Mechanistic understanding of speciated oxide growth in high entropy alloys

Complex multi-element alloys are gaining prominence for structural applications, supplementing steels, and superalloys. Understanding the impact of each element on alloy surfaces due to oxidation is vital in maintaining material integrity. This study investigates oxidation mechanisms in these alloys using a model five-element equiatomic CoCrFeNiMn alloy, in a controlled oxygen environment. The oxidation-induced surface changes correlate with each element's interactive tendencies with the environment, guided by thermodynamics. Initial oxidation stages follow atomic size and redox potential, with the latter becoming dominant over time, causing composition inversion. The study employs in-situ atom probe tomography, transmission electron microscopy, and X-ray absorption near-edge structure techniques to elucidate the oxidation process and surface oxide structure evolution. Our findings deconvolute the mechanism for compositional and structural changes in the oxide film and will pave the way for a predictive design of complex alloys with improved resistance to oxidation under extreme conditions

Developing Precipitation Hardenable High Entropy Alloys

High entropy alloys (HEAs) is a concept wherein alloys are constructed with five or more elements mixed in equal proportions; these are also known as multi-principle elements (MPEs) or complex concentrated alloys (CCAs). This PhD thesis dissertation presents research conducted to develop precipitation-hardenable high entropy alloys using a much-studied fcc-based equi-atomic quaternary alloy (CoCrFeNi). Minor additions of aluminium make the alloy amenable for precipitating ordered intermetallic phases in an fcc matrix. Aluminum also affects grain growth kinetics and Hall-Petch hardenability. The use of a combinatorial approach for assessing composition-microstructure-property relationships in high entropy alloys, or more broadly in complex concentrated alloys; using laser deposited compositionally graded AlxCrCuFeNi2 (0 < x < 1.5) complex concentrated alloys as a candidate system. The composition gradient has been achieved from CrCuFeNi2 to Al1.5CrCuFeNi2 over a length of ~25 mm, deposited using the laser engineered net shaping process from a blend of elemental powders. With increasing Al content, there was a gradual change from an fcc-based microstructure (including the ordered L12 phase) to a bcc-based microstructure (including the ordered B2 phase), accompanied with a progressive increase in microhardness. Based on this combinatorial assessment, two promising fcc-based precipitation strengthened systems have been identified; Al0.3CuCrFeNi2 and Al0.3CoCrFeNi, and both compositions were subsequently thermo-mechanically processed via conventional techniques. The phase stability and mechanical properties of these alloys have been investigated and will be presented. Additionally, the activation energy for grain growth as a function of Al content in these complex alloys has also been investigated. Change in fcc grain growth kinetic was studied as a function of aluminum; the apparent activation energy for grain growth increases by about three times going from Al0.1CoCrFeNi (3% Al (at%)) to Al0.3CoCrFeNi. (7% Al (at%)). Furthermore, Al addition leads to the precipitation of highly refined ordered L12 (γ′) and B2 precipitates in Al0.3CoCrFeNi. A detailed investigation of precipitation of the ordered phases in Al0.3CoCrFeNi and their thermal stability is done using atom probe tomography (APT), transmission electron microscopy (TEM) and Synchrotron X-ray in situ and ex situ analyses. The alloy strengthened via grain boundary strengthening following the Hall-Petch relationship offers a large increment of strength with small variation in grain size. Tensile strength of the Al0.3CoFeNi is increased by 50% on precipitation fine-scale γ′ precipitates. Furthermore, precipitation of bcc based ordered phase B2 in Al0.3CoCrFeNi can further strengthen the alloy. Fine-tuning the microstructure by thermo-mechanical treatments achieved a wide range of mechanical properties in the same alloy. The Al0.3CoCrFeNi HEA exhibited ultimate tensile strength (UTS) of ~250 MPa and ductility of ~65%; a UTS of ~1100 MPa and ductility of ~30%; and a UTS of 1850 MPa and a ductility of 5% after various thermo-mechanical treatments. Grain sizes, precipitates type and size scales manipulated in the alloy result in different strength ductility combinations. Henceforth, the alloy presents a fertile ground for development by grain boundary strengthening and precipitation strengthening, and offers very high activation energy of grain growth aptly suitable for high-temperature applications

