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.

Crystal nucleation and growth processes in Cu-rich glass-forming Cu-Zr alloys.

The glass formation ability of an alloy depends on two competing processes: glass-transition, on one hand, and crystal nucleation and growth, on the other hand. While these phenomena have been widely studied before in nearly equiatomic Cu-Zr alloys, studies are lacking for solute/solvent-rich ones. In the present work, molecular dynamics simulations show that the addition of a small amount of Zr (1-10 at. %) to Cu drastically increases the incubation time and slows down crystal growth, thus, leading to an improved glass forming ability. The crystal nucleation and growth processes of a competing face-centered cubic (FCC) Cu crystalline phase are analyzed in detail. In particular, the values of the critical cooling rate, incubation period for crystallization, and growth rate of FCC Cu crystals in these Cu-rich alloys are obtained. The growth of a supersaturated FCC Cu solid solution is found to be polymorphic at the interface (except for alloys with 9 and 10 at. % Zr) though a Zr concentration gradient is observed within growing crystals at high enough Zr content. The crystal growth rate before crystal impingement is nearly constant in all alloys, though it decreases exponentially with the Zr content. Crystallization kinetics are also analyzed within the existing theories and compared with the experimental values available in the literature.

Atomic structure of an FeCrMoCBY metallic glass revealed by high energy x-ray diffraction.

Amorphous bulk metallic glasses with the composition Fe48Cr15Mo14C15B6Y2have been of interest due to their special mechanical and electronic properties, including corrosion resistance, high yield-strength, large elasticity, catalytic performance, and soft ferromagnetism. Here, we apply a reverse Monte Carlo technique to unravel the atomic structure of these glasses. The pair-distribution functions for various atomic pairs are computed based on the high-energy x-ray diffraction data we have taken from an amorphous sample. Monte Carlo cycles are used to move the atomic positions until the model reproduces the experimental pair-distribution function. The resulting fitted model is consistent with ourab initiosimulations of the metallic glass. Our study contributes to the understanding of functional properties of Fe-based bulk metallic glasses driven by disorder effects.

Shear-induced chemical segregation in a Fe-based bulk metallic glass at room temperature.

Shear-induced segregation, by particle size, is known in the flow of colloids and granular media, but is unexpected at the atomic level in the deformation of solid materials, especially at room temperature. In nanoscale wear tests of an Fe-based bulk metallic glass at room temperature, without significant surface heating, we find that intense shear localization under a scanned indenter tip can induce strong segregation of a dilute large-atom solute (Y) to planar regions that then crystallize as a Y-rich solid solution. There is stiffening of the material, and the underlying chemical and structural effects are characterized by transmission electron microscopy. The key influence of the soft Fe-Y interatomic interaction is investigated by ab-initio calculation. The driving force for the induced segregation, and its mechanisms, are considered by comparison with effects in other sheared media.

Vitrification and nanocrystallization of pure liquid Ni studied using molecular-dynamics simulation.

Structural variation, vitrification, and crystallization processes in liquid nickel are simulated on continuous cooling and isothermal holding using a classical molecular-dynamics computer simulation procedure with an embedded-atom method potential at constant pressure. Structural changes are monitored with direct structure observation in the simulation cells, as well as by pair distribution and radial distribution functions created using the atomic coordinates. A cluster analysis is also performed. The crystallization kinetics is analyzed under isothermal conditions by monitoring density and energy variation as a function of time. As a result, a time-temperature-transformation diagram can be constructed over a wide temperature range.

Novel electrical transport properties of native Fe-Nb oxide layers leading to unilateral conductivity of a refractory metallic glass.

Fe-based metallic glasses (also called amorphous alloys) are known to have high hardness and high wear resistance. Here we study and present a Fe-Nb amorphous material with an unusual type of electrical conductivity behavior. The electrical transport properties of Fe-Nb oxide layers were studied by measuring local current-voltage characteristics by the atomic-force microscopy technique. At certain voltage levels the samples containing native oxides showed clearly asymmetrical conductivity relative to polarity of the applied potential. Fe-Nb metallic glassy surface oxide film growth process was monitored at ambient conditions. The growth rate keeps constant during the initial 2.5 hours. After that the growth rate drastically decreases and becomes almost zero while the final oxide thickness is 1.0-1.5 nm. The Fe-Nb film sample annealed for 15 minutes at 300 °C demonstrates several times larger oxide thickness and becomes an insulator. X-ray photoelectron spectroscopy was used to characterize the oxidation states in the surface amorphous oxides. This material can be readily applied as inexpensive nanoscale tunnel diode operating at the commonly utilized voltage of ±5 V.

Wave nature of conduction electrons in amorphous Co90Sc10 and Fe90Sc10 alloys.

The resistivity of amorphous Fe90Sc10 and Co90Sc10 alloys can be described well in terms of a simple model based on the wave character of electrons and their associated tunnelling over the temperature ranges ~1.9 K to 135 K and ~1.9 K to 12 K respectively. The extended range of agreement between experiment and theory for amorphous Fe90Sc10 is linked with its relatively small mean free path of [Formula: see text] = 0.32 nm, thus allowing electron waves to tunnel between clusters. On the other hand the restricted region of tunnelling of electron waves for amorphous Co90Sc10 alloys is linked with its relatively large mean free path of [Formula: see text] = 0.48 nm which restricts the ability for tunnelling between clusters while enabling electron waves to tunnel between different regions with a cluster.

Microstructure and mechanical behavior of metallic glass fiber-reinforced Al alloy matrix composites.

