energy (SFE), such as Cu and Ag, have shown outstanding strength and tensile ductility. Twin boundaries play a critical role to enhance the strength and work hardening ability of these metals and alloys, and thus lead to significant plasticity. Al alloys have ultra-high stacking fault energy, and thus are often considered to be nearly free from growth twins and SFs. However, our recent studies show that a significant number of nanotwins and 9R phase can be introduced in Al and certain Al alloys, and lead to high flow stresses.

36 MATERIALS SCIENCE

Tailoring Mechanical Properties of a Multi-Principle-Element Alloy by a Multi-Length-Scale Approach

A multiscale strengthening approach was employed to tailor the mechanical properties of a NiCoCr-based multi-principal element alloy (MPEA). Initially, the addition of Mo was utilized to strengthen the alloys by achieving grain size refinement, severe lattice distortion, and a reduction in stacking fault energy (SFE). Subsequently, the Suzuki segregation phenomenon was leveraged by carefully controlling stacking fault (SF) density via pre-straining and a subsequent 500°C heat treatment. Consequently, the Mo-added MPE alloys that were pre-strained and subsequently heat-treated exhibited a true yield stress of 2.3 GPa, with a corresponding fracture elongation of 12%. The Mo promotes complex SF interactions and the SFs formed during prior straining serve as sites for Suzuki segregation during subsequent heat treatment, varying the local SFE with Cr segregation, creating a roughened landscape and hindering dislocation dynamics. This multiscale strengthening approach presents a promising route for achieving desired mechanical properties in MPEAs.

mechanical properties

Temperature-Dependent Mechanical Properties of Ni-Based Concentrated Alloys: Insights from First-Principles Calculations

The present work focuses on predicting temperature-dependent mechanical properties of Ni-based concentrated alloys Ni 18 Cr 10 Co 10 Fe 6 M 4 (abbreviated by X 44 M 4 , with M = Al, V, Mn, Fe, Nb, Mo, and W) using density functional theory (DFT). These predictions are based on shear (plastic) and elastic deformations, utilizing the special quasirandom structure (SQS), the phonon-based quasiharmonic approach (QHA), and the quasistatic approach. The resulting properties include coefficient of thermal expansion via QHA, ideal shear strength (τ IS ), and stable and unstable stacking fault energies (γ SF and γ US ) through pure alias shear deformation, and elastic constants (c ij ), bulk modulus (B 0 ), and shear modules (G 0 ) via elastic deformation. Notably, predicting accurate γ SF is challenging due to uncertainties that can exceed the γ SF values. τ IS and γ US exhibit a strong linear relationship, enabling the accurate prediction of γ US based on the precisely determined τ IS . All mechanical properties of X 44 M 4 decrease with increasing temperature, except for some γ SF cases such as X 44 M 4 with M = V, Mn, Fe, Mo, and W. Among the X 44 M 4 alloys, X 44 Nb 4 exhibits the lowest τ IS , γ US , and G 0 values, and the highest B 0 /G 0 ratio, while X 44 Mn 4 has the lowest B 0 and B 0 /G 0 ratio. We found that volume is a crucial descriptor for understanding and modeling mechanical properties (except B0 and maybe also γ SF ) affected by alloying elements and temperature. Ni-based dilute alloys (e.g., Ni 11 M 1 and Ni 31 M 1 ) and concentrated alloys (e.g., X 44 M 4 ) show similar trends in mechanical properties influenced by alloying elements and temperature, simplifying the analysis and design of Ni-based alloys.

Elastic properties

Understanding the deformation behavior of the γ rich transformative Fe 38.5 Mn 20 Co 20 Cr 15 Si 5 Cu 1.5 complex concentrated alloy using in situ synchrotron diffraction

In situ tensile testing coupled with synchrotron x-ray diffraction was used to study the deformation behavior of metastability-engineered Fe 38.5 Mn 20 Co 20 Cr 15 Si 5 Cu 1.5 complex concentrated alloy. Monitoring the evolution of phase fraction and strain hardening response allowed the determination of true critical stress for the onset of the transformation-induced plasticity (TRIP) to be ∼375 MPa, preceded by slip starting at ∼255 MPa. In situ EBSD was used to validate the critical stress for transformation at the microstructure level and observe slip traces to confirm prior slip activity before the transformation. Further, a modeling framework based on stacking fault energy (SFE) was developed to predict the critical stress for transformation. Modeling suggested the SFE of the alloy to fall nearly 15 mJ/m 2 , which agrees well with SFE values calculated using synchrotron peak shifting (12 mJ/m 2 ) and thermodynamic calculation (11 mJ/m 2 ). As a result of γ-fcc to ε-hcp phase transformation, new {0002} ε planes emerged parallel to unaligned {111} γ planes with the tensile loading following S-N orientation relationship. Such selective emergence of new diffraction rings corresponding to ε phase is understood based on the reorientation of γ crystals with reference to tensile axis. In conclusion, this approach can be extended to effectively design alloys based on critical stress required for activating different deformation mechanisms to further push the limits of the strength-ductility envelope.

