Recent progress in the CoCrNi alloy system

The exceptional mechanical properties, particularly at cryogenic temperatures, of the equiatomic CoCrNi alloy are documented in numerous published studies. Similar to the equiatomic CoCrFeMnNi (so called Cantor alloy), from which the ternary alloy was derived, the CoCrNi ternary possesses low stacking fault energy that promotes complex deformation modes, as well as the activation of deformation twinning at ambient temperatures and increased strain. In addition to outstanding deformation mechanisms, chemical short-range order and face-centered cubic (FCC)-hexagonal close packed (HCP) transitions have been verified in this alloy and prove to be key factors contributing to the alloy\u27s notable properties. The relationship between stacking fault energy and FCC→HCP phase transitions has been developed over the years through other low stacking fault materials, but the question that arises is: do well established physical metallurgical mechanisms require modification when applied to systems such as CoCrNi given their compositional complexity? Local chemical order plays an important role in that it brings the deviation from the random solid solution behavior generally expected from complex concentrated alloys. In this review, the fundamental atomistic deformation mechanisms of the CoCrNi alloy will be reviewed with a focus on deformation substructures and chemical short-range ordering. Recent studies on microstructural engineering through thermo-mechanical processing and efforts to enhance the tensile properties of the CoCrNi derived systems with minor alloying additions are discussed. Finally, future directions of research, which involve applying current understanding of the underlying mechanisms towards alloy design strategies, are discussed

On the enhanced hardening ability and plasticity mechanisms in a novel Mn-added CoCrNi medium entropy alloy during high-pressure torsion

Microstructure and texture evolution during high-pressure torsion (HPT) of a novel Mn-added CoCrNi medium entropy alloy (Co33Ni33Cr19Mn15) is investigated for the first time. The alloy exhibited a rapid rise in hardness at relatively low shear strains (gamma <= 20). It is attributed to an extensive dislocation activity to achieve saturation in dislocation density of similar to 10(16) m(-2), combined TWIP and TRIP effects and microstructural refinement. At higher shear strain, hardness increased at much reduced rates owing to saturation of dislocation density, twin fault probability and the TRIP effect, besides continued grain refinement for severe nano-structuring led to subsequent strengthening. The FCC phase showed remarkable stability except a small degree of initial deformation-induced HCP martensitic transformation in an early stage of HPT. The ideal shear texture components were observed at low shear strain, and these continued to evolve up to 5 turns of HPT processing. For similar HPT processing conditions, the studied alloy showed superior hardness (similar to 650 Hv) compared to a wide spectrum of FCC materials, which is ascribed to a combination of the strengthening mechanisms of Taylor hardening, the TRIP and TWIP effects and Hall-Petch strengthening resulting from the nano-structured grains having an average size of similar to 35 nm. (c) 2022 The Author(s). Published by Elsevier B.V. CC_BY_4.

Non-equilibrium solidification of high-entropy alloys monitored in situ by X-ray diffraction and high-speed video

