CrCoNi Medium-entropy Alloy Research Articles

Enhanced strength-ductility synergy in a gradient hetero-structured CrCoNi medium-entropy alloy

A CrCoNi medium-entropy alloy (MEA) with gradient hetero-structure (GHS) composing of gradient nanostructured surface layer and hetero-structured matrix was prepared via a two-step process: pre-cold rolling (CR) deformation and subsequent annealing followed by surface mechanical grinding treatment (SMGT) and secondary annealing. The GHS CrCoNi exhibits an excellent synergy of strength and ductility, as evidenced by a yield strength of approximately 1.2 GPa and a uniform elongation of about 20%. The GHS displays a pronounced hetero-deformation induced (HDI) hardening effect, whereby the central layer (CL) and surface layer (SL) undergo local strain hardening in a mutually compatible manner. This process facilitates the multiplication and accumulation of geometrically necessary dislocations (GNDs) at intra- and inter-layer hetero-interfaces and also activates the deformation faulting and twinning in both CL and SL, thus enhancing the overall mechanical response. The interlayer compatible deformation observed in the GHS significantly bolsters the sustainability of strain hardening at the microscopic scale. This effect is of significant importance in redistributing stress and strain more rationally across the entire GHS sample, effectively reducing the risk of localized deformation failures. This study offers insight into the correlation between macroscopic strain hardening and micromechanical behavior in gradient-/hetero-structured materials.

Phase reversion mediated the dual heterogeneity of grain size and dislocation density in an equiatomic CrCoNi medium-entropy alloy

An ultra-high strain rate (104 s-1) dynamic plastic deformation treatment at liquid nitrogen temperature (LNT-DPD) followed by annealing is carried out to obtain dual heterogeneity of grain size and dislocation density in an equiatomic CrCoNi medium entropy alloy (MEA). Such extreme loading conditions resulted in extensive phase transformation in this MEA. Subsequent annealing at 650°C for 1 h further induced reverse phase transformation and partial recrystallization, forming a complex heterogeneous microstructure characterized by nested trimodal grain sizes and partitioned dislocation density. A superior yield strength of ∼800MPa and a good ductility of ∼40% were simultaneously achieved in this heterogeneous alloy. In order to reveal the effects of grain size and dislocation density distributions on the mechanical property improvements, the underlying deformation mechanisms were systematically discussed. High density of geometrically necessary dislocations (GNDs) would be induced in complex heterogeneous structures during tensile deformation due to strain gradients or partitioning between different regions, which would lead to additional strengthening and work hardening. These results provide a novel approach to overcome the strength-ductility trade-off dilemma for FCC-structured MEAs.

Enhanced cryogenic mechanical properties of heterostructured CrCoNi multicomponent alloy: Insights from in-situ neutron diffraction

Heterostructured materials (HSMs) has been shown to improve the strength-ductility trade-off of conventional alloys but their cryogenic performance has not been studied during real-time deformation. We investigated heterostructured CrCoNi medium-entropy alloy by in-situ neutron diffraction at cryogenic (77 K) and room (293 K) temperatures. The significant mechanical mismatch at interfaces between fine and coarse grains, due to pronounced grain size disparity, resulted in exceptional yield strength of 918 MPa at 293 K. The yield strength further increased to 1244 MPa at 77 K with an excellent uniform elongation of 34 %. The exceptional strength–ductility combination at 77 K can be attributed to enhanced geometrically necessary dislocation pile-up density boosted from high-mechanical mismatch interfaces, as well as higher planar faults, and martensitic phase transformation. Comparison with homogenous counterparts demonstrates the potential of HSMs as a new strategy to improve the mechanical performance of different materials, including medium-/high-entropy alloys for cryogenic applications.