Complex concentrated alloy

Local chemical ordering of a neutron-irradiated CrFeMnNi compositionally complex alloy

While ion-irradiation studies are a critical first step in studying compositionally complex alloys (CCAs) for nuclear applications, they do not capture all the microstructural changes occurring under the low irradiation dose rates and different particles’ scattering patterns experienced in a nuclear reactor setting. To explore these phenomena in reactor-relevant conditions for the first time in CCA, the single-phase solid-solution Cr 10 Fe 30 Mn 30 Ni 30 was neutron irradiated up to 6.61 displacements per atom at 395 and 579 °C. Irradiation-enhanced local chemical ordering (LCO) well beyond the range of short range ordering was observed, and is predicted to be the precursor to the precipitation of a coherent Ni-Mn L1 0 phase and a Cr-rich α’ phase, though TEM analysis did not indicate the presence of either in any irradiation condition. The line density of faulted dislocation loops decreased from 6.47 to 1.69 ∙ 10 15 m -2 from 3.43 to 6.61 dpa at 579 °C despite no appreciable faulted loop content in the unirradiated material. LCO is expected to increase the complexity of the energy landscape within this alloy, restricting interstitial point defect mobility and creating local regions of greater stacking fault energy. These contribute to the negative correlation between irradiation dose and faulted dislocation loop density in this study, as well as the lack of void swelling observed.

36 MATERIALS SCIENCE

Resolving Lonsdaleite's decade-long controversy: Atomistic insights into a metastable diamond polymorph

Lonsdaleite, a theoretically proposed hexagonal diamond polymorph, has remained at the center of a five-decade scientific controversy since its 1967 identification. While some studies claim it exhibits superior hardness through compression-induced structural changes, others contend it is merely a stacking-faulted cubic diamond. Meteoritic samples and synthetic preparations have yielded conflicting evidence, with even advanced characterisation techniques like XRD and TEM failing to provide definitive proof. In this work, we employ first-principles density functional theory (DFT) and molecular dynamics (MD) simulations to generate unambiguous theoretical fingerprints through XRD, Raman, and SAED patterns that distinguish true Lonsdaleite from cubic diamond and its defective variants. Our atomistic approach quantifies the thermodynamic metastability of Lonsdaleite under realistic pressure-temperature conditions, reveals distinct spectral signatures through simulated Raman and resolves the structural ambiguity through generalised stacking fault energy analysis. By establishing clear criteria for definitive identification, this study provides long-awaited clarity to the Lonsdaleite debate while offering a robust computational framework for characterising metastable carbon phases in meteoritic, synthetic and industrial materials.

DFT

Tailoring mechanical properties of a multi-principal element alloy through a multi-length-scale approach

In this study, a multi-length-scale strengthening approach was used to tailor the microstructure and the mechanical properties of a NiCoCr-based multi-principal element alloy (MPEA). Grain size refinement, severe lattice distortion, and stacking fault energy (SFE) reduction with Mo addition (up to 10 at.%) enhance yield strength by 85% with only 10% reduction in ductility in as-annealed MPEAs. A pronounced increase in the strain hardening rate was observed with the addition of Mo, which is ascribed to the promotion of complex stacking fault (SF) interaction and intersection, accompanied by Lomer-Cottrell (L-C) and Hirth locks inhibiting dislocation motion and substantial increase in the accumulation of back stress. To push the limit of the yield strength further, the Suzuki segregation phenomenon was manipulated by a careful control of SF density by pre-straining and a subsequent 500 °C heat treatment. The stress-strain responses of the pre-strained and heat treated MPEAs showed an obvious SF density and Mo concentration dependence. Furthermore, the yield strength of the pre-strained Mo-added MPEAs with subsequent heat treatment was increased up to true stress of 2.3 GPa with a corresponding fracture elongation of 12% true strain. SFs formed during pre-straining served as Cr segregation sites during subsequent heat treatment, which substantially varies the local SFE within the SF, presenting a roughened landscape and frustrating the dislocation dynamics.

