Molten Salt Corrosion Behavior of Dual-Phase High Entropy Alloy for Concentrating Solar Power Systems.

Dual-phase high entropy alloys have recently attracted widespread attention as advanced structural materials due to their unique microstructure, excellent mechanical properties, and corrosion resistance. However, their molten salt corrosion behavior has not been reported, which is critical in evaluating their application merit in the areas of concentrating solar power and nuclear energy. Here, the molten salt corrosion behavior of AlCoCrFeNi2.1 eutectic high-entropy alloy (EHEA) was evaluated in molten NaCl-KCl-MgCl2 salt at 450 °C and 650 °C in comparison to conventional duplex stainless steel 2205 (DS2205). The EHEA showed a significantly lower corrosion rate of ~1 mm/year at 450 °C compared to ~8 mm/year for DS2205. Similarly, EHEA showed a lower corrosion rate of ~9 mm/year at 650 °C compared to ~20 mm/year for DS2205. There was selective dissolution of the body-centered cubic phase in both the alloys, B2 in AlCoCrFeNi2.1 and α-Ferrite in DS2205. This was attributed to micro-galvanic coupling between the two phases in each alloy that was measured in terms of Volta potential difference using a scanning kelvin probe. Additionally, the work function increased with increasing temperature for AlCoCrFeNi2.1, indicating that the FCC-L12 phase acted as a barrier against further oxidation and protected the underlying BCC-B2 phase with enrichment of noble elements in the protective surface layer.

Model Metallic Glasses for Superior Electrocatalytic Performance in a Hydrogen Oxidation Reaction.

Metallic glasses or amorphous alloys, with their excellent chemical stability, disordered atomic arrangement, and ability for thermoplastic nanostructuring, show promising performance toward a range of electrocatalytic reactions in proton-exchange membrane fuel cells. However, there are knowledge gaps and a distinct lack of understanding of the role of amorphous alloy chemistry in determining their catalytic activity. Here, we demonstrate the influence of alloy chemistry and the associated electronic structure on the hydrogen oxidation reaction (HOR) activity of a systematic series of Pt42.5-xPdxCu27Ni9.5P21 bulk metallic glasses (BMGs) with x = 0 to 42.5 at%. The HOR activity and electrochemical active surface area as a function of composition were in the form of volcano plots, with a peak around equal proportion of Pt and Pd. The lower relative electron work function and higher binding energy of the Pt core level explain the reduced charge-transfer resistance and improved electrocatalytic activity due to weakened chemisorption of protons in the mid-range composition. Density functional theory calculations show the lower free energy change and higher hydrogen adsorption density for these Pt42.5-xPdxCu27Ni9.5P21 BMGs, suggesting a synergistic effect from the presence of both noble metals, Pt and Pd.

Multiscale Manufacturing of Amorphous Alloys by a Facile Electrodeposition Approach and Their Property Dependence on the Local Atomic Order.

Metallic glasses are a unique class of materials combining ultrahigh strength together with plastic-like processing ability. However, the currently used melt quenching route to obtain amorphous alloys has a high cost basis in terms of manufacturing and expensive constituent elements often necessary to achieve the glassy state, thus hindering widespread adoption. In contrast, multimaterial electrodeposition offers a low-cost and versatile alternative to obtain amorphous alloys. Here, we demonstrate multiscale manufacturing of a model binary amorphous system by a facile and scalable pulsed electrodeposition approach. The structural and mechanical characteristics of electrodeposited Ni-P metallic glasses are investigated by a combination of experiments and molecular dynamics simulations. The property dependence on slight change in alloy chemistry is explained by the fraction of short-range-order clusters and geometrically unfavorable motifs. Bicapped square antiprism polyhedra clusters with two-atom connections result in more homogeneous deformation for Ni90P10 metallic glass, whereas a relatively higher fraction of three-atom connections in Ni85P15 metallic glass leads to higher strength, albeit localized and relatively brittle failure. The practicality of our approach is likely to stimulate the use of amorphous alloys in simple chemistries for multiscale use with systematic property optimization for specific applications.

Small-scale mechanical behavior of a eutectic high entropy alloy.