Effect of Deposit Scale on Mechanical Properties of In-Situ Alloyed CrCoNi Medium Entropy Alloys Formed by Directed Energy Deposition

Directed energy deposition (DED), as an additive manufacturing technology, has shown unique advantages in multi-material additive manufacturing and remanufacturing. In this study, two types in-situ alloyed CrCoNi medium entropy alloys that have thin-walled structures with different thicknesses (T1 and T2) were manufactured by the DED process, and the mechanisms of differences in relative density, microstructure, and mechanical properties at different heights were systematically analyzed. In terms of microstructure, the T1 and T2 samples along the building direction exhibit significant differences in crystallographic orientation, grain size, and dislocation density, which are related to the local temperature gradient differences caused by the scanning path and heat accumulation. In terms of mechanical properties at different heights of the two types of thin-walled structures, the yield strength is higher but the elongation is lower at the bottom position of sample, while the yield strength is lower but the elongation is higher at the middle and top positions. The differences of mechanical properties at different heights of the T1 and T2 samples are related to the microstructure and relative density. This finding provides new insights for the design and performance analysis of complex thin-walled structures formed by additive manufacturing.

Chemical short-range ordering accompanies shear band initiation in CrCoNi medium entropy alloy

Extended X-ray absorption fine structure (EXAFS), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction have been used to monitor the structural development, on atomic-to-nanometer scale, prior to and along with shear band initiation in a face-centered-cubic CrCoNi medium-entropy alloy (MEA) under impact punch shear loads. Our findings provide clear evidence of chemical ordering with accompanying compositional inhomogeneity, on the length scale of one nanometer at the beginning of shear banding initiation. This chemical short-range atomic rearrangement of the three constituent elemental species is a result of atomic diffusion during high-strain-rate straining. The increasing chemical/structural inhomogeneity is likely to exert perturbations to cause uneven energy dissipation and encourage dislocation slip plane softening, both promoting strain localization that may have helped to instigate shear banding. Dynamic recrystallization is observed in later mature shear bands.

Enhanced Strength–Ductility Combination in Laser Welding of CrCoNi Medium-Entropy Alloy with Ultrasonic Assistance

The welded joints of high/medium entropy alloys (H/MEAs) have shown sound mechanical properties, indicating high promise for the industrial application of this new type of metal alloy. However, these joints possess either relatively low strength or low ductility. In this paper, we used ultrasonic-assisted laser welding to weld CrCoNi MEA with the nitrogen as shielding gas. The results showed that the tensile strength of the joint at room and cryogenic temperature is 686 MPa and 1071 MPa, respectively. The elongation at room and cryogenic temperature is 26.8% and 27.7%, respectively. The combination of the strength and ductility in our joints exceeds that of other welded H/MEA joints. We attributed this excellent combination to the refined dendrite, the solution of nitrogen into the matrix, and the low stacking fault energy of the CrCoNi MEA. The findings in this paper not only provide a novel way to weld H/MEAs with high strength and ductility, also are useful for additively manufacturing the high-performance component of H/MEAs.

Compressive Mechanical Properties of Gradient Structured CrCoNi Medium-Entropy Alloy under High-Temperature and High-Strain-Rate Coupling

Compressive Mechanical Properties of Gradient Structured CrCoNi Medium-Entropy Alloy under High-Temperature and High-Strain-Rate Coupling

Effect of grain size on spall fracture of CrCoNi medium-entropy alloy under Taylor-wave loading

The effect of grain size on spall properties of medium-entropy alloy CrCoNi under Taylor-wave loading is investigated. Three different grain sizes, 300 μm, 20 μm, and 3 μm, are explored. The free surface velocity histories are measured to obtain such quantities as dynamic yield strength and spall strength. With decreasing grain size, there is a slight decrease in spall strength, but a significant increase in damage rate. The shock-recovered samples are characterized with scanning electron microscopy and electron backscatter diffraction. In coarse-grained samples, voids tend to nucleate within grain interiors, while in fine-grained samples, voids nucleate preferentially at grain boundaries (GBs). Molecular dynamics simulations show that the nucleation of intergranular or intragranular voids is dominated by GB–slip and slip–slip intersections, respectively. The higher GB density results in more extensive GB–slip intersections, consistent with the experimental results.

