Structural and chemical homogeneity of chalcogenide glass prepared by melt-rocking.

The chemical and structural homogeneity of selenide glasses produced by mechanical homogenization of the melt in a rocking furnace is investigated by Raman and Energy Dispersive Spectroscopy (EDS). Both techniques demonstrate that the glass is macroscopically homogeneous along the entire length of a 6 cm rod. EDS imaging performed over four orders of magnitude in scale further confirms that the glass is homogeneous down to the sub-micron scale. An estimate of the diffusion coefficient from experimental viscosity data shows that the diffusion length is far larger than the resolution of EDS and therefore confirms that the glass is homogeneous at any length scale. In order to investigate a systematic mismatch in physical properties reported in the literature for glasses produced by extended static homogenization, two germanium selenide samples are produced under the same conditions except for the homogenization step: one in a rocking furnace for 10 h and the other in a static furnace for 192 h. No difference in physical properties is found between the two glasses. The properties of an ultra-high purity glass are also found to be identical. The origin of the systematic deviation reported in the literature for germanium selenide glasses is therefore still unknown, but the present results demonstrate that homogeneity or dryness does not have a significant contribution in contrast to previous suggestions. The implications of glass homogeneity for technological applications and industrial production are discussed.

Structure of ZnCl2 Melt. Part II: Fragile-to-Strong Transition in a Tetrahedral Liquid.

The fraction of edge- and corner-sharing tetrahedra in liquid ZnCl2 is quantified as a function of temperature using Raman spectroscopy and ab initio molecular dynamic simulations. Two distinct regimes are found in the temperature dependence of the change in these structural units. This behavior is consistent with the existence of a fragile-to-strong transition in liquid ZnCl2 as suggested by calorimetric and viscosity measurements. The structural origin of this transition is rationalized in terms of a constraint counting formalism. It is suggested that the ratio of edge- to corner-sharing tetrahedra controls the configurational entropy and in turn the viscosity of the melt. The temperature dependence of this ratio above the melting point is also found to be qualitatively consistent with neutron diffraction data. The observation of a similar fragile-to-strong transition in the isostructural GeSe2 melt indicates that it may be a common feature of tetrahedral liquids.