Metallic glass-reinforced metal matrix composites are an emerging class of composite materials. The metallic nature and the high mechanical strength of the reinforcing phase offers unique possibilities for improving the engineering performance of composites. Understanding the structure at the amorphous/crystalline interfaces and the deformation behavior of these composites is of vital importance for their further development and potential application. In the present work, Zr-based metallic glass fibers have been introduced in Al7075 alloy (Al-Zn-Mg-Cu) matrices using spark plasma sintering (SPS) producing composites with low porosity. The addition of metallic glass reinforcements in the Al-based matrix significantly improves the mechanical behavior of the composites in compression. High-resolution TEM observations at the interface reveal the formation of a thin interdiffusion layer able to provide good bonding between the reinforcing phase and the Al-based matrix. The deformation behavior of the composites was studied, indicating that local plastic deformation occurred in the matrix near the glassy reinforcements followed by the initiation and propagation of cracks mainly through the matrix. The reinforcing phase is seen to inhibit the plastic deformation and retard the crack propagation. The findings offer new insights into the mechanical behavior of metal matrix composites reinforced with metallic glasses.

Ti-Ag-Pd alloy with good mechanical properties and high potential for biological applications.

Ti-based alloys containing Ag were produced by tilt-casting method and their properties were studied. Even in its as-cast state, Ti94Ag3Pd3 showed relatively high tensile properties, good electrochemical behavior, and good biocompatibility. The relatively good mechanical properties of the as-cast α-Ti-type Ti94Ag3Pd3 alloy (tensile strength up to 850 MPa and elongation of ~10%) can be explained by its severely deformed, fine crystalline structure. The high biocompatibility of Ti94Ag3Pd3 can be explained by the Ag-Pd interaction, which inhibits the release of Ag ions from the surface. Ag, in combination with Pd has no toxic effects and demonstrates useful antimicrobial properties. The Ti94Ag3Pd3 alloy shows a good potential to be applied as a biomedical implant alloy.

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.

Localized shear deformation and softening of bulk metallic glass: stress or temperature driven?

Metallic glasses due to their unique combination of physical and chemical properties have a great potential in various applications: materials for construction, medical, MEMs devices and so on. The deformation mechanism in metallic glasses is very much different from that in conventional crystalline materials and not yet fully understood. Here we are trying to find out what drives shear deformation in metallic glasses. The compression experiments of the bulk metallic glassy (BMG) samples coated with tin, Rose metal and indium were performed. There were no melting sites of the coating observed near individual shear bands. Melting occurred only near fracture surface, near microcracks and in the places of shear band concentrations. The results indicate that shear banding is rather a stress driven process while the temperature rise that was observed takes place due to friction forces in the viscous supercooled liquid thin layer in the shear bands.

Structural investigation and mechanical properties of a representative of a new class of materials: nanograined metallic glasses.

A new class of materials: Au-based nanograined metallic glasses (NGMGs) were synthesized using magnetron sputtering with powder targets. A detailed study by x-ray diffraction and high-resolution transmission electron microscopy (TEM) documents the unique nanoscale granular structure of the Au-based NGMG. This material inherited the good mechanical properties of metallic glasses, showing a high hardness of ∼5.3 GPa and a low elastic modulus of ∼79 GPa. In addition, in contrast to most MGs the nanoglassy particles can deform along the loading direction, exhibiting unique tensile elongation up to 100%. During thermal crystallization of NGMG material, even smaller sized Au solid solution nanocrystals are formed within the glassy nanograins, offering a new way for production of the nanocomposites with tailored structural length scales.

Structure and nano-mechanical characteristics of surface oxide layers on a metallic glass.

Owing to their low elastic moduli, high specific strength and excellent processing characteristics in the undercooled liquid state, metallic glasses are promising materials for applications in micromechanical systems. With miniaturization of metallic mechanical components down to the micrometer scale, the importance of a native oxide layer on a glass surface is increasing. In this work we use TEM and XPS to characterize the structure and properties of the native oxide layer grown on Ni(62)Nb(38) metallic glass and their evolution after annealing in air. The thickness of the oxide layer almost doubled after annealing. In both cases the oxide layer is amorphous and consists predominantly of Nb oxide. We investigate the friction behavior at low loads and in ambient conditions (i.e. at T = 295 K and 60% air humidity) of both as-cast and annealed samples by friction force microscopy. After annealing the friction coefficient is found to have significantly increased. We attribute this effect to the increase of the mechanical stability of the oxide layer upon annealing.

Fabrication of Ni-Nb-Sn metallic glassy alloy powder and its microwave-induced sintering behavior.

In the present study, we prepared Ni59.35Nb34.45Sn6.2 metallic glassy alloy powder by an argon gas atomization process. Microwave (MW)-induced heating and sintering was carried out by a single-mode 2.45 GHz MW applicator in the separated magnetic field or electric field using the obtained glassy powders. The structure and thermal stability of the sintered glassy alloy specimens were investigated.

Microwave radiation processing of metallic glassy powders.

In the present study we investigate the stability of Cu50Zr45Al5 and Ni59Ti16Zr20Sn5 glassy powders and the formation of the bulk metallic glassy samples by microwave heating in a single mode cavity (915 MHz) in the alternating magnetic field maximum. Metallic glasses exhibit low viscosity at temperatures close to the glass-transition which allows for the processing of glassy powders. Microwave heating being a volumetric heating has significant advantages over conventional heating in materials processing, such as substantial energy savings, high heating rates and process cleanness.