Eutectic high entropy alloys, with lamellar arrangement of solid solution phases, represent a new paradigm for simultaneously achieving high strength and ductility, thereby circumventing this well-known trade-off in conventional alloys. However, dynamic strengthening mechanisms and phase-boundary interactions during external loading remain unclear for these eutectic systems. In this study, small-scale mechanical behavior was evaluated for AlCoCrFeNi2.1 eutectic high entropy alloy, consisting of a lamellar arrangement of L12 and B2 solid-solution phases. The ultimate tensile strength was 1165 MPa with ductility of ~18% and ultimate compressive strength was 1863 MPa with a total compressive fracture strain of ~34%. Dual mode fracture was observed with ductile failure for L12 phase and brittle mode for B2 phase. Phase-specific mechanical tests using nano-indentation and micro-pillar compression showed higher hardness and strength and larger strain rate sensitivity for B2 compared with L12. Micro-pillars on B2 phase deformed by plastic barreling while L12 micro-pillars showed high density of slip steps due to activation of more slip systems and homogenous plastic flow. Mixed micro-pillars containing both the phases exhibited dual yielding behavior while the interface between L12 and B2 was well preserved without any sign of separation or cracking. Phase-specific friction analysis revealed higher coefficient of friction for B2 compared to L12. These results will pave the way for fundamental understanding of phase-specific contribution to bulk mechanical response of concentrated alloys and help in designing structural materials with high fracture toughness.

Noble-Metal based Metallic Glasses as Highly Catalytic Materials for Hydrogen Oxidation Reaction in Fuel Cells.

Electro-catalyst design with superior performance and reduced precious metal content (compared to state-of-the-art Pt/C) has been a challenge in proton exchange membrane fuel cells, preventing their widespread adoption. Metallic glasses have recently shown promising performance and large electrochemical surface area in catalytic reactions. The electro-catalytic behavior of recently developed Pt-, Pd-, and Pt/Pd-based metallic glasses was evaluated in this study using scanning electrochemical microscopy. The influence of chemistry and electronic structure on catalytic behavior was studied using scanning kelvin probe technique. The work function for the metallic glasses was lower by 75 mV to 175 mV compared to pure Pt. This resulted in higher catalytic activity for the amorphous alloys, which was attributed to the ease of charge transfer on the surface. The binding energy for the metallic glasses, measured using X-ray photoelectron spectroscopy, was higher by 0.2 eV to 0.4 eV. This explained easier removal of adsorbed species from the surface of amorphous alloys. The synergistic effect of Pt and Pd in alloys containing both the noble metals was demonstrated towards hydrogen oxidation reaction.

Electrochemical and Friction Characteristics of Metallic Glass Composites at the Microstructural Length-scales.

Metallic glass composites represent a unique alloy design strategy comprising of in situ crystalline dendrites in an amorphous matrix to achieve damage tolerance unseen in conventional structural materials. They are promising for a range of advanced applications including spacecraft gears, high-performance sporting goods and bio-implants, all of which demand high surface degradation resistance. Here, we evaluated the phase-specific electrochemical and friction characteristics of a Zr-based metallic glass composite, Zr56.2Ti13.8Nb5.0Cu6.9Ni5.6Be12.5, which comprised roughly of 40% by volume crystalline dendrites in an amorphous matrix. The amorphous matrix showed higher hardness and friction coefficient compared to the crystalline dendrites. But sliding reciprocating tests for the composite revealed inter-phase delamination rather than preferred wearing of one phase. Pitting during potentiodynamic polarization in NaCl solution was prevalent at the inter-phase boundary, confirming that galvanic coupling was the predominant corrosion mechanism. Scanning vibration electrode technique demonstrated that the amorphous matrix corroded much faster than the crystalline dendrites due to its unfavorable chemistry. Relative work function values measured using scanning kelvin probe showed the amorphous matrix to be more electropositive, which explain its preferred corrosion over the crystalline dendrites as well as its characteristic friction behavior. This study paves the way for careful partitioning of elements between the two phases in a metallic glass composite to tune its surface degradation behavior for a range of advanced applications.