High-entropy alloys (HEAs) have attracted significant interest in the materials science community over the last 15 years. At the first moment, what caught the attention was the fact that these alloys tend to form solid solutions at room temperature, despite being composed of multiple elements in equiatomic or near-equiatomic concentrations. It was initially concluded that the configurational entropy plays a key role in the stabilization of the solid solutions. Later studies revealed the importance of lattice strain enthalpies, enthalpies of mixing, structural mismatch of constituents, and kinetics in phase formation/stability. The study presented in this thesis was branched into three major parts, all related to understanding phase formation, stability, or metastability in this class of alloys. The first part deals with developing an empirical method to predict single-phase solid solution formation in multi-principal element alloys. The second, which makes the core of this thesis, are non-equilibrium solidification studies of CrFeNi and CoCrNi medium-entropy alloys, and CoCrFeNi, Al0.3CoCrFeNi, and NbTiVZr high-entropy alloys. The last part is devoted to understanding the thermophysical properties of CrFeNi, CoCrNi, and CoCrFeNi medium- and high-entropy alloys. An empirical approach, based on the theoretical elastic-strain energy, has been developed to predict the phase formation and its stability for complex concentrated alloys. The conclusiveness of this approach is compared with the traditional empirical rules based on the atomic-size mismatch, enthalpy of mixing, and valence-electron concentration for a database of 235 alloys. The proposed “elastic-strain energy vs. valence-electron concentration” criterion shows an improved ability to distinguish between single-phase solid solutions, mixtures of solid solutions, and intermetallic phases when compared to the available empirical rules used to date. The criterion is especially strong for alloys that precipitate the μ phase. The elastic-strain-energy parameter can be combined with other known parameters, such as those noted above, to establish new criteria which can help in designing novel complex concentrated alloys with the on-demand combination of mechanical properties. The solidification behavior of the CoCrFeNi high-entropy alloy and the ternary CrFeNi and CoCrNi medium-entropy suballoys has been studied in situ using high-speed video-camera and synchrotron X-ray diffraction (XRD) on electromagnetically levitated samples at Leibniz Institute for Solid State and Materials Research Dresden (IFW Dresden) and German Synchrotron DESY, Hamburg. In all alloys, the formation of a primary metastable body-centered cubic bcc phase was observed if the melt was sufficiently undercooled. The delay time for the onset of the nucleation of the stable face-centered cubic fcc phase, occurring within bcc crystals, is inversely proportional to the melt undercooling. The experimental findings agree with the stable and metastable phase equilibria for the (CoCrNi)-Fe section. Crystal-growth velocities for the CrFeNi, CoCrNi, and CoCrFeNi medium- and high-entropy alloys, extracted from the high-speed video sequences in the present study, are comparable to the literature data for Fe-rich Fe-Ni and Fe-Cr-Ni alloys, evidencing the same crystallization kinetics. The effect of melt undercooling on the microstructure of solidified samples is analyzed and discussed in the thesis. To understand the effect of Al addition on the non-equilibrium solidification behavior of the equiatomic CoCrFeNi alloy, the Al0.3CoCrFeNi HEA has been studied. While the quaternary alloy melt could be significantly undercooled, this was not possible in the five-component alloy. Therefore, the investigations on phase formation, crystal growth, and microstructural evolution were confined to the low undercooling regime. In situ XRD measurements revealed that the liquid crystallized into a fcc single-phase solid solution at this undercooling level. However, ex situ XRD revealed the precipitation of the ordered L12 phase for a sample solidified with ΔT = 30 K. Crystal growth velocities are shown to be smaller than in the CoCrFeNi, CrFeNi, and CoCrNi alloys; nonetheless, they are in the same order of magnitude. Spontaneous grain refinement, without the formation of crystal twins, is observed at low undercooling of ΔT = 70 K, which could be explained by the dendrite tip radius dependence on melt undercooling. In situ studies of the equiatomic NbTiVZr refractory high-entropy alloys revealed the effect of processing conditions on the high-temperature phase formation. When the melt was undercooled over 80 K, it crystallized as a bcc single-phase solid solution despite solute partitioning between the dendritic and interdendritic regions. When the sample was solidified from the semisolid state, it resulted in the formation of two additional bcc phases at the interdendritic regions. The crystal growth velocity, as estimated from the high-speed videos, showed pronounced sluggish kinetics: it is 1 to 2 orders of magnitude smaller compared to literature data of other medium and high-entropy alloys. The study of the linear expansion coefficient α and heat capacity at constant pressure of the equiatomic CoCrFeNi and the medium-entropy CrFeNi and CoCrNi alloys revealed an anomalous behavior with S-shaped curves in the temperature range of 700 – 950 K. The anomalous behavior is shown to be reversible as it occurred during the first and second heating. However, a minimum is only observed on the first heating, while in the second heating a sudden increase of both the α and occurs at the temperature of the onset of the minima in the first heating. Magnetic moment measurements as a function of temperature showed that the observed anomaly is not associated with the Curie temperature. Consideration of the structural and microstructural evaluation discards a first-order phase transformation or recrystallization as probable causes, at least for the CoCrFeNi and CoCrNi alloys. Based on literature evidence, the anomalies in the temperature dependences of the linear expansion coefficient and heat capacity are believed to be caused by a chemical short-range order transition known as the K-state effect. However, to reveal the exact nature of this phenomenon, further experimental and theoretical studies are required, which is outside the frame of the present work.:Abstract ....................................................................................................................... I Kurzfassung .............................................................................................................. IV Chapter 1: Motivation and Fundamentals .................................................................. 1 1.1 Introduction .......................................................................................................... 1 1.2 The high-entropy alloy (HEA) design concept ...................................................... 4 1.3 Empirical rules of phase formation for HEAs ....................................................... 6 1.4 Calculation of phase diagrams of HEAs ............................................................. 18 1.5 The core effects of HEAs ................................................................................... 20 1.5.1 Lattice distortion .............................................................................................. 20 1.5.2 Sluggish diffusion ............................................................................................ 