High Entropy Amorphous Alloys Research Articles

Electronic structure and properties of (TiZrNbCu)1-xNix high entropy amorphous alloys

A comprehensive study of selected properties of four (TiZrNbCu)1-xNix (x ≤ 0.25) amorphous high entropy alloys (a-HEA) has been performed. The samples were ribbons about 20 μm thick and their fully amorphous state was verified by X-ray diffraction and thermal analysis. The surface morphology, precise composition and the distribution of components were studied with a Scanning electron microscope (SEM) with an energy dispersive spectroscopy (EDS) attachment. The properties selected were the melting temperature (Tm), the low temperature specific heat (LTSH), the magnetic susceptibility χexp and the Young's modulus (E). Whereas LTSH and χexp were measured for the as-cast samples, E was measured both for as-cast samples and relaxed samples (after a short anneal close to the glass transition temperature). The LTSH showed that the electronic density of states at the Fermi level, N0(EF), decreases with increasing x, whereas the Debye temperature (θD) increases with x. This is similar to what is observed in binary and ternary amorphous alloys of early transition metals (TE) with late transition metals (TL) and indicates that N0(EF) is dominated by the d-electrons of the TE. The LTSH also showed the absence of superconductivity down to 1.8 K and indicated the emergence of the Boson peak above 4 K in all alloys. The free-electron like paramagnetic contribution to χexp also decreases with x, whereas E, like θD, increases with x, indicating enhanced interatomic bonding on addition of Ni. The applicability of the rule of mixtures to these and other similar HEAs is briefly discussed.

Thermodynamic modeling and composition design for the formation of Zr–Ti–Cu–Ni–Al high entropy bulk metallic glasses

This work explores the idea of predicting metallic glass forming composition in a multi component alloy for which an equilibrium phase diagram is yet to be deciphered. Deep eutectic regions in a quaternary alloy (Zr–Ti–Cu–Ni) have been extrapolated to the quinary Zr–Ti–Cu–Ni–Al system for designing a potential bulk glass forming composition. PHSS parameter which is the product of mixing enthalpy, mismatch entropy and configurational entropy of an alloy, has been utilized for thermodynamic modeling. PHSS values are computed through substitution of Al into the each of the fifteen quaternary eutectics that have been reported in the literature in the Zr–Ti–Cu–Ni system. A good correlation of PHSS range between modeled alloys and established glass formers indicates the subtle efficacy of this method for high entropy amorphous alloy design through a rationale thermodynamic approach.

Structural evolution during mechanical milling and subsequent annealing of Cu–Ni–Al–Co–Cr–Fe–Ti alloys

This study reports the structural evolution of high-entropy alloys from elemental materials to amorphous phases during mechanical alloying, and further, to equilibrium phases during subsequent thermal annealing. Four alloys from quaternary Cu 0.5NiAlCo to septenary Cu 0.5NiAlCoCrFeTi were analyzed. Microstructure examinations reveal that during mechanical alloying, Cu and Ni first formed a solid solution, and then other elements gradually dissolved into the solid solution which was finally transformed into amorphous structures after prolonged milling. During thermal annealing, recovery of the amorphous powders begins at 100 °C, crystallization occurs at 250–280 °C, and precipitation and grain growth of equilibrium phases occur at higher temperatures. The glass transition temperature usually observed in bulk amorphous alloys was not observed in the present amorphous phases. These structural evolution reveal three physical significances for high-entropy alloys: (1) the annealed state of amorphous powders produces simple equilibrium solid solution phases instead of complex phases, confirming the high-entropy effect; (2) amorphization caused by mechanical milling still meets the minimum criterion for amorphization based on topological instability proposed by Egami; and (3) the nonexistence of a glass transition temperature suggests that Inoue's rules for bulk amorphous alloys are still crucial for the existence of glass transition for a high-entropy amorphous alloy.