In situ visualization of Ni-Nb bulk metallic glasses phase transition

We report the results of the Ni-based bulk metallic glass structural evolution and crystallization behavior in situ investigation. The X-ray diffraction (XRD), transmission electron microscopy (TEM), nano-beam diffraction (NBD), differential scanning calorimetry (DSC), radial distribution function (RDF) and scanning probe microscopy/spectroscopy (STM/STS) techniques were applied to analyze the structure and electronic properties of Ni63.5Nb36.5 glasses before and after crystallization. It was proved that partial surface crystallization of Ni63.5Nb36.5 can occur at the temperature lower than for the full sample crystallization. According to our STM measurements the primary crystallization is originally starting with the Ni3Nb phase formation. It was shown that surface crystallization drastically differs from the bulk crystallization due to the possible surface reconstruction. The mechanism of Ni63.5Nb36.5 glass alloy 2D-crystallization was suggested, which corresponds to the local metastable (3x3)-Ni(111) surface phase formation. The possibility of different surface nano-structures development by the annealing of the originally glassy alloy in ultra high vacuum at the temperature lower, than the crystallization temperature was shown. The increase of mean square surface roughness parameter Rq while moving from glassy to fully crystallized state can be caused by concurrent growth of Ni3Nb and Ni6Nb7 bulk phases. The simple empirical model for the estimation of Ni63.5Nb36.5 cluster size was suggested, and the obtained values (7.64 A, 8.08 A) are in good agreement with STM measurements data (8 A-10 A)

An atomistic study of the structural changes in a Zr–Cu–Ni–Al glass-forming liquid on vitrification monitored in-situ by X-ray diffraction and molecular dynamics simulation

Structural changes in the Zr55Cu30Ni5Al10 liquid alloy on cooling from above the equilibrium liquidus temperature are studied by synchrotron radiation X-ray diffraction and compared with the results of first-principles molecular dynamics simulation. In-situ vitrification of the studied alloy is achieved using a containerless levitation technique. Subsequent analysis of the atomic and electronic structure of the alloy in liquid and glassy states reveals formation of medium-range order on cooling and its relationship with liquid fragility. The structural changes in this alloy are smaller in comparison with a more fragile one

Rejuvenation of metallic glasses by non-affine thermal strain.

When a spatially uniform temperature change is imposed on a solid with more than one phase, or on a polycrystal of a single, non-cubic phase (showing anisotropic expansion-contraction), the resulting thermal strain is inhomogeneous (non-affine). Thermal cycling induces internal stresses, leading to structural and property changes that are usually deleterious. Glasses are the solids that form on cooling a liquid if crystallization is avoided--they might be considered the ultimate, uniform solids, without the microstructural features and defects associated with polycrystals. Here we explore the effects of cryogenic thermal cycling on glasses, specifically metallic glasses. We show that, contrary to the null effect expected from uniformity, thermal cycling induces rejuvenation, reaching less relaxed states of higher energy. We interpret these findings in the context that the dynamics in liquids become heterogeneous on cooling towards the glass transition, and that there may be consequent heterogeneities in the resulting glasses. For example, the vibrational dynamics of glassy silica at long wavelengths are those of an elastic continuum, but at wavelengths less than approximately three nanometres the vibrational dynamics are similar to those of a polycrystal with anisotropic grains. Thermal cycling of metallic glasses is easily applied, and gives improvements in compressive plasticity. The fact that such effects can be achieved is attributed to intrinsic non-uniformity of the glass structure, giving a non-uniform coefficient of thermal expansion. While metallic glasses may be particularly suitable for thermal cycling, the non-affine nature of strains in glasses in general deserves further study, whether they are induced by applied stresses or by temperature change.This research was supported by the World Premier International Research Center Initiative (WPI), MEXT, Japan, by NSF China and MOST 973 China, and by the Engineering and the Engineering and Physical Sciences Research Council, UK (Materials World Network project). Y.H.S. acknowledges support from a China Scholarship Council (CSC) scholarship.This is the author accepted manuscript. The final version is available from Nature Publishing Group via http://dx.doi.org/10.1038/nature1467

Structural Changes in Metallic Glass-Forming Liquids on Cooling and Subsequent Vitrification in Relationship with Their Properties

The present review is related to the studies of structural changes observed in metallic glass-forming liquids on cooling and subsequent vitrification in terms of radial distribution function and its analogues. These structural changes are discussed in relationship with liquid’s properties, especially the relaxation time and viscosity. These changes are found to be directly responsible for liquid fragility: deviation of the temperature dependence of viscosity of a supercooled liquid from the Arrhenius equation through modification of the activation energy for viscous flow. Further studies of this phenomenon are necessary to provide direct mathematical correlation between the atomic structure and properties

Glassy and icosahedral phases in rapidly solidified Ti-Zr-Hf-(Fe, Co or Ni) alloys

The icosahedral quasicrystalline, amorphous plus crystalline and glassy phases were formed in Ti40Zr20Hf20(3d-LTM)20 alloys (3d-LTM=3d late transition metals Fe, Co and Ni). The icosahedral phase formed in the melt-spun Ti40Zr20Hf20Fe20 alloy is metastable and the average size of the quasicrystalline icosahedral particles precipitated in the amorphous matrix is 5 nm. The metastable icosahedral phase transformed to a big-cubic fcc Hf2Fe phase with the grain size of about 20 nm after annealing for 1.8 ks at 841 K. The glassy phase was formed in the melt-spun Ti40Zr20Hf20Co20 alloy and no metastable phase was found to form during the transformation from glassy phase to a stable crystalline phase. Icosaheadral phase formed in the melt-spun Ti40Zr20Hf20Ni20 alloy transformed to a big-cubic fcc (Zr, Ti)2Ni solid solution phase by a solid state reaction

Formation of amorphous and icosahedral phases in Ti-Zr-Hf-LTM (LTM = Ni, Pd or Pt) alloys

A nanoscale icosahedral (I) phase was formed in the melt-spun Ti<SUB>40</SUB>Zr<SUB>20</SUB>Hf<SUB>20</SUB>(LTM)<SUB>20</SUB> (LTM = Ni, Pd, or Pt) alloys. However, in Pd-bearing alloy it is presumed to be a distorted I-phase or a high-order approximation. I phase, Hf<SUB>2</SUB>Pt and β -(Ti, Zr, Hf, Ni) solid solution phases are formed in the arc-melted Ti<SUB>40</SUB>Zr<SUB>20</SUB>Hf<SUB>20</SUB>Pt<SUB>20</SUB> ingot

Effect Of Multiple Alloying Elements On The Glass-Forming Ability, Thermal Stability, And Crystallization Behavior Of Zr-Based Alloys

Effect of multiple alloying elements on the glass-forming ability, thermal stability, and crystallization behavior of Zr-based glass-forming alloys were studied in the present work. We investigated the effect of complete or partial substitution of Ti and Ni with similar early and late transition metals, respectively, on the glass-forming ability and crystallization behavior of the Zr50Ti10Cu20Ni10Al10 alloy. Poor correlation was observed between different parameters indicating the glass-forming ability and the critical size of the obtained glassy samples. Importance of the width of the crystallization interval is emphasized. The kinetics of primary crystallization, i.e., the rate of nucleation and rate of growth of the nuclei of primary crystals is very different from that of the eutectic alloys. Thus, it is difficult to estimate the glass-forming ability only on the basis of the empirical parameters not taking into account the crystallization behavior and the crystallization interval