Roles of lattice and grain boundary on hydrogen diffusion and trap behaviors in single-and poly-crystalline CrCoNi medium-entropy alloy

In this study, single-crystalline and poly-crystalline CrCoNi alloys are utilized as model systems to analyze the distinct roles of each GB and interstitial lattice sites. To effectively reveal hydrogen behavior, both electrochemical and gaseous hydrogen pre-charging methods are applied. Hydrogen content, diffusivity, and trap behaviors are quantified using thermal desorption analysis and hydrogen permeation tests, which determines (1) changes in hydrogen behavior depending on the presence of GB and (2) alterations in hydrogen behavior depending on lattice crystallographic orientation. The results indicate that GB and interstitial lattice sites exhibit comparable binding energies for hydrogen trapping. However, the introduction of GB alters the primary trapping sites from interstitial lattice sites to GB. In this case, the hydrogen content in the poly-crystalline alloy is determined by the trap site density of the primary trapping site. On the other hand, in the single-crystalline alloy, where only interstitial lattice sites exist, the crystallographic orientation of the hydrogen-charged plane is an important variable that determines hydrogen content and hydrogen diffusivity. Such insights contribute to a deeper understanding of hydrogen behavior within a more intricate microstructure, suggesting the alloy design approach to enhance resistance to HE.

Cryogenic mechanical behavior and FCC → HCP phase transformation mechanism in a Si-added CrCoNi medium-entropy alloy under quasi-static and dynamic tension

The CrCoNiSi0.3 MEA exhibits excellent cryogenic mechanical properties upon both quasi-static and dynamic tension. Under quasi-static tension at cryogenic temperature, the engineering yield and ultimate tensile strengths (UTS) reach 980 MPa and 1800 MPa, respectively, with notable ductility (62 %). The product of UTS and total elongation (TE) is 111.6 GPa %, surpassing most cryogenic high strength-ductility alloys. The significant mechanical strength enhancement is attributed to the denser deformation twins (DTs), multiple twinning, and extensive face-centered-cubic to hexagonal-close-packed (HCP) phase transitions, resulting in a high work hardening capacity. Upon dynamic tension at cryogenic temperature, the strength and strain hardening are further improved, which originates from the thickening DTs and HCP sequence and localized plastic deformation. The effects of temperature and strain rate on phase transition are studied. It is proposed that there is a competing relationship between high strain rate and increased stacking fault energy (SFE) due to temperature rise. The coupling effect of cryogenic temperature and high strain rate inhibits phase transition due to the deformation inhomogeneity in CrCoNiSi0.3 MEA. The findings make a valuable contribution to understand the influence of temperature and strain rate on the mechanism of FCC-to-HCP phase transition.

Tunable interstitial and vacancy diffusivity by chemical ordering control in CrCoNi medium-entropy alloy

In this study, we utilized a quantitative atomistic analysis approach to investigate the impact of chemical ordering structures on the diffusion behavior of interstitials and vacancies within the CrCoNi medium entropy alloy (MEA), employing an advanced neural network interatomic potential (NNP). We discovered that the degree of chemical ordering, which can be precisely controlled through annealing at elevated temperatures, significantly influences both interstitial and vacancy diffusion. This phenomenon contributes to the notable sluggish diffusion characteristic of CrCoNi, largely attributable to the restriction of diffusion pathways in regions with lower degree of chemical ordering. We also emphasized the crucial role of operating temperature on diffusion, which should be remained well below the annealing temperature to preserve the sluggish diffusion effect. Our research sheds light on the interplay between chemical ordering and defect diffusion in MEAs, and it proposes effective strategies for tailoring the diffusivity of MEAs by altering their chemical ordering. These insights are instrumental in the development of next-generation materials, which are optimized for use in challenging environments, such as high-temperature and irradiation conditions.

Suppressing hydrogen embrittlement of a CrCoNi medium-entropy alloy by triggering co-segregation of carbon, boron, and Cr

The CrCoNi medium-entropy alloy has drawn extensive attention due to its outstanding mechanical properties, yet it suffers severe gaseous hydrogen embrittlement (HE). Here we report that co-doping of carbon and boron could greatly suppress such embrittlement, resulting in a significant reduction in ductility loss from 71 % to merely 16 %. The minor doping has no significant influence on the phase structure, grain size, and grain-boundary character. However, the co-segregation of carbon, boron, and Cr was triggered, which not only improves the grain-boundary cohesive strength but also hinders the diffusion and accumulation of hydrogen at GBs, thereby leading to improved HE resistance.