22 1.5.3 Cocktail effect................................................................................................... 23 1.6 Mechanical properties ........................................................................................ 24 1.6.1 Lightweight high-entropy alloys ....................................................................... 24 1.6.2 Overcoming the strength-ductility tradeoff ...................................................... 26 1.6.3 Cryogenic high-entropy alloys ......................................................................... 28 1.6.4 Refractory high-entropy alloys ........................................................................ 30 1.7 Functional properties .......................................................................................... 33 1.7.1 Soft magnetic properties ................................................................................. 33 1.7.2 Magnetocaloric properties ............................................................................... 35 1.7.3 Hydrogen storage ............................................................................................ 36 Chapter 2: Experimental .......................................................................................... 38 2.1 Sample preparation ............................................................................................ 38 2.2 Electromagnetic levitation .................................................................................. 40 2.3 In situ X-ray diffraction ........................................................................................ 43 2.4 Microstructural and structural analysis ............................................................... 44 2.5 Thermal analysis ................................................................................................ 45 2.6 Dilatometry ......................................................................................................... 45 2.7 Magnetic moment ............................................................................................... 46 2.8 Heat treatment ................................................................................................... 46 Chapter 3: In situ study of non-equilibrium solidification of CoCrFeNi high-entropy alloy and CrFeNi and CoCrNi ternary suballoys ...................................................... 47 3.1 Introduction ........................................................................................................ 47 3.2 Results ............................................................................................................... 48 3.2.1 In situ synchrotron X-ray diffraction ................................................................. 48 3.2.2 High-speed video imaging ............................................................................... 52 3.2.3 Microstructure of the solidified samples .......................................................... 62 3.3 Discussion .......................................................................................................... 64 3.3.1 bcc-fcc nucleation and growth competition ..................................................... 64 3.3.2. Crystal growth kinetics ................................................................................... 68 3.3.3. Microstructural evolution ................................................................................ 70 Chapter 4: The effect of Al addition to the CoCrFeNi alloy on the non-equilibrium solidification behaviour.............................................................................................. 72 4.1 Introduction ........................................................................................................ 72 4.2 Results and Discussion ...................................................................................... 73 Chapter 5: Non-equilibrium solidification of the NbTiVZr refractory high-entropy alloy ................................................................................................................................. 84 5.1 Introduction ........................................................................................................ 84 5.2 Results ............................................................................................................... 85 5.2.1 In situ synchrotron X-ray diffraction ................................................................. 85 5.2.2 Room temperature synchrotron X-ray diffraction ............................................ 88 5.2.3 High-speed video imaging ............................................................................... 89 5.2.4 Microstructure and structure analysis ............................................................. 91 5.3 Discussion .......................................................................................................... 94 5.3.1 Phase formation upon solidification ................................................................ 94 5.3.2 Crystal growth kinetics .................................................................................... 98 5.3.3 Structural and microstructural features............................................................ 99 Chapter 6: Solid-state thermophysical properties of CrFeNi, CoCrNi, and CoCrFeNi medium- and high-entropy alloys ........................................................................... 101 6.1 Introduction ...................................................................................................... 101 6.2 Results ............................................................................................................. 102 6.3 Discussion ........................................................................................................ 106 6.3.1 Thermophysical properties ............................................................................ 106 6.3.2 Short-range order in medium- and high-entropy alloys ................................. 109 Chapter 7: Summary ............................................................................................... 111 7.1 Empirical rule of phase formation of complex concentrated alloys ................... 111 7.2 Non-equilibrium solidification of medium- and high-entropy alloys ................... 111 7.3 Thermophysical properties of the medium- and high-entropy alloys ................ 113 Chapter 8: Outlook ................................................................................................. 115 Appendix 1 .............................................................................................................. 117 Appendix 2 ............................................................................................................. 123 Appendix 3 ............................................................................................................. 133 Appendix 4 ............................................................................................................. 134 References.............................................................................................................. 140 Acknowledgments .................................................................................................. 164 List of publications .................................................................................................. 166 Erklärung ......................................................................................................................... 16