mechanical properties

A Review of Medium-Mn, Low-Density Steels for Transportation Applications

Low-density steels constitute a broad and complex alloy space (Fe–Mn–Al–C) suitable for a variety of applications. In particular, there has been growing interest in duplex (ferrite + austenite) or multiphase (+ martensite, carbides) low-density steels as a lightweight, advanced high-strength steel (AHSS) for vehicle applications, spurred by extensive decarbonization efforts. Medium-Mn (med-Mn) (3 to 12 wt pct) steels with 3.5 to 10 wt pct Al additions have decreased densities, presenting an interesting opportunity for high-specific strength, intrusion-resistant, and energy-absorbing sheet components with reduced alloying contents compared to high-Mn grades like austenitic Fe–Mn–Al–C or twinning-induced plasticity steels. Compared to leaner med-Mn steels, the physical metallurgy of med-Mn, low-density steels (MMLS) is complex and distinguished by increased δ-ferrite fractions and austenite stacking fault energies, decreased martensite start temperatures, and modified phase transformation windows. Mechanical properties of MMLS are comparable to 3rd generation AHSS, attributable to the unique, multiphase microstructures, and the array of strengthening mechanisms that can be accessed. Despite this, challenges and unknowns remain with respect to their industrial implementation, and new processing routes may need to be developed. Here, this review aims to highlight the composition effects, processing methods, microstructural evolution, deformation behavior, and application properties geared toward manufacturing and performance, altogether assessing the potential of MMLS for transportation applications.

36 MATERIALS SCIENCE

Effect of Zn Addition on Phase Evolution in AlCrFeCoNiZn High–Entropy Alloy

The addition of Zn to AlCrFeCoNi high-entropy alloy (HEA) poses intriguing questions as to how it would affect phase evolution. Herein, the phase evolution in AlCrFeCoNiZn is studied using a combination of experimental techniques (X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and differential scanning calorimetry) and computational (density-functional theory [DFT], calculation of phase diagrams, and machine-learning) methods. Mechanically alloyed and spark-plasma-sintered AlCrFeCoNiZn assumes a metastable single-phase, body-centered-cubic (BCC) structure that undergoes diffusion-controlled phase separation upon subsequent heat treatment to form separate (Al, Cr)-rich, (Fe, Co)-rich, and (Zn, Ni)-rich phases. The formation of (Al, Cr)-rich phase, not reported previously in AlCrFeCoNi-based HEAs, is attributed to strong clustering tendency of Cr–Zn and Cr–Ni pairs, combined with the strong ordering of Zn–Ni pair, driving out Cr that in turn combines with Al to form a (Al, Cr)-rich phase. In the DFT results, the formation of thermodynamically stable L1 2 phase is shown wherein Cr–Fe–Zn [Al–Ni-Co] preferably occupy1a (000) [3c (0 ½ ½)] positions. Furthermore, the sluggish diffusional transformation to L1 2 phase from BCC precursors is attributed to the small stacking-fault energy of AlCrFeCoNiZn. The equilibrated HEA exhibits a high microhardness of 8.24 GPa with an elastic modulus of 184 GPa.

36 MATERIALS SCIENCE

Deformation Behaviors in Single BCC‐Phase Refractory Multi‐Principal Element Alloys under Dynamic Conditions

The mechanical behavior and microstructural evolution of a BCC-phase NbTaTiV refractory multi-principal element alloy (RMPEA) is studied over a wide range of strain rates (10 −3 to 10 3 s −1 ) and temperatures (room temperature to 850 °C). The mechanical property of present RMPEA shows less strain-rate dependence and strong resistance to softening at high temperatures. Under high strain-rate loading, the formation of thin type-I twins is observed, which could lead to an increase in strain-hardening rates. However, this hardening mechanism competes with adiabatic heating effects, resulting in the deterrence of strain-hardening behaviors. In contrast, substantial strain-hardening occurs at cryogenic temperatures due to the formation of twins, which act as stronger barriers to dislocation motion and interact with each other. To further understand the different strain-hardening behaviors, density functional theory (DFT) calculations predict relatively low stacking fault energies and high twinning stress for the NbTaTiV RMPEA.

36 MATERIALS SCIENCE

Nanotwinned alloys under high pressure

Nanotwinned alloys are of interest due to their high strength and ductility, but twin boundaries may not be stable under shear. Computational studies indicate that high hydrostatic pressure may suppress detwinning mechanisms. Here, in this study, we investigate the microstructural changes of nanotwinned-nanocrystalline copper-nickel and Inconel 725 alloys under quasi-hydrostatic pressures up to 50 gigapascals (GPa). The alloys are compressed in a diamond anvil cell. In-situ x-ray diffraction (XRD) and ex-situ transmission electron microscopy (TEM) were employed to monitor microstructural changes. Twin boundary deformation and grain growth occur at 11.4 GPa quasi-hydrostatic pressure in the copper-nickel alloy. Molecular dynamics (MD) simulations reveal that hydrostatic pressure causes elevated local shear stress at grain boundaries, which leads to atomic rearrangements. A superposition of hydrostatic and deviatoric pressures lead to partial dislocation mediated twin boundary migration. In contrast, the Inconel 725 alloy showed stable twin and grain boundaries up to a quasi-hydrostatic pressure of 12.7 GPa. Texture, high solid solution strengthening, and low stacking fault energy are hypothesized to the enhanced microstructural stability in Inconel 725.

36 MATERIALS SCIENCE