Simultaneous improvement of strength and ductility in a P-doped CrCoNi medium-entropy alloy

A newly developed P-doped CrCoNi medium-entropy alloy (MEA) provides both higher yield strength and larger uniform elongation than the conventional CrCoNi MEA, even superior tensile ductility to the other-element-doped CrCoNi MEAs at similar yield strength levels. P segregation at grain boundaries (GBs) and dissolution inside grain interiors, together with the related lower stacking fault energy (SFE) are found in the P-doped CrCoNi MEA. Higher hetero-deformation-induced (HDI) hardening rate is observed in the P-doped CrCoNi MEA due to the grain-to-grain plastic deformation and the dynamic structural refinement by high-density stacking fault-walls (SFWs). The enhanced yield strength in the P-doped CoCrNi MEA can be attributed to the strong substitutional solid-solution strengthening by severer lattice distortion and the GB strengthening by phosphorus segregation at GBs. During the tensile deformation, the multiple SFW frames inundated with massive multi-orientational tiny planar stacking faults (SFs) between them, rather than deformation twins, are observed to induce dynamic structural refinement for forming parallelepiped domains in the P-doped CoCrNi MEA, due to the lower SFE and even lower atomically-local SFE. These nano-sized domains with domain boundary spacing at tens of nanometers can block dislocation movement for strengthening on one hand, and can accumulate defects in the interiors of domains for exceptionally high hardening rate on the other hand.

Microstructure, corrosion resistance and wear properties of laser directed energy deposited CrCoNi medium-entropy alloy after cyclic deep cryogenic treatment

ABSTRACT Subjected to repeated heating and cooling, laser directed energy deposited (LDED) parts always possess considerable residual stress, which severely limits their industrial applications. In this work, cyclic deep cryogenic treatment (CDCT) was performed to finely tune the residual stress and microstructure of LDED-fabricated CrCoNi medium-entropy alloy (MEA). With increasing number of CDCT cycles, crystalline defects within the sample became denser due to the repeated visco-plastic deformation. The compressive residual stress (CRS) of the sample was estimated to be 361.9 ± 16.8 MPa after 30 cycles of CDCT, 64.2% higher than that in the as-built condition. Due to the existence of dense crystalline defects and high CRS, the corrosion and wear rates of CDCT-treated CrCoNi MEA were significantly decreased compared with the as-built condition. This work demonstrated CDCT as an effective means for regulating the residual stress, microstructure, and surface performance of LDED-fabricated MEA.

Microstructures and mechanical properties of laser-directed energy deposited CrCoNi medium-entropy alloy

Microstructures and mechanical properties of laser-directed energy deposited CrCoNi medium-entropy alloy

Extensive phase transformation in an equiatomic CrCoNi medium entropy alloy under extreme uniaxial tension

The dynamic tension behavior of an equiatomic CrCoNi medium entropy alloy (MEA) has been studied at both room temperature (RT, 298 K) and liquid nitrogen temperature (LNT, 77 K). Microstructural observations show that extensive phase transformations were activated in this alloy under dynamic tension at LNT instead of the activation of the deformation twins under high strain rate only or quasi-static loading at LNT. The appearance of massive nanoscale phase transformation bands along multiple slip directions even created a network structure of HCP lamellae in the FCC grains. This leads to defect accumulation at the intersection regions and results in the formation of new HCP variants, inverse phase transformations to FCC structure and even amorphous domains. Such transformation induced plasticity (TRIP) effects including the mutual interactions of crossover phase transformation bands on the plasticity and tension fracture of the MEA under extreme loading conditions were further discussed. These findings provide a deeper understanding of the deformation mechanisms in the equiatomic MEA under extreme loads.

Atomic-Scale In Situ Observations of Reversible Phase Transformation Assisted Twinning in a CrCoNi Medium-Entropy Alloy.

