The development of metal alloys that form glasses at modest cooling rates has stimulated broad scientific and technological interest. However, intervening crystallization of the liquid in even the most robust bulk metallic glass-formers is orders of magnitude faster than in many common polymers and silicate glass-forming liquids. Crystallization limits experimental studies of the undercooled liquid and hampers efforts to plastically process metallic glasses. We have developed a method to rapidly and uniformly heat a metallic glass at rates of 10(6) kelvin per second to temperatures spanning the undercooled liquid region. Liquid properties are subsequently measured on millisecond time scales at previously inaccessible temperatures under near-adiabatic conditions. Rapid thermoplastic forming of the undercooled liquid into complex net shapes is implemented under rheological conditions typically used in molding of plastics. By operating in the millisecond regime, we are able to "beat" the intervening crystallization and successfully process even marginal glass-forming alloys with very limited stability against crystallization that are not processable by conventional heating.
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http://dx.doi.org/10.1126/science.1201362 | DOI Listing |
Proc Natl Acad Sci U S A
January 2025
Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011.
From molecular dynamics (MD) simulations of melt-quenching and thermal aging procedures in pure Ag, Cu, Ag-Cu binary alloys, and Cu-Zr binary alloys, we have identified two distinct amorphous phases for a metastable undercooled liquid: the homogeneous L-phase with low shear rigidity and the heterogenous G-phase with much higher shear rigidity and a heterogeneity length scale Λ. Here, we examine two-phase equilibration studies showing that the G-phase melts to form the L-phase above ~1,000 K, which then transforms to form the crystal (X) phase; however, below the melting point of the G-Phase (~990 K), the X- and G-phases do not transform into each other. We suggest the presence of a G-phase is likely responsible for embrittlement often observed in metallic glasses.
View Article and Find Full Text PDFMolecules
January 2025
Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, nam. Cs Legii 565, 532 10 Pardubice, Czech Republic.
The particle size-dependent processes of structural relaxation and crystal growth in amorphous nifedipine were studied by means of non-isothermal differential scanning calorimetry (DSC) and Raman microscopy. The enthalpy relaxation was described in terms of the Tool-Narayanaswamy-Moynihan model, with the relaxation motions exhibiting the activation energy of 279 kJ·mol for the temperature shift, but with a significantly higher value of ~500 kJ·mol being obtained for the rapid transition from the glassy to the undercooled liquid state (the latter is in agreement with the activation energy of the viscous flow). This may suggest different types of relaxation kinetics manifesting during slow and rapid heating, with only a certain portion of the relaxation motions occurring that are dependent on the parameters of a given temperature range and time frame.
View Article and Find Full Text PDFMaterials (Basel)
December 2024
Dipartimento di Ingegneria Meccanica, Chimica e dei Materiali, Università degli Studi di Cagliari, Via Marengo 2, 09123 Cagliari, Italy.
Liquid metals and metallic alloys often exist as metastable phases or can be undercooled below their equilibrium melting point. The Traditional CALPHAD (CALculation of PHAse Diagrams) approach struggles to accurately model these metastable conditions, which are important in rapid quenching techniques like additive manufacturing, and to understand glass formation or oxidation phenomena occurring in the liquid phase during nuclear and high-temperature aerospace applications. On the contrary, the third-generation CALPHAD models have the potential to accurately describe metastable phase diagrams to provide better predictions of molten phase behavior under non-equilibrium conditions.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
October 2024
Department of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843, United States.
Nucleation particles, solid phases dispersed throughout a medium to decrease the energy barrier for solidification or other reversible phase transitions, are generally selected on the basis of structural or interfacial energy considerations between the host phase and the solid phase that is crystallizing. However, the existence of chemical reactions between the nucleation particles and the host phase can obscure these underlying relationships, thereby complicating the process of selection of active nucleation particle phases. Here, we reveal the origin of nucleation activity of barium-based nucleation particles in the salt hydrate calcium chloride hexahydrate (CCH), a candidate for near room temperature thermal energy storage.
View Article and Find Full Text PDFPhys Rev E
September 2024
School of Physical Science and Technology, Northwestern Polytechnical University, Xi'an 710072, China.
The liquid state thermophysical properties and amorphous solidification kinetics of Fe_{50-x}Co_{x}Cr_{14}Mo_{14}C_{9}B_{8}Tm_{5} (x=10, 15, 20, and 25) alloys were explored by electromagnetic and electrostatic levitation techniques. It was found that the surface tension of liquid alloys with Fe contents below 30 at. % had a strong temperature dependence.
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