Deformation induced intermediate metastable lattice structures facilitate ordered B2 nucleation in a fcc-based high entropy alloy

Ordered B2 precipitates typically nucleate at the grains-boundaries of fcc-based high entropy alloys. Here, we report a novel mixed-mode coupled displacive-diffusional transformation resulting in homogeneously distributed intra-granular B2 precipitates within the fcc matrix. Severe plastic deformation forms compositionally invariant, metastable distorted fcc structures, resembling hexagon-like templates, at the deformation twin-boundaries. These shear-induced hexagon-like templates correspond to the symmetry of the {111}bcc planes, and act as sites for B2 nucleation, establishing the fcc-bcc Kurdjumov–Sachs (KS) orientation relationship. However, the composition of these B2 precipitates is far-from-equilibrium. Subsequent isothermal annealing causes solute partitioning driving the composition of the B2 precipitates towards equilibrium

Engineering transformation pathways in an Al0.3CoFeNi complex concentrated alloy leads to excellent strength–ductility combination

Guided by thermodynamic modeling, engineering phase transformation pathways via thermo-mechanical processing, in a complex concentrated alloy/high entropy alloy (HEA) of composition Al0.3CoFeNi, lead to a novel multi-scale microstructure consisting of fine-scale FCC + L12 grains mixed with B2 + BCC grains. The two-step pathway comprises initial decomposition of the parent single-phase FCC to form a fine-grained FCC + B2 microstructure, which further decomposes in the second step into the complex four-phase mixture, exhibiting an excellent combination of tensile yield stress of ∼1490 MPa, ultimate tensile strength of ∼1663 MPa, with a good ductility of ∼12% at room temperature

Hierarchical eutectoid nano-lamellar decomposition in an Al0.3CoFeNi complex concentrated alloys

This paper reports a novel eutectoid nano-lamellar (FCC + L12)/(BCC + B2) microstructure that has been discovered in a relatively simple Al0.3CoFeNi high entropy alloy (HEA) or complex concentrated alloy (CCA). This novel eutectoid nano-lamellar microstructure presumably results from the complex interplay between Al-mediated lattice distortion (due to its larger atomic radius) in a face-centered cubic (FCC) CoFeNi solid solution, and a chemical ordering tendency leading to precipitation of ordered phases such as L12 and B2. This eutectoid microstructure is a result of solid-state decomposition of the FCC matrix and therefore distinct from the commonly reported eutectic microstructure in HEAs which results from solidification. This novel nano-lamellar microstructure exhibits a tensile yield strength of 1074 MPa with a reasonable ductility of 8%. The same alloy can be tuned to form a more damage-tolerant FCC + B2 microstructure, retaining high tensile yield stress (~900 MPa) with appreciable tensile ductility (>20%), via annealing at 700 °C. Such tunability of microstructures with dramatically different mechanical properties can be effectively engineered in the same CCA, by exploiting the complex interplay between ordering tendencies and lattice distortion

Tensile yield strength of a single bulk Al0.3CoCrFeNi high entropy alloy can be tuned from 160 MPa to 1800 MPa

While there have been multiple recent reports in the literature of exceptional combinations of yield strength and ductility in high entropy alloys, there have been no reports discussing the extraordinary tunability of the mechanical properties in the same alloy in these systems. This paper shows that the tensile yield-strength of a single Al0.3CoCrFeNi high entropy alloy (or complex-concentrated alloy), can be enhanced from 160 MPa to over 1800 MPa (1.8 GPa), a 1025% increase, via microstructural engineering enabled by thermo-mechanical processing of the bulk alloy. Such strength variations for the same composition are unprecedented in any other class of alloys