Nucleation kinetics model for primary crystallization in Al-Y-Fe metallic glass.

The high density of aluminum nanocrystals (>1021 m-3) that develop during the primary crystallization in Al-based metallic glasses indicates a high nucleation rate (∼1018 m-3 s-1). Several studies have been advanced to account for the primary crystallization behavior, but none have been developed to completely describe the reaction kinetics. Recently, structural analysis by fluctuation electron microscopy has demonstrated the presence of the Al-like medium range order (MRO) regions as a spatial heterogeneity in as-spun Al88Y7Fe5 metallic glass that is representative for the class of Al-based amorphous alloys that develop Al nanocrystals during primary crystallization. From the structural characterization, an MRO seeded nucleation configuration is established, whereby the Al nanocrystals are catalyzed by the MRO core to decrease the nucleation barrier. The MRO seeded nucleation model and the kinetic data from the delay time (τ) measurement provide a full accounting of the evolution of the Al nanocrystal density (Nv) during the primary crystallization under isothermal annealing treatments. Moreover, the calculated values of the steady state nucleation rates (Jss) predicted by the nucleation model agree with the experimental results. Moreover, the model satisfies constraints on the structural, thermodynamic, and kinetic parameters, such as the critical nucleus size, the interface energy, and the volume-free energy driving force that are essential for a fully self-consistent nucleation kinetics analysis. The nucleation kinetics model can be applied more broadly to materials that are characterized by the presence of spatial heterogeneities.

Liquid-liquid transition kinetics in D-mannitol.

The kinetics of the first order liquid-liquid transition (LLT) in a single-component liquid D-mannitol have been examined in detail by the high rate of flash differential scanning calorimetry measurements. By controlling the annealing temperature, the phase X formation from the supercooled liquid is distinguished by either a nucleation-growth or a spinodal-decomposition type of LLT. In the measured time-temperature-transformation curve the portion covering the nucleation-growth type of LLT can be well fitted with a classical nucleation theory analysis.

Surface Diffusion Is Controlled by Bulk Fragility across All Glass Types.

Surface diffusion is vastly faster than bulk diffusion in some glasses, but only moderately enhanced in others. We show that this variation is closely linked to bulk fragility, a common measure of how quickly dynamics is excited when a glass is heated to become a liquid. In fragile molecular glasses, surface diffusion can be a factor of 10^{8} faster than bulk diffusion at the glass transition temperature, while in the strong system SiO_{2}, the enhancement is a factor of 10. Between these two extremes lie systems of intermediate fragility, including metallic glasses and amorphous selenium and silicon. This indicates that stronger liquids have greater resistance to dynamic excitation from bulk to surface and enables prediction of surface diffusion, surface crystallization, and formation of stable glasses by vapor deposition.

A pulse oxidation facility for the study of oxide nucleation behavior.

A pulse oxidation experimental facility was developed to examine the oxide nucleation behavior at different temperatures under a controlled oxygen atmosphere. An electromagnetic induction heater, a sample holder, and a controlled oxygen atmosphere are the key components of this facility. This experimental facility can also be used up to 1200 °C and Po2 levels from 1.3 × 10-5 to 0.1 Pa under isothermal conditions for times as short as 10 s. The efficacy of the method was illustrated by a study of the oxidation behavior of Ni-30 wt. % Cr at 600 °C for 45 s at Po2 of 1.3 × 10-2 Pa where the influence of grain orientation on oxidation behavior was highlighted by studying the nucleation rate on grains of known orientation. By using a single grain-orientation-mapped sample, pairs of grains each of known crystallographic orientation can be selected to be subjected to identical conditions. For example, new oxidation behavior was discovered where on a (111) oriented grain, corundum islands form with a nucleation density of 2.9 × 1011 islands/m2 and exhibited inward growth, whereas rock salt oxide islands formed on (100) grains at a density of 7 × 1012 islands/m2 and exhibited outward growth. The corundum oxide islands are in the range of 50-300 nm, whereas rock salt oxide islands are in the range of 50-600 nm and are well separated. The pulse oxidation facility with accurately controlled temperature and oxidation environment enables a new domain of study for the initial oxidation on bulk samples with a native oxide that represents realistic exposure conditions.

Coating Reactions on Vanadium and V-Si-B Alloys during Powder Pack-Cementation.

Alloys in the V-Si-B system are a new and promising class of light-weight refractory metal materials for high temperature applications. Presently, the main attention is focused on three-phase alloy compositions that consist of a vanadium solid solution phase and the two intermetallic phases V3Si and V5SiB2. Similar to other refractory metal alloys, a major drawback is the poor oxidation resistance. In this study, initial pack-cementation experiments were performed on commercially available pure vanadium and a three-phase alloy V-9Si-5B to achieve an oxidation protection for this new type of high temperature material. This advance in oxidation resistance now enables the attractive mechanical properties of V-Si-B alloys to be used for high temperature structural applications.

