Among the superionic conductors that show a Faraday transition – the continuous increase in the ionic conductivity over a range of temperatures – the fluorite structures have enjoyed incisive examinations over the past four decades; yet the fundamental nature of superionicity has remained largely inconclusive. Departing from the traditional quasi-static defect framework, we provide weighty evidence for string-like dynamical structures that govern the fast ion conduction process in fluorites. We show that lower temperatures encourage the growth of longer but slowly relaxing strings and vice-versa – a direct manifestation of heterogeneous dynamics. Remarkably, the ionic conductivity is inversely correlated to the lifetime of the ions that participate in the strings and not explicitly to the ion population. Our analysis methodology, which resolves a long-standing disagreement on defect structures and the mechanism of ionic transport in fcc fluorite structures, is well-positioned to describe the dynamics of low dimensional conduction in a larger class of superionic conductors.
Using Raman and X-ray photoelectron spectroscopy, we delineate the bond and defect structures in nuclear block graphite (NBG-18) under neutron and ion irradiation. The strengthening of the defect (D) peak in the Raman spectra under irradiation is attributed to an increase in the topological, sp2-hybridized defects. Using transmission electron microscopy, we provide evidence for prismatic dislocations as well as a number of basal dislocations dissociating into Shockley partials. The non-vanishing D peak in the Raman spectra, together with a generous number of dislocations, even at low irradiation doses, indicates a dislocation-mediated amorphization process in graphite.
Using molecular dynamics simulations of UO${}_{2}$\char22{}a type II superionic conductor\char22{}we identify a well-defined onset of dynamic disorder (${T}_{$\alpha${}}$), which is remarkably correlated to a nontrivial advance of dynamical heterogeneity (DH). Quantified by the correlations in the dynamic propensity and van Hove self-correlation function, the DH is shown to grow with increasing temperature from ${T}_{$\alpha${}}$, peak at an intermediate temperature between ${T}_{$\alpha${}}$ and ${T}_{$\lambda${}}$\char22{}the superionic transition temperature\char22{}and then recede. Surprisingly, the DH attributes are not uniform across the temperatures\char22{}our investigation shows a low temperature (${$\alpha${}}_{T}$) stage DH, which is characterized by weak correlations and a plateaulike period in the correlations of the propensity, and a high temperature (${$\lambda${}}_{T}$) stage DH with strong correlations that are analogous to those in typical supercooled liquids. Our work, which has rigorously identified the onset of superionicity, gives a different direction for interpreting scattering experiments on the basis of statistical, correlated dynamics.