Electronegativity difference as a factor for evaluating the thermal stability of Al-rich metallic glasses

This article proposes a factor, the critical electronegativity difference Δx _cri, to correlate alloy composition with thermal stability and glass-forming ability of Al–Ni–RE (RE: Rare Earth element) ternary metallic glasses. The Al-rich metallic glasses with Δx > Δx _cri exhibit glassy behavior, whereas alloys with Δx < Δx _cri are nanocrystalline. Nanoglassy alloys occur when Δx ≈ Δx _cri. The best glass formers are located near Δx _cri. Furthermore, an equation has been deduced to calculate Δx _cri with varying RE covalent atomic radius.     

Bulk metallic glass formation near the TiCu–TiNi pseudo-binary eutectic composition

No bulk metallic glass (BMG) has been observed so far in the Ti–Cu binary system. It has been found that by choosing a pseudo-binary eutectic (L?→?TiCu +TiNi) deeper than that in the binary, reachable via only small substitution of Cu with Ni, the glass-forming ability can be effectively elevated. BMGs of 1–1.5 mm diameter have been formed over a composition range around Ti₅₀Cu₄₃Ni₇. The new BMGs are reproducibly malleable with significant compressive plastic strains.     

Structural and thermal investigations of a high-strength Cu-Zr-Ti-Co bulk metallic glass

Cu 55 Zr 30 Ti 10 Co 5 bulk metallic glass exhibits a high compressive fracture strength of 2.31 GPa and Young's modulus of 130 GPa, values that are higher than those of other Cu- and Zr-based metallic glasses. The addition of Co to the ternary Cu-Zr-Ti alloy stabilizes the supercooled liquid. On heating, the Cu 55 Zr 30 Ti 10 Co 5 metallic glass devitrified and formed an intermediate intermetallic compound prior to reaching equilibrium by diffusion-controlled growth at constant nucleation rate. In the fully annealed state the structure consists of the equilibrium Cu 10 Zr 7 phase with the slightly reduced lattice parameters a = 0.933 nm, b = 0.928 nm and c = 1.254 nm and a small fraction of an unidentified phase.     

Comparative study of local structure in Zr70Al10Ni20 and quasi-crystal-forming Zr70Al9Ni20Pd1 metallic glasses

The local structure of Zr₇₀Al₉Ni₂₀Pd₁ metallic glass, in which a nano-icosahedral quasi-crystalline phase (I-phase) is formed in the primary stage of crystallization, has been examined and compared with that of Zr₇₀Al₁₀Ni₂₀, the supercooled liquid state of which has a high stability. Since the local environments around the Zr and Ni atoms do not change drastically by the addition of 1 at.% Pd to Zr₇₀Al₁₀Ni₂₀, as evidenced by radial distribution function (RDF) and extended x-ray absorption fine structure (EXAFS) studies, we deduce that the icosahedral phase formed in the Zr₇₀Al₉Ni₂₀Pd₁ metallic glass has a local structure similar to that in Zr₇₀Al₁₀Ni₂₀. Although a very slight rearrangement of Zr–Zr atomic pairs occurs during quasi-crystallization, the I-phase formation is achieved without disturbing the dominant local structure in the glassy state of the Zr₇₀Al₉Ni₂₀Pd₁. An icosahedral local structure is proposed for Zr–Al–Ni metallic glass system as well as for primary quasi-crystal (QC)-forming Zr-based metallic glasses.     

Calculation of alloying effect on formation enthalpy of TiCu intermetallics from first-principles calculations for designing Ti–Cu-system metallic glasses

The effect of alloying on the formation enthalpy of TiCu intermetallics was investigated via first-principles calculations to propose a new design method for Ti–Cu-system metallic glasses. The calculation results showed good agreement with the reported experimental results that Ni, Pd, Sn and Zr improve this system’s glass-forming ability. According to the calculation results, a Ti–Zr–Cu–Ga system was designed as a potential new bulk Ti-based metallic glass, and a bulk sample with a 2-mm diameter was fabricated.     

Structural heterogeneity in a binary Pd–Si metallic glass

A Pd₈₁Si₁₉ bulk metallic glassy rod with a diameter of 4.5 mm was produced by water quenching the fluxed alloy. Despite a negative heat of mixing between Pd and Si elements and very simple components constituting the binary Pd–Si glass-forming system, structural heterogeneity was induced either by slow cooling of a liquid or sub-T_g annealing of glassy ribbons. The sub-T_g annealing experiments evidenced that a more ordered amorphous phase emerged from the original glassy matrix. Our work provides an alternative way to tune the microstructure of metallic glasses by subsequent thermal treatment on an as-prepared single glassy phase.     