Mapping the Viscoelastic Heterogeneity at the Nanoscale in Metallic Glasses by Static Force Spectroscopy.

Nanoscale viscoelastic heterogeneity is an important concept for understanding the relationship between the microscopic atomic structure and the macroscopic mechanical behaviors in metallic glasses. However, the direct measurement of viscoelastic behavior at the nanoscale is still missing. Here we report a new measurement method based on static force microscopy to directly measure the viscoelastic properties at the nanoscale. The observed adhesive force and elastic modulus maps clearly display a typical hierarchical viscoelastic microstructure consisting of local hard and soft regions. Moreover, the adhesive force is more sensitive than the elastic modulus to viscoelastic heterogeneity and exhibits a bimodal distribution. In addition, we found that the structural relaxation and the rejuvenation effects induce the transition between the solid-like and liquid-like modes. The new measurement technique provides a powerful and quantative tool to investigate the nanoscale heterogeneity and build a connection between the microscopic structure and macroscopic mechanical behaviors in amorphous materials.

Nonequilibrium Solute Capture in Passivating Oxide Films.

We report experimental results on the composition and crystallography of oxides formed on NiCrMo alloys during both high-temperature oxidation and aqueous corrosion experiments. Detailed characterization using transmission electron microscopy and diffraction, aberration-corrected chemical analysis, and atom probe tomography shows unexpected combinations of composition and crystallography, far outside thermodynamic solubility limits. The results are explained using a theory for nonequilibrium solute capture that combines thermodynamic, kinetic, and density functional theory analyses. In this predictive nonequilibrium framework, the composition and crystallography are controlled by the rapidly moving interface. The theoretical framework explains the unusual combinations of composition and crystallography, which we predict will be common for many other systems in oxidation and corrosion, and other solid-state processes involving nonequilibrium moving interfaces.

Quantitative characterization of high temperature oxidation using electron tomography and energy-dispersive X-ray spectroscopy.

We report quantitative characterization of the high temperature oxidation process by using electron tomography and energy-dispersive X-ray spectroscopy. As a proof of principle, we performed 3D imaging of the oxidation layer of a model system (Mo3Si) at nanoscale resolution with elemental specificity and probed the oxidation kinetics as a function of the oxidation time and the elevated temperature. Our tomographic reconstructions provide detailed 3D structural information of the surface oxidation layer of the Mo3Si system, revealing the evolution of oxidation behavior of Mo3Si from early stage to mature stage. Based on the relative rate of oxidation of Mo3Si, the volatilization rate of MoO3 and reactive molecular dynamics simulations, we propose a model to explain the mechanism of the formation of the porous silica structure during the oxidation process of Mo3Si. We expect that this 3D quantitative characterization method can be applied to other material systems to probe their structure-property relationships in different environments.

Evolution of NiO Island Size Distributions during the Oxidation of a Ni-5Cr Alloy: Experiment and Modeling.

The classic models of metal oxidation developed by Wagner and Cabrera and Mott presuppose the existence of a planar oxide film and develop expressions for the rate at which the film thickens. Missing from those models is a description of how that initially planar film forms. Using scanning tunneling microscopy, we study the growth of NiO islands on the (100) surface of a Ni-5Cr alloy during the oxidation regime where the initial planar film is formed as oxide islands. The island height and area distributions as a function of the oxygen exposure in Langmuir (1 L = 10-6 Torr s) are measured. Lateral island growth and thickening occur as seemingly separate processes, and after a critical thickness of ≈0.4 nm is achieved, growth is purely in the lateral direction. We develop a surface diffusion model for the evolution of the island size distribution that accounts for the lateral growth and coalescence of the NiO islands. Our results indicate that the oxygen surface diffusion screening length [Formula: see text] controls the island evolution. The screening length is found to be 0.3-0.4 nm, which suggests that the processes leading to island growth are highly localized to the island edge.

Deformation-driven catalysis of nanocrystallization in amorphous Al alloys.

Nanocrystals develop in amorphous alloys usually during annealing treatments with growth- or nucleation-controlled mechanisms. An alternative processing route is intense deformation and nanocrystals have been shown to develop in shear bands during the deformation process. Some controversy surrounded the idea of adiabatic heating in shear bands during their genesis, but specific experiments have revealed that the formation of nanocrystals in shear bands has to be related to localized deformation rather than thermal effects. A much less debated issue has been the spatial distribution of deformation in the amorphous alloys during intense deformation. The current work examines the hypothesis that intense deformation affects the regions outside shear bands and even promotes nanocrystal formation in those regions upon annealing. Melt-spun amorphous Al88Y7Fe5 alloy was intensely cold rolled. Microcalorimeter measurements at 60 °C indicated a slight but observable growth of nanocrystals in shear bands over the annealing time of 10 days. When the cold-rolled samples were annealed at 210 °C for one hour, transmission electron images did not show any nanocrystals for as-spun ribbons, but nanocrystals developed outside shear bands for the cold rolled samples. X-ray analysis indicated an increase in intensity of the Al peaks following the 210 °C annealing while the as-spun sample remained "X-ray amorphous". These experimental observations strongly suggest that cold rolling affects regions (i.e., spatial heterogeneities) outside shear bands and stimulates the formation of nanocrystals during annealing treatments at temperatures well below the crystallization temperature of undeformed ribbons.