Complex Concentrated Alloys (CCAs)

This book is a collection of several unique articles on the current state of research on complex concentrated alloys, as well as their compelling future opportunities in wide ranging applications. Complex concentrated alloys consist of multiple principal elements and represent a new paradigm in structural alloy design. They show a range of exceptional properties that are unachievable in conventional alloys, including high strength–ductility combination, resistance to oxidation, corrosion/wear resistance, and excellent high-temperature properties. The research articles, reviews, and perspectives are intended to provide a wholistic view of this multidisciplinary subject of interest to scientists and engineers

Effect of Strain Rate on the Tensile Behavior of CoCrFeNi and CoCrFeMnNi High Entropy Alloys

High entropy alloys (HEAs) are a new class of alloys with the potential to be used in critical load bearing applications instead of conventional alloys. The HEAs studied in this research were CoCrFeNi and CoCrFeMnNi. Both were single-phase face-centered cubic materials. The focus of this study was on the tensile behavior of the two materials at quasi-static and dynamic strain-rates (〖10〗^(-4) to 〖10〗^3 s^(-1)) and the underlying microstructural phenomena driving the behaviors. Electron back-scatter diffraction was performed on both HEAs to study the microstructure before mechanical testing. To study the effect of strain rate, tensile experiments were performed at quasi-static strain rates on hydraulic MTS load frames and dynamic strain-rates on a Split-Hopkinson Pressure Bar. HEAs stress-strain curves, modulus of elasticity, yield strength, ultimate strength, strain-rate sensitivity and work hardening rates were calculated with the data from the tensile experiments. Transmission electron microscopy was performed post-mortem to study the plastic deformation mechanisms activated at different strain rates. The dominant deformation mechanism changed from dislocation slip at quasi-static strain-rates to the addition of deformation nano-twins at dynamic strain-rates. Ultimate strength and ductility both improved with the increase of strain-rate, which can be attributed to the activation of deformation nano-twins in HEAs. CoCrFeNi and CoCrFeMnNi both have low stacking fault energies which encouraged twinning at high strains to accommodate plastic deformation. The strain-rate sensitivity component increased with increasing strain-rate, beginning with negligible strain-rate sensitivity in the quasi-static range to high strain-rate sensitivity in the dynamic range. CoCrFeMnNi showed greater strain-rate sensitivity. CoCrFeNi, with the less configurational entropy, had higher mechanical properties and strain hardening rates at different strain-rates compared to CoCrFeMnNi

Severe Plastic Deformation and Phase Transformations in High Entropy Alloys: A Review

This review discusses an area of expertise that is at the intersection of three large parts of materials science. These are phase transformations, severe plastic deformation (SPD), and high-entropy alloys (HEA). First, SPD makes it possible to determine the borders of single-phase regions of existence of a multicomponent solid solution in HEAs. An important feature of SPD is that using these technologies, it is possible to obtain second-phase nanoparticles included in a matrix with a grain size of several tens of nanometers. Such materials have a very high specific density of internal boundaries. These boundaries serve as pathways for accelerated diffusion. As a result of the annealing of HEAs subjected to SPD, it is possible to accurately determine the border temperature of a single-phase solid solution area on the multicomponent phase diagram of the HEA. Secondly, SPD itself induces phase transformations in HEAs. Among these transformations is the decomposition of a single-phase solid solution with the formation of nanoparticles of the second phase, the formation of high-pressure phases, amorphization, as well as spinodal decomposition. Thirdly, during SPD, a large number of new grain boundaries (GBs) are formed due to the crystallites refinement. Segregation layers exist at these new GBs. The concentration of the components in GBs differs from that in the bulk solid solution. As a result of the formation of a large number of new GBs, atoms leave the bulk solution and form segregation layers. Thus, the composition of the solid solution in the volume also changes. All these processes make it possible to purposefully influence the composition, structure and useful properties of HEAs, especially for medical applications

Effect of nickel addition on enhancing nano-structuring and suppressing TRIP effect in Fe40Mn40Co10Cr10 high entropy alloy during high-pressure torsion