Effect of network connectivity on thermal properties of As30Te70– x Tl x glasses

Alternating differential scanning calorimetry (ADSC) studies were undertaken to investigate the effect of Tl addition on the thermal properties of As₃₀Te_{70– x} Tl _x (6?≤?x?≤?22 at%) glasses. These include parameters such as glass-transition temperature (T _g), changes in specific heat capacity (ΔC _p) and relaxation enthalpy (ΔH ^NR) at the glass transition. It was found that T _g of the glasses decreased with the addition of Tl, which is in contrast to the dependence of T _g in As–Te glasses on the addition of Al and In. The change in heat capacity ΔC _p through the glass transition was also found to decrease with increasing Tl content. The addition of Tl to the As–Te matrix may lead to a breaking of As–Te chains and the formation of Tl⁺Te^?AsTe_2/2 dipoles. There was no significant dependence of the change of relaxation enthalpy, through the glass transition, with composition.     

Coexistence of adjacent vacancy-ordered and eutectic phases in Al–Cu–Ni alloys

ABSTRACT

Copper-mould-cast Al–Cu–Ni alloys show adjacent coexistence of in situ grown ordered and eutectic phases. A bimodal microstructure of α–Al and eutectic α-Al+θ-Al₂Cu phases with length-scale hierarchy evolves during solidification. Microstructural analysis through Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) shows the presence of Vacancy-ordered phases (VOPs) with different morphologies in two different compositions.     

Cluster formulae for alloy phases

Composition formulae for alloy phases are developed using first-neighbour coordination polyhedra plus their connections. The resultant cluster formulae [cluster](glue atom) _x , similar to molecular formulae for chemicals, contain key structural and composition information on the alloy phases. As examples, Al–Ni–Zr alloy phases are analysed with the objective of revealing cluster formula properties such as the principal cluster, the cluster phase and the definition of complex alloy phases.     

Formation of plate-shaped Guinier–Preston zones during natural aging of an Al–Zn–Mg–Cu–Zr Alloy

Plate-shaped Guinier–Preston (G–P) zone formation in an Al–Zn–Mg–Cu–Zr alloy has been studied using transmission electron microscopy. The results provide, for the first time, direct evidence showing nucleation and growth of plate-shaped coherent G–P zones during natural aging.     

High temperature mechanics of nanomoulded amorphous metals

High temperature mechanics of nanomoulded amorphous metals was investigated by in situ nanomechanical testing. Nanopillars of Pd₄₃Cu₂₇Ni₁₀P₂₀ metallic glass were synthesized by thermoplastic forming and their stress–strain response was obtained concurrent with direct observation of their deformation behaviour. This allowed the measurement of mechanical behaviour from nanopillars and the corresponding bulk substrate with identical thermal history. A rise in elastic modulus was seen with increase in temperature for both the nanopillars and substrate, which was explained by diffusive rearrangement of atomic-scale viscoelastic units. The results provide fundamental insights into structural rearrangement in metallic glasses.     

Nanocrystallization in a Zr 57 Ti 5 Cu 20 Al 10 Ni 8 bulk metallic glass

The first stages of thermal relaxation towards equilibrium in a Zr 57 Ti 5 Cu 20 Al 10 Ni 8 bulk metallic glass have been studied by differential scanning calorimetry, X-ray diffraction, transmission electron microscopy and high-resolution electron microscopy. These coupled experiments rule out for this glass the existence of a phase separation on the nanometric scale preceding the onset of crystallization. The first step of crystallization is of the primary type, that is it consists of the nucleation of nanocrystallites in the amorphous matrix with which they coexist in metastable equilibrium. The very high nucleation rate leads to a nanometric composite structure with a number density of about 7 2 10 24 m -3 of 3-4nm crystallites, occupying a volume fraction of about 15%. These features, as well as the crystallization kinetics observed during isochronal or isothermal heating, are discussed.     

Compositions of different phases appearing during devitrification of Zr46.75Ti8.25Cu7.5Ni10Be27.5 bulk metallic glass

The devitrification process of Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 metallic glass during annealing in the supercooled liquid region has been studied by conventional, high-resolution and analytical transmission electron microscopy (TEM). Two kinds of particle appear during devitrification: quasicrystals and crystalline precipitates. Nanoanalysis with energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy reveal that quasicrystals are Be free, while the crystallites have the ZrBe₂ hexagonal structure. These experiments confirm the key role of Be during devitrification. They also indicate that quasicrystals can form in the system Zr–Ti–Cu–Ni (without Be), as further evidenced by direct synthesis and an in situ neutron diffraction investigation, according to the chemical composition deduced from the TEM analysis.     

Effect of Sn on microstructure and mechanical properties of (Ti–Cu)-based bulk metallic glasses

A Ti₄₃Zr₇Cu₄₃Ni₇ bulk metallic glass (BMG) exhibits a plastic strain of less than 0.2% under room-temperature compression. However, a Ti₄₅Zr₅Cu₄₀Ni_7.5Sn_2.5 BMG developed by addition of Sn to Ti₄₃Zr₇Cu₄₃Ni₇ shows a significant improvement of ～14.8% to the plastic strain with work hardening. Microstructural comparison of these BMGs reveals that the addition of Sn leads to formation of nano-scale chemical heterogeneities throughout the material. These nano-scale chemical fluctuations play an important role in enhancing the plastic strain of (Ti–Cu)-based BMGs.     