Direct observation of incommensurate structure in Mo3Si.

Z-contrast imaging, electron diffraction, atom-probe tomography (APT) and density functional theory calculations were used to study the crystal structure of the Mo3Si phase which was previously reported to have an A15 crystal structure. The results showed that Mo3Si has an incommensurate crystal structure with a non-cubic unit cell. The small off-stoichiometry in composition of the sample which was revealed by APT and atomic resolution Z-contrast imaging suggested that site substitution caused the development of split atomic positions, disorder and vacancies.

Possible existence of two amorphous phases of D-mannitol related by a first-order transition.

We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature Tg (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near Tg + 50 K, enabling a determination of their equilibrium temperature. The presence of D-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from D-mannitol's SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near Tg with substantial enthalpy decrease toward the crystalline phases; the processes in water and D-mannitol both strengthen the hydrogen bonds. In contrast to TPP, D-mannitol's Phase X forms more rapidly and can transform back to the SCL. These features make D-mannitol a valuable new model for understanding polyamorphism.

Dependence of crystal nucleation on prior liquid overheating by differential fast scanning calorimeter.

The degree of overheating of a melt often plays an important role in the response of the melt to subsequent undercooling, it determines the nucleation and growth behavior and the properties of the final crystalline products. However, the dependence of accessible undercooling of different bulk melt samples on prior liquid overheating has been reported to exhibit a variety of specific features which could not be given a satisfactory explanation so far. In order to determine uniquely the dependence of accessible undercooling on prior overheating and the possible factors affecting it, the solidification of a pure Sn single micro-sized droplet was studied by differential fast scanning calorimeter with cooling rates in the range from 500 to 10,000 K/s. It is observed experimentally that (i) the degree of undercooling increases first gradually with increase of prior overheating; (ii) if the degree of prior superheating exceeds a certain limiting value, then the accessible undercooling increases always with increasing cooling rate; in the alternative case of moderate initial overheating, the degree of undercooling reaches an undercooling plateau; and (iii) in latter case, the accessible undercooling increases initially with increasing cooling rate. However, at a certain limiting value of the cooling rate this kind of response is qualitatively changed and the accessible undercooling decreases strongly with a further increase of cooling rate. The observed rate dependent behavior is consistent with a kinetic model involving cavity induced heterogeneous nucleation and cavity size dependent growth. This mechanism is believed to be relevant also for other similar rapid solidification nucleation processes.

Nucleation of shear bands in amorphous alloys.

The initiation and propagation of shear bands is an important mode of localized inhomogeneous deformation that occurs in a wide range of materials. In metallic glasses, shear band development is considered to center on a structural heterogeneity, a shear transformation zone that evolves into a rapidly propagating shear band under a shear stress above a threshold. Deformation by shear bands is a nucleation-controlled process, but the initiation process is unclear. Here we use nanoindentation to probe shear band nucleation during loading by measuring the first pop-in event in the load-depth curve which is demonstrated to be associated with shear band formation. We analyze a large number of independent measurements on four different bulk metallic glasses (BMGs) alloys and reveal the operation of a bimodal distribution of the first pop-in loads that are associated with different shear band nucleation sites that operate at different stress levels below the glass transition temperature, Tg. The nucleation kinetics, the nucleation barriers, and the density for each site type have been determined. The discovery of multiple shear band nucleation sites challenges the current view of nucleation at a single type of site and offers opportunities for controlling the ductility of BMG alloys.

Excellent capability in degrading azo dyes by MgZn-based metallic glass powders.

The lack of new functional applications for metallic glasses hampers further development of these fascinating materials. In this letter, we report for the first time that the MgZn-based metallic glass powders have excellent functional ability in degrading azo dyes which are typical organic water pollutants. Their azo dye degradation efficiency is about 1000 times higher than that of commercial crystalline Fe powders, and 20 times higher than the Mg-Zn alloy crystalline counterparts. The high Zn content in the amorphous Mg-based alloy enables a greater corrosion resistance in water and higher reaction efficiency with azo dye compared to crystalline Mg. Even under complex environmental conditions, the MgZn-based metallic glass powders retain high reaction efficiency. Our work opens up a new opportunity for functional applications of metallic glasses.