Precipitation of an icosahedral quasicrystalline phase in Hf59Ni8Cu20Al10Ti3 metallic glass

The crystallization process of a Hf₅₉Ni₈Cu₂₀Al₁₀Ti₃     

Low-temperature mechanical properties of Ce68Al10Cu20Co2 bulk metallic glass

Although it is well known that traditional metals and alloys will become brittle at low temperatures, the effect of low temperature on the mechanical properties of bulk metallic glasses (BMGs) is yet to be fully understood. In this research, the mechanical properties of Ce₆₈Al₁₀Cu₂₀Co₂ BMG are investigated at low temperatures. It is found that the yield strength of the Ce-based BMG increases significantly with the decrease of temperature. The elastic moduli of the BMG also increase monotonically with the drop of temperature, indicating the continuous stiffening of the BMG, while both Poisson's ratio and global plasticity decline at low temperatures. It is considered that the stiffer atomic bonds of the Ce-based BMG at low temperatures result in the increase of strength, and the higher energy required for nucleation of shear bands also leads to the increase in yield strength.     

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.     

Formation of icosahedral quasicrystals in an annealed Zr65Al7.5Ni10Cu12.5Ag5 metallic glass

The formation and thermal stability of an icosahedral quasicrystalline phase in an annealed Zr₆₅Al_7.5Ni₁₀Cu_12.5Ag₅ metallic glass have been investigated by X-ray diffraction and transmission electron microscopy analyses. It was found that the quasicrystalline phase can precipitate from the glassy state and the supercooled liquid of the alloy over a wide range of annealing temperatures. After optimizing the heat-treatment conditions, the volume fraction of the quasicrystalline phase in the alloy can reach as high as about 80%. Investigation of the thermal stability of the quasicrystalline phase demonstrates that it is very stable when the annealing temperature is below the glass transformation temperature T _g of the alloy.     

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.     

Phase transitions of Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass at pressures up to 27 GPa

The phase transitions of Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass have been investigated under high pressures and at room temperature. Direct resistance measurements in a diamond anvil cell provide evidence of a reversible transition between amorphous and crystalline phases; crystallization events occurred at 24 and 26.2 GPa on uploading, and crystalline-to-amorphous phase transitions were observed at 16 and 10.6 GPa on downloading. The phase transitions were confirmed by transmission electron microscopy observations.     

Changes of hardness and electronic work function of Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass on annealing

The hardness and electronic work function (EWF) of a bulk metallic glass, namely Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5, have been studied experimentally, with an emphasis on the effect of heat treatments. The glass was annealed at different time and temperatures, and its hardness and EWF measured using the Rockwell indentation technique and a scanning Kelvin probe system, respectively. It is found that the EWF decreases with annealing time and temperature, whereas the hardness increases. This study shows a close relationship between hardness and EWF, indicating that the EWF could be a sensitive parameter for characterising and investigating the mechanical behaviour of BMG at the electronic level.     

Effect of strain rate on the compressive behaviour of a Zr56Al10.9Ni4.6Cu27.8Nb0.7 bulk metallic glass

We report the study of the effect of strain rate on the compressive behaviour of a Zr₅₆Al_10.9Ni_4.6Cu_27.8Nb_0.7 bulk metallic glass. The results indicated that both the strength and plasticity of the glass increase with increasing the strain rate up to 10^?5 s^?1, above which the strength and plasticity start to decrease. The enhanced mechanical properties under a strain rate of 10^?5 s^?1 are due to the emission/propagation rate of the shear bands being consistent with the strain rate.     

Effect of local chemistry,structure and length scale of heterogeneities on the mechanical properties of a Ti45Cu40Ni7.5Zr5Sn2.5 bulk metallic glass

We report on distinct variations in local chemistry, structure and length scale of heterogeneous regions in Ti₄₅Cu₄₀Ni_7.5Zr₅Sn_2.5 fully glass rods of different diameters, i.e. rods subjected to different cooling rates. The present investigations indicate that the mechanical properties of the Ti₄₅Cu₄₀Ni_7.5Zr₅Sn_2.5 bulk metallic glass can be modified within a wide range of strength and plastic deformability by controlling the scale of the heterogeneous regions in the glass through appropriate variation of the cooling rate applied for solidification.     

Effects of Ag and Pd on the nucleation and growth of the nano-icosahedral phase in Zr65Al7.5Ni10Cu7.5M10 (M = Ag or Pd) metallic glasses

The nucleation and growth of a nano-icosahedral phase from a supercooled liquid region of Zr₆₅Al_7.5Ni₁₀Cu_7.5M₁₀ (M = Ag or Pd) glasses have been examined by differential scanning calorimetry and transmission electron microscopy. The growth rate of the icosahedral phase is nearly constant at the initial stage and much slower than that of the Zr₂Ni phase in the Zr₆₅Al_7.5Ni₁₀Cu_17.5 metallic glass. The homogeneous nucleation rate has a maximum value of 4.4 x 10²⁰ m^-3 s^-1 at 695 K in the Zr₆₅Al_7.5Ni₁₀Cu_7.5Ag₁₀ glass, which is approximately 10² times higher than that for the formation of quasicrystalline phase in the Zr_69.5Al_7.5Ni₁₁Cu₁₂ glass and 10⁴ times higher than that of the Zr₂Ni phase in the Zr₆₅Al_7.5Ni₁₀Cu_17.5 glass. With increasing Pd content, the nucleation rate of the primary phase increases significantly and the growth rate decreases at the crystallization temperature. Thus, the addition of Ag and Pd is effective for an increase in the number of nucleation sites and the suppression of grain growth, which is the main reason for the formation of icosahedral nanoparticles. The significant increase in the nucleation rate is due to an increase in the number of nucleation sites resulting from the short-range ordering consisting of Zr-(Ag or Pd) strong pairs. It is implied that the strong pair Zr-(Ag or Pd) also contributes to the restraint of the long-range rearrangements of the constitutional elements. The formation of the nanoicosahedral phase suggests that icosahedral short-range order exists in the glassy state in the present alloys.     

Difference in microstructure of Zr41Ti14Cu12.5Ni10Be22.5 glasses prepared in a 52 m drop tube and by water quenching

A 52 m drop tube has been used to solidify bulk-glass-forming Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 alloy. Glassy balls with different sizes solidified from the droplets whose structural features, glass-transition behaviour and crystallization kinetics have been investigated. The results indicate that the apparent activation energies of the glass transition and main crystallization reaction are significantly different from those of samples prepared by water quenching. The structural difference between the two types of glassy specimen is revealed by compression studies and in situ energy-dispersive X-ray diffraction. The results are important for understanding the structural features of bulk-forming glasses.