Twinning is an important deformation mode of face-centered-cubic (FCC) medium- and high-entropy alloys, especially under extreme loading conditions. However, the twinning mechanism in these alloys that have a low or even negative stacking fault energy remains debated. Here, we report atomic-scale in situ observations of the deformation process of a prototypical CrCoNi medium-entropy alloy under tension. We found that the parent FCC phase first transforms into a hexagonal close-packed (HCP) phase through Shockley partial dislocations slipping on the alternate {111} planes. Subsequently, the HCP phase rapidly changes to an FCC twin band. Such reversible phase transformation assisted twinning is greatly promoted by external tensile loads, as elucidated by geometric phase analysis. These results indicate the previously underestimated role of the metastable HCP phase in nanotwin nucleation and early plastic deformations of CrCoNi alloys and shed light on microstructure regulation of medium-entropy alloys with enhanced mechanical properties.

Rejuvenation as the origin of planar defects in the CrCoNi medium entropy alloy

High or medium- entropy alloys (HEAs/MEAs) are multi-principal element alloys with equal atomic elemental composition, some of which have shown record-breaking mechanical performance. However, the link between short-range order (SRO) and the exceptional mechanical properties of these alloys has remained elusive. The local destruction of SRO by dislocation glide has been predicted to lead to a rejuvenated state with increased entropy and free energy, creating softer zones within the matrix and planar fault boundaries that enhance the ductility, but this has not been verified. Here, we integrate in situ nanomechanical testing with energy-filtered four-dimensional scanning transmission electron microscopy (4D-STEM) and directly observe the rejuvenation during cyclic mechanical loading in single crystal CrCoNi at room temperature. Surprisingly, stacking faults (SFs) and twin boundaries (TBs) are reversible in initial cycles but become irreversible after a thousand cycles, indicating SF energy reduction and rejuvenation. Molecular dynamics (MD) simulation further reveals that the local breakdown of SRO in the MEA triggers these SF reversibility changes. As a result, the deformation features in HEAs/MEAs remain planar and highly localized to the rejuvenated planes, leading to the superior damage tolerance characteristic in this class of alloys.

Synergistic effect of Al and Ti micro-alloying in CoCrNi-based medium entropy alloy

Recently, medium and high-entropy alloys with heterogeneous features have exhibited excellent synergistic effects of strength and toughness. In this work, we have produced a series of cast CrCoNi medium entropy alloys with various heterogeneous microstructures through Al and Ti elements micro-alloying. The heterogeneous microstructure and deformation mechanism are systematically analyzed. The result showed that Al/Ti ratio ranging from 0.5 to 2 has a significant influence on the microstructure and mechanical properties of the CrCoNi-based alloy. The present findings provided efficient guidance for developing of microstructure tailoring method in high and medium-entropy alloys.

High-Temperature Corrosion of High- and Medium-Entropy Alloys CrMnFeCoNi and CrCoNi Exposed to a Multi-Oxidant Atmosphere H2O–O2–SO2

The high-temperature corrosion behaviors of the equimolar CrCoNi medium-entropy alloy and CrMnFeCoNi high-entropy alloy were studied in a gas atmosphere consisting of a volumetric mixture of 10% H2O, 2% O2, 0.5% SO2, and 87.5% Ar at 800 °C for up to 96 h. Both alloys were initially single-phase fcc with a mean grain size of ~ 50 μm and a homogeneous chemical composition. The oxide layer thickness of CrMnFeCoNi increased linearly with exposure time while it remained constant at ~ 1 μm for CrCoNi. A Cr2O3 layer and minor amounts of (Co,Ni)Cr2O4 developed on the latter while three oxide layers were detected on the former, i.e., a thin and continuous chromium rich oxide layer at the oxide/alloy interface, a dense (Mn,Cr)3O4 layer in the center and a thick and porous layer of Mn3O4 and MnSO4 at the gas/oxide interface. Additionally, a few metal sulfides were observed in the CrMnFeCoNi matrix. These results were found to be in reasonable agreement with thermodynamic calculations.