The spherulitic crystal growth velocity in selenium supercooled liquid has been measured by infrared microscopy in isothermal conditions for rapidly heated samples of a-Se from temperatures well below T g . These data are compared and analyzed along with previously published data obtained on samples quenched from a temperature well above the melting point. The spherulites grew linearly over a course of time that corresponds to crystal growth controlled by crystal−liquid interface kinetics. The crystal growth velocity data obtained for these two different thermal histories can be described by the normal growth model for moderate supercoolings (ΔT <60 K). The screw dislocation growth provides a better description for larger supercoolings (ΔT > 90 K) that is also consistent with morphological observations. However, the prediction based on this model still significantly deviates for intermediate supercoolings. It is shown that all experimental data in the whole temperature range (T g < T < T m ) can be described by a combined approach including both these models, taking into account actual viscosity scaling of crystal growth η −1 . The kinetic information captured in the DSC curve is analyzed, providing evidence that the non-isothermal crystallization process can be described by the Johnson-Mehl-Avrami model. Two distinct regions characterized by different values of apparent activation energy were found. The transition between these regions coincides with morphological changes of spherulitic crystals and other properties. These regions are characterized by distinct apparent activation energies whose values are consistent with those obtained from microscopic measurement of crystal growth velocity.
Crystal growth, viscosity, and melting were studied in Ge2Sb2Se5 bulk samples. The crystals formed a compact layer on the surface of the sample and then continued to grow from the surface to the central part of the sample. The formed crystalline layer grew linearly with time, which suggests that the crystal growth is controlled by liquid-crystal interface kinetics. Combining the growth data with the measured viscosities and melting data, crystal growth could be described on the basis of standard crystal growth models. The screw dislocation growth model seems to be operative in describing the temperature dependence of the crystal growth rate in the studied material in a wide temperature range. A detailed discussion on the relation between the kinetic coefficient of crystal growth and viscosity (ukin ∝ η(-ξ)) is presented. The activation energy of crystal growth was found to be higher than the activation energy of crystallization obtained from differential scanning calorimetry, which covers the whole nucleation-growth process. This difference is considered and explained under the experimental conditions.
Co-crystallization of cyclic nitramines with sterically crowded molecules, i.e., ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-CL-20) with cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole, is difficult, but co-agglomeration given good results.
Chalcogenide glass-formers are being used in a remarkable range of various optoelectronic, photonics, photoconducting, sensing and memory device applications. The knowledge of viscosity is essential for the processing of any glass-forming material, in particular for the fabrication of precise optical elements, which is the main application field of chalcogenide glasses. This work presents an extensive collection of all available viscosity data for chalcogenides, including the measurement methods. The Mauro-Yue-Ellison-Gupta-Allan (MYEGA), Arrhenius and VFT equations are used to fit the temperature dependences of viscosity. The viscosity glass transition temperatures, fragilities and apparent activation energies are calculated from these fits. Consequently, these parameters are discussed with regard to the compositional evolution of the respective chalcogenide systems.
The
crystal growth velocity of spherulitic As2Se3 in a supercooled melt of the same composition was studied
by optical microscopy and thermoanalytical methods in isothermal and
nonisothermal conditions. The time dependence of crystal size is linear,
which suggests the crystal growth is controlled by interface kinetics.
Crystal growth velocity was determined as the slope of these linear
dependences. The experimental results presented in this paper considerably
extend the previously reported range of crystal growth velocity. All
isothermal crystal growth velocity data can be well described by the
standard two-dimensional surface nucleated growth model (2Dsg) including
crystal growth viscosity decoupling (ξ = 0.647). The activation
energy of crystal growth for microscopic experiments is in a good
agreement with values obtained from thermoanalytical experiments,
and the ratio of the activation energy of crystal growth and the activation
energy of viscous flow well corresponds to an independently determined
decoupling parameter. The same model successfully describes also crystalline
layer thickness and growth pattern at the amorphous As2Se3 surface in nonisothermal conditions.
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