Controlling crystallization kinetics is key to overcome the temperature-time dilemma in phase change materials employed for data storage. While the amorphous phase must be preserved for more than 10 years at slightly above room temperature to ensure data integrity, it has to crystallize on a timescale of several nanoseconds following a moderate temperature increase to near 2/3 T to compete with other memory devices such as dynamic random access memory (DRAM). Here, a calorimetric demonstration that this striking variation in kinetics involves crystallization occurring either from the glassy or from the undercooled liquid state is provided. Measurements of crystallization kinetics of Ge Sb Te with heating rates spanning over six orders of magnitude reveal a fourfold decrease in Kissinger activation energy for crystallization upon the glass transition. This enables rapid crystallization above the glass transition temperature T . Moreover, highly unusual for glass-forming systems, crystallization at conventional heating rates is observed more than 50 °C below T , where the atomic mobility should be vanishingly small.
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http://dx.doi.org/10.1002/adma.201900784 | DOI Listing |
Molecules
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 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.
View Article and Find Full Text PDFMolecules
March 2024
Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 532 10 Pardubice, Czech Republic.
The processes of structural relaxation, crystal growth, and thermal decomposition were studied for amorphous griseofulvin (GSF) by means of thermo-analytical, microscopic, spectroscopic, and diffraction techniques. The activation energy of ~395 kJ·mol can be attributed to the structural relaxation motions described in terms of the Tool-Narayanaswamy-Moynihan model. Whereas the bulk amorphous GSF is very stable, the presence of mechanical defects and micro-cracks results in partial crystallization initiated by the transition from the glassy to the under-cooled liquid state (at ~80 °C).
View Article and Find Full Text PDFJ Phys Chem B
December 2021
Laboratoire de Chimie des Polymères, Faculté des Sciences, Université Libre de Bruxelles (ULB), CP 206/1, Boulevard du Triomphe, 1050 Brussels, Belgium.
Materials (Basel)
October 2021
Department of Materials, Imperial College London, London SW7 2AZ, UK.
A second melting temperature occurs at a temperature T higher than T in glass-forming melts after heating them from their glassy state. The melting entropy is reduced or increased depending on the thermal history and on the presence of antibonds or bonds up to T. Recent MD simulations show full melting at T = 1.
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