Malleable hypoeutectic Zr–Ni–Cu–Al bulk glassy alloys with tensile plastic elongation at room temperature

A new bulk glassy alloy (BGA) showing macroscopic tensile plastic elongation at room temperature has been developed in the hypoeutectic Zr–Ni–Cu–Al alloy system. The hypoeutectic Zr–Ni–Cu–Al BGA shows a high Poisson's ratio, a low Young's modulus, and is highly malleable in compression. It exhibits a Poisson's ratio of 0.39, a Young's modulus of 73 GPa, and a distinct tensile plastic elongation of about 1.7% at room temperature with necking due to the operation of many shear bands. The tensile plastic deformability seems to originate from modifications of the glass structure with increasing the number of Zr–Zr atomic pairs in the hypoeutectic composition.     

A new orthorhombic approximant of the icosahedral Al–Cu–Fe quasicrystal

We report on the formation of a new crystalline approximant phase of the icosahedral (i-)Al–Cu–Fe quasicrystal. This phase is formed during sintering of Al-based composites reinforced with i-AlCuFeB quasicrystalline particles. The structure of this phase has been characterized by transmission electron microscopy (TEM) and high-resolution electron microscopy (HREM). TEM revealed that it is a B-centred orthorhombic phase with lattice parameters a = 1.166 nm, b = 1.195 nm and c = 3.44 nm. Its chemical composition, as determined by electron energy loss spectroscopy (EELS), is close to Al_76.9Cu_2.7Fe_20.4, with an average number of valence electrons per atom e/a of 1.92, similar to the value in all other approximants of the i-phase discovered thus far. Initial results on local atomic arrangements along one of its pseudo-5-fold axes are also presented.     

Interplay of diffusion and phase transformations in microstructural evolution of the interaction zone between U–9 wt.% Mo and Zr–1 wt.% Nb alloys

Metallurgical interaction between U–9?wt.% Mo metallic fuel alloy and Zr–1?wt.% Nb clad material has been assessed. Interdiffusion of constituent elements across their interface, together with the phase reactions occurring at high temperature and during subsequent cooling, resulted in development of a layered interaction zone where coexistence of a bcc solid solution phase with varying compositions, along with α-U, α-Zr and Mo₂Zr phases could be noticed.     

Microstructural development during transient directional solidification of a hypomonotectic Al–In alloy

Upward directional non-steady-state solidification experiments have been performed on a hypomonotectic Al–5.5?wt%In alloy. The alloy developed cellular as-solidified microstructure for tip growth rates, V _L, higher than 0.95?mm/s. The casting regions associated with V _L?<?0.95?mm/s were shown to be characterized by a microstructure formed by In droplets disseminated in the Al matrix. Tip growth rate and microstructural features, such as cell spacing and interphase spacing, have been experimentally determined. The experimental cell spacings have been compared with theoretical predictions furnished by the Hunt–Lu model. It was found that the experimental scatter lies below the minimum range of values theoretically predicted. Moreover, the experimental cell spacing evolution with V _L is characterized by a ?1.1 power law. The droplets’ interphase spacing, λ, is related to the growth rate by the Jackson–Hunt relationship (λ ² V _L?=?constant).     

TEM observation of oxide scale formed on a Ti–Al–Zr alloy oxidized at 360°C in alkaline steam

Ti–Al–Zr alloy has been oxidized at 360°C in alkaline steam at a pressure of 10.3?±?0.7?MPa. Cross-sectional transmission electron microscopy (TEM) observations indicated that the oxide scale of Ti–Al–Zr alloy was composed of outer and inner subscales, in which the outer layer consists of anatase-TiO₂ and the inner layer a mixture of TiO and Ti₂O. The thickness of the Ti₂O, TiO and anatase-TiO₂ were approximately 50, 100 and 400?nm, respectively. These results were confirmed by X-ray energy dispersive spectrometry (EDS) measurements. The enhanced corrosion of titanium alloys in LiOH solution is attributed to a high hexagonal Ti₂O to tetragonal TiO₂ phase transformation rate induced by the substitution of Li⁺ for Ti⁴⁺ in the oxide layer.     

Efficient atomic packing clusters and glass formation in ternary Al-based metallic glasses

In this article, we propose an efficient atomic packing cluster-based composition protocol to help design Al-based metallic glasses. Its validity is verified by some typical experimental data from the literatures. Furthermore, with this understanding, the Al–Ni–Y alloy system is re-evaluated. As a result, the best glass former Al₈₆Ni₉Y₅ in this system, with the critical thickness of about 500 µm, is successfully fabricated by wedge casting.