When annealed below T g , the melt-spun material exhibits a steadily decreasing nucleation rate, 4 which suggests heterogeneous nucleation. 5 The nucleation site has so far eluded structural or chemical detection, ruling out common sites like second phase interfaces or large impurity clusters. This suggests that the nucleation sites in quenched Al 92 Sm 8 may be a form of nanometer-length structure or medium-range order ͑MRO͒. Such structure is difficult to detect in amorphous materials using conventional techniques such as x-ray diffraction. 6 Here, we report fluctuation electron microscopy ͑FEM͒ ͑Refs. 7 and 8͒ measurements and simulations which find MRO associated with primary crystallization in amorphous Al 92 Sm 8 .FEM measures diffraction from nanoscale volumes using dark-field transmission electron microscopy ͑TEM͒ at a deliberately low ͑5-50 Å͒ image resolution. The magnitude of the spatial fluctuations in diffraction, measured by the normalized variance V as a function of scattering vector k, gives information about MRO at the length scale of the image resolution. 7,9 V͑k͒ depends on the three-and four-body atomic position correlation functions. 9 Peaks in V͑k͒ give information about the type of MRO from their position in k and the degree of MRO from their height. A polycrystalline sample is an extreme example of order: in a dark-field image each grain will appear brightest when it satisfies a Bragg condition in k, leading to a high peaks in V͑k͒ at the crystal reciprocal lattice k's.Samples of amorphous Al 92 Sm 8 were prepared by rapid quenching in a single wheel melt spinner at a tangential wheel speed of 55 m / s and by cold-rolling elemental foil multilayers at a 0.003 s −1 strain rate. Melt-spun ribbon samples were annealed at 130°C ͑ϽT g of 171°C͒ 3,10 under vacuum. TEM samples were prepared by electropolishing only, as ion milling can introduce spurious peaks in V͑k͒ of amorphous metals. 11 FEM was done in hollow-cone darkfield mode on a LEO 912 EFTEM at 120 kV and 16 Å resolution. Each V͑k͒ data set is the mean of measurements from at least seven areas of the sample, quoted with one standard deviation of the mean error bars.
Primary crystallization is the key reaction that controls the synthesis of nanostructured bulk volumes comprised of a high density (10 21 -10 23 m À3 ) of nanocrystals (7-20 nm) within an amorphous matrix. The primary crystallization kinetics in response to the annealing and the deformation of amorphous Al alloys are assessed in specific sample types and selected thermal treatments to evaluate primary nanocrystallization reactions. All amorphous Al alloy compositions are hypereutectic so that the initial phase selection of primary Al proceeds at a reduced driving free energy compared to thermodynamically favored intermetallic phases. Differential scanning calorimetry (DSC) studies on powders and melt spun ribbon (MSR) samples based upon thermal cycling and annealing below the glass transition, T g , demonstrate a strong sensitivity of the primary crystallization onset and reaction enthalpy to thermal history and the as-quenched state. Microcalorimetry investigations and careful analysis of nanocrystal size distributions for Al 92 Sm 8 MSRs following sub-T g anneals reveal a partial nanocrystallization reaction resulting from a transient, decaying nucleation rate and a limited supply of heterogeneous nucleation sites. While crystallization is generally thought of as a thermally activated process, it can also be induced in response to external forcing such as irradiation or mechanical alloying. Intense deformation of amorphous Al 88 Y 7 Fe 5 MSR, for example, yields a distribution of Al-nanocrystallites in the amorphous matrix without thermal annealing. Moreover, the results of cold-rolling experiments with melt-spun amorphous Al 85 Ni 10 Ce 5 ribbons show that the deformation process can alter the phase selection upon annealing. These results suggest that the shear process during rolling effects a local rearrangement of atoms in the amorphous matrix. The kinetics behavior highlights the important role of the as-synthesized amorphous structure, reaction pathways and transient conditions on the evolution of nanoscale microstructures during primary crystallization.
Several proposals involving solute effects, phase separation or quenched-in nuclei and heterogeneous nucleation have been advanced to account for the high nanocrystal density that evolves during primary crystallization in marginal glass-forming alloys, but recent crystallization measurements and kinetics analyses provide new evidence for the role of the as-quenched structure on nanocrystal synthesis. Here, isothermal microcalorimetry investigations and quantitative electron microscopy measurements including high-resolution imaging and electron spectroscopy analyses were performed on a model system at different temperatures well below the glass transition to monitor the nanocrystallization isothermally as a function of time. From the combined measurements, the size distribution and the transformed fraction can be determined with a high accuracy for extended ranges of temperatures and times. In addition, calorimetric measurements in the glassy, liquid and crystalline states of the model alloy serves to analyze, for the first time, the fragility characteristics of a marginal glass-former that presents an important parameter in the context of the kinetic stability of the material against premature crystallization.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.