The present work unravels the effect of nickel (Ni) addition on the deformation mechanism and hardness evolution in a Fe40Mn40Co10Cr10 high entropy alloy (HEA) during high-pressure torsion (HPT) processing. For this purpose, two variants of the high entropy Cantor alloy, with compositions (atomic%) Fe40Mn40Co10Cr10 (Ni0 alloy) and Fe35Mn35Co10Cr10Ni10 (Ni10 alloy) were selected. The study revealed a transition in the predominant plasticity mechanism with addition of Ni from TRIP in Ni0 to dislocation slip in Ni10 alloy. Such transition of plasticity mechanism was the direct consequence of an increase in the free energy of phase transformation, delta G(gamma ->epsilon) towards a more positive value with Ni addition. Interestingly, the Ni10 alloy showed a greater extent of nano-structuring than the Ni0 alloy with nearly three-fold refined grain sizes, that is, lesser than 30 nm in Ni10 alloy and ~90 nm in Ni0 alloy. Furthermore, a 3-4 times higher dislocation density was observed in the FCC phase of the Ni10 alloy compared to that in the transformed HCP phase in the Ni0 alloy for any given HPT processing conditions. These differences in mechanism(s) of deformation and the extent of nano-structuring manifested as a greater ability of Ni added Ni10 alloy to harden itself during HPT. The present study suggests that a large fraction of hard HCP phase originating from TRIP effect in the Ni0 alloy has a lower hardening ability than the high dislocation density and nano-structuring in the Ni10 alloy

Global understanding of deformation behavior in CoCrFeMnNi high entropy alloy under high-strain torsion deformation at a wide range of elevated temperatures

A number of recent studies have investigated deformation behavior of CoCrFeMnNi (Cantor) alloy at elevated temperatures by using plastic deformation to relatively small strains such as tensile testing. Therefore, little has been known about the deformation behavior of this typical FCC high-entropy alloy (HEA) in case that the material is subjected to ultra-high strains at various temperatures. In the present study, the equi-atomic CoCrFeMnNi HEA was successfully deformed over a wide range of strains (von Mises equivalent strains (ε) of 1∼5.5) by torsion at various temperatures ranging from 25 °C to 1100 °C. Deformation twinning was extensively activated at moderate to high strains (ε ≥ 1) and even found in the deformation at elevated temperatures as high as 600 °C where deformation twinning is not normally expected in Cantor alloy. The HEA showed outstanding deformability and the highest strains to fracture reached 4.0∼5.5 at low temperatures below 400 °C. The excellent deformability was attributed to the extensive twin activities including the formation of twin bundles and thin nanotwins as well as microbands formation. However, localized shear deformation that was promoted by the high straining at low temperatures could negatively affect the deformability. The heavy deformation led to a significant reduction of the grain sizes down to 50 nm∼150 nm. A sudden shortage of ductility occurred at intermediate temperatures, where small strains to fracture (1.2∼1.3) were realized at 600 °C∼700 °C. The embrittlement was accompanied by the formation of micro-voids at grain boundaries and intergranular fracture. The susceptibility to the embrittlement was caused by the precipitation of Cr-rich σ-phases at grain boundaries. Dynamic recrystallization (DRX) of the FCC matrix led to an accelerated softening at high temperatures above 600 °C. Nucleation and growth of DRX grains in Cantor alloy were not fundamentally different from those in conventional FCC alloys. This study gives an insight into the microstructure evolution and mechanical response in Cantor alloy under shear deformation over a wide range of strains and temperatures

A Review on Heterogeneous Nanostructures: A Strategy for Superior Mechanical Properties in Metals

Generally, strength and ductility are mutually exclusive in homogeneous metals. Nanostructured metals can have much higher strength when compared to their coarse-grained counterparts, while simple microstructure refinement to nanoscale generally results in poor strain hardening and limited ductility. In recent years, heterogeneous nanostructures in metals have been proven to be a new strategy to achieve unprecedented mechanical properties that are not accessible to their homogeneous counterparts. Here, we review recent advances in overcoming this strength-ductility trade-off by the designs of several heterogeneous nanostructures in metals: heterogeneous grain/lamellar/phase structures, gradient structure, nanotwinned structure and structure with nanoprecipitates. These structural heterogeneities can induce stress/strain partitioning between domains with dramatically different strengths, strain gradients and geometrically necessary dislocations near domain interfaces, and back-stress strengthening/hardening for high strength and large ductility. This review also provides the guideline for optimizing the mechanical properties in heterogeneous nanostructures by highlighting future challenges and opportunities