Abstract
e present the Raman spectroscopic results concerning the structure and the dynamics of several inorganic melts and glasses in a broad temperature range. The development of pioneering methods appropriate for high temperature material research and their combination with Raman spectroscopy provided spectroscopic results of high-purity materials at temperatures up to 2000oC. High-temperature Raman data are limited at temperatures below 1000oC due to several experimental difficulties concerning high-temperature vibrational measurements. The main difficulty is the intensive black body radiation, which overwhelms the weak Raman signal and consequently no spectrum can be recorded. In order to overcome the experimental difficulties, we developed a Raman setup, which combines the “containerless techniques” with the use of an infrared laser (CO2-laser) as a heating source permitting the recording of Raman spectra at temperatures up to 2000oC. The “containerless techniques” are divided in two main categories. The “levitation technique”, where the liquid sample is levitated using a nozzle with the appropriate geometry and a supporting gas and the “self-support technique”, where the liquid sample is supported from the solid part of the same material. The main advantage of the Raman spectroscopy-containerlees techniques-laser heating combination is the effective limitation of the black body radiation giving the opportunity to use the desirable atmosphere on the sample and study high-melting materials preventing contamination, heterogeneous nucleation, reactions between materials and containers at high temperatures. We studied several non-oxide (ZnCl2, ZnBr2, xZnCl2-(1-x)AlCl3) and oxide (SiO2, K2Si4O9, xCaO-(1-x)SiO2, xCaO-(1-x)Al2O3) systems with intrinsic experimental difficulties, such as high melting points (~2000oC), hygroscopic nature, high vapor pressures etc. We recorded Raman spectra in extensive temperature range covering the crystalline, the glassy, the supercooled and the molten state in order to elucidate the structure and the involved dynamics of these materials. Information concerning the local coordination polyhedra in short range order have been used for clarifying the role of “network modifiers” inside the fully polymerized threedimensional tetrahedral networks (“network formers”). The structure in medium range order (low-frequency Raman spectrum), the Boson peak, the Quasi-Elastic line and characteristics such as the fragile/strong character and the non-exponential/exponential behavior of these materials have been put under focus and the results are discussed in the framework of the current phenomenological status of the field.
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