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Zr65Al7.5Ni10Cu12.5Nb5 glass was found to exhibit a large plastic compressive strain of over 10% and the property was suggested to be due to deformation-induced nanocrystallization. A transmission electron microscopic observation, however, only revealed obscure ordered clusters with a size of ˜2 nm in the fracture surface of a deformed sample, instead of well-identified crystals as previously reported for the Zr–Al–Ni–Cu–Pd system. This phenomenon is suggested to correlate with the higher viscosity of supercooled liquid and the slower grain growth of icosahedral phase during primary crystallization in the Zr65Al7.5Ni10Cu12.5Nb5 compared to those in the Zr65Al7.5Ni10Cu12.5Pd5 alloy. The role of the deformation-induced nanoclusters on the enhanced compressive plasticity was discussed.
The transformation behavior from glassy state was investigated in Zr- and Hf-based glassy alloys. The primary phases are metastable face-centered-cubic (fcc) Zr2Ni and fcc Hf2Ni phases in the Zr65Al7.5Ni10Cu17.5 and Hf65Al7.5Ni10Cu17.5 glassy alloys, respectively. By substitution of 5 at.% Pd for Cu, the primary phase changes to an icosahedral quasicrystalline phase in both alloys. It is found that the addition of elements, which have a positive or weak chemical affinity with one of the constitutional elements in the Zr–Al–Ni–Cu and Hf–Al–Ni–Cu glassy alloys, is effective for the precipitation of the icosahedral phase. It is suggested that Pd plays a dominant role in an increase in the number of nucleation sites. Since an icosahedron is contained as a structure unit in the icosahedral, fcc Zr2Ni and fcc Hf2Ni phases, it is implied that these phases are correlated with the local icosahedral order. The high-resolution transmission electron microscopy images of the as-spun Zr65Al7.5Ni10Cu7.5Pd10 and Hf65Al7.5Ni10Cu12.5Pd5 alloys reveal a possibility of the existence of the icosahedral ordered regions. It is therefore, concluded that the icosahedral short- or medium-range order exists and it stabilizes the glassy state in the Zr- and Hf-based multicomponent alloys.
A magnesium (Mg) solid solution with a long periodic hexagonal structure was found in a Mg97Zn1Y2 (at.%) alloy in a bulk form prepared by warm extrusion of atomized powders at 573 K. The novel structure has an ABACAB-type six layered packing with lattice parameters of a = 0.322 nm and c = 3 × 0.521 nm. The Mg solid solution has fine grain sizes of 100 to 150 nm and contains 0.78 at.% Zn and 1.82 at.% Y. In addition, cubic Mg24Y5 particles with a size of about 7 nm are dispersed at small volume fractions of less than 10% in the Mg matrix. The specific density (ρ) of the extruded bulk Mg–Zn–Y alloy was 1.84 Mg/m3. The tensile yield strength (σy) and elongation (δ) are 610 MPa and 5%, respectively, at room temperature, and the specific yield strength defined by the ratio of σy to ρ is as high as 3.3 × 105 Nm/kg. High σy values exceeding 400 MPa are also maintained at temperatures up to 473 K. It is noticed that the σy levels are 2.5 to 5 times higher than those for conventional high-strength type Mg-based alloys. The Mg-based alloy also exhibits a high-strain-rate superplasticity with large δ of 700 to 800% at high strain rates of 0.1 to 0.2 s−1 and 623 K. The excellent mechanical properties are due to the combination of the fine grain size, new long periodic hexagonal solid solution containing Y and Zn, and dispersion of fine Mg24Y5 particles. The new Mg-based alloy is expected to be used in many fields.
Glass-forming ability, thermal stability and nucleation behavior of a Pd40Cu30Ni10P20 alloy prepared using a high purity polycrystalline phosphorus are investigated. The critical cooling rate for glass formation for the high purity alloy is the same as that for the previous result, but the improvement of undercooling reaches about 80 K as compared with the fluxed ordinary alloy. In comparison with the non-fluxed alloy, the solidified structure of the present highly purified alloy is significantly different. The non-fluxed sample shows the characteristic “island-like” structure consisted of acicular fcc-Pd2Ni2P solid solution and Cu3Pd intermetallic compound. These acicular phases appear to be caused by the growth of quenched-in nuclei. In the isothermal experiment, nucleus density exhibits time dependence even at 683 K near the nose temperature. It is assumed that the crystallization behavior for the highly purified alloy is closer to homogeneous nucleation from quenched-in nuclei dominant behavior. In order to investigate the nucleation behavior, in-situ TEM observation was carried out. Spherical Pd15P2 particle with a diameter about 15 nm is observed, and this spherical region repeats generation and annihilation during isothermal annealing. The reason for the high glass-forming ability is discussed on the basis of the obtained results.
It is found that a nano icosahedral phase with diameters below 50 nm is formed as a primary phase in the Zr70Ni10M20, Zr70TM10Pd20, Zr70Au10Pd20 and Zr75Pt10Pd15 ternary and Zr70Pd30 binary glassy alloys. The nanoscale icosahedral phase in the diameter range below 10 nm was also found to be formed directly in the melt-spun Zr80Pt20 binary alloy. These icosahedral phases transform to the crystalline phase(s) at the higher annealing temperature. The nucleation kinetics for the precipitation of the icosahedral phase from supercooled liquid were examined in the Zr70Pd30 and Zr70Ni10Pd20 glassy alloys. It was clarified that the transformation of both alloys proceeds in the diffusion-controlled growth mode with increasing nucleation rate. The formation of the nanometer-scale icosahedral phase is due to the transformation mode. The activation energy of nucleation is evaluated to be 267 kJmol−1 for the binary alloy and 311 kJmol−1 for the ternary alloy. The difference between the two alloy systems seems to originate from the difference in the number of atoms for rearrgements in the nucleation mode. The short-range ordering is observed in the as-quenched Zr70Pd30 glassy alloy, which is indicative of the icosahedral structure. The formation of the nano-scale icosahedral phase in the Zr-based binary and ternary alloys is due to the existence of an icosahedral short-range order in the glassy or liquid state. It is suggested that the icosahedral short-range order is stabilized by the restraint of the long-range atomic rearrangements that lead to the transition to a periodic structure by the strong chemical affinities of Pd or Pt with Zr.
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