Revealing structural changes at glass transition via radial distribution functions.

Transformation of glasses into liquids is discussed in terms of configuron (broken chemical bond or transformation of an atom from one to another atomic shell) percolation theory with structural changes caused. The first sharp diffraction minimum (FSDM) in the pair distribution function (PDF) is shown to contain information on structural changes in amorphous materials at the glass transition temperature (Tg). A method to determine the glass transition temperature is proposed based on allocating Tg to the temperature when a sharp kink in FSDM occurs. The method proposed is more sensitive compared with empirical criterion of Wendt-Abraham; e.g., for amorphous Ni the kink that determines Tg is almost twice sharper. Connection between the kink in fictive temperature behavior of PDF and Wendt-Abraham criterion is discussed

On structural rearrangements during the vitrification of molten copper

We utilise displacement analysis of Cu-atoms between the chemical bond-centred Voronoi polyhedrons to reveal structural changes at the glass transition. We confirm that the disordered congruent bond lattice of Cu loses its rigidity above the glass transition temperature (Tg) in line with Kantor–Webman theorem due to percolation via configurons (broken Cu-Cu chemical bonds). We reveal that the amorphous Cu has the Tg = 794 ± 10 K at the cooling rate q = 1 × 1013 K/s and that the determination of Tg based on analysis of first sharp diffraction minimum (FDSM) is sharper compared with classical Wendt–Abraham empirical criterion

Zirconolite polytypes and murataite polysomes in matrices for the REE-actinide fraction of HLW

Electron backscatter diffraction (EBSD) has been used for more than 30 years for analyzing the structure of minerals and artificial substances. In recent times, EBSD has been widely applied for investigation of irradiated nuclear fuel and matrices for the immobilization of radioactive waste. The combination of EBSD and scanning electron microscopy (SEM/EDS) methods allows researchers to obtain simultaneously data on a specimen's local composition and structure. The article discusses the abilities of SEM/EDS and EBSD techniques to identify zirconolite polytype modifications and members of the polysomatic murataite-pyrochlore series in polyphase ceramic matrices, with simulations of Pu (Th) and the REE-actinide fraction (Nd) of high-level radioactive waste

On alteration rate renewal stage of nuclear waste glass corrosion

The three generically accepted stages of glass corrosion are reviewed with focus on final stage termed alteration rate renewal (or resumption) stage when the glass may re-start corroding with the rate similar to that at the initial stage. It is emphasized that physical state and physical changes that occur in the near-surface layers can readily lead to an effective increase of leaching rate which is similar to alteration rate renewals. Experimental data on long-term (during few decades) corrosion of radioactive borosilicate glass K26 designed to immobilize high-sodium operational NPP radioactive waste evidence on resumption-like effects of radionuclides (137,134Cs) leaching. The cause of that was however related not to chemical changes in the leaching environment but rather to physical state of glass surface due to formation of small cracks and new pristine glass areas in contact with water

On viscous flow in glass-forming organic liquids

The two-exponential Sheffield equation of viscosity η(T) = A1·T·[1 + A2·exp(Hm/RT)]·[1 + C·exp(Hd/RT)], where A1, A2, Hm, C, and Hm are material-specific constants, is used to analyze the viscous flows of two glass-forming organic materials—salol and α-phenyl-o-cresol. It is demonstrated that the viscosity equation can be simplified to a four-parameter version: η(T) = A·T·exp(Hm/RT)]·[1 + C·exp(Hd/RT)]. The Sheffield model gives a correct description of viscosity, with two exact Arrhenius-type asymptotes below and above the glass transition temperature, whereas near the Tg it gives practically the same results as well-known and widely used viscosity equations. It is revealed that the constants of the Sheffield equation are not universal for all temperature ranges and may need to be updated for very high temperatures, where changes occur in melt properties leading to modifications of A and Hm for both salol and α-phenyl-o-cresol

The Modified Random Network (MRN) model within the Configuron Percolation Theory (CPT) of glass transition

A brief overview is presented of the modified random network (MRN) model in glass science emphasizing the practical outcome of its use. Then, the configuron percolation theory (CPT) of glass–liquid transition is concisely outlined, emphasizing the role of the actual percolation thresholds observed in a complex system. The MRN model is shown as an important tool enabling to understand within CPT the reduced percolation threshold in complex oxide systems

Challenges in the long-term behaviour of highly radioactive materials

Highly radioactive materials are at the core in many useful applications ranging from operating nuclear reactors (including fast breeder reactors) to vitrified high-level radioactive waste, which is currently stored and awaiting final disposal into dedicated facilities within deep geological formations [...

Undercooled phase behind the glass phase with superheated medium-range order above glass transition temperature

Rapidly quenched glass formers are amorphous and transformed into glass phases by relaxing enthalpy during the first heating. Two liquids give rise, at first, to an intermediate Phase 3 below T3 < Tg respecting the entropy constraints and then, the enthalpy increases towards that of the glass phase up to Tg. The negative activation energy shows that Phase 3 is hidden behind the glassy phase acting as an intermediate invasive phase during the second cooling. Phase 3 carries a medium-range order above Tg which can be superheated above the melting temperature up to Tn+. The two-liquid state model predicts the thermodynamic properties as well as the relaxation times from liquids 1 to 2. The configuron model is successfully applied to 54 glasses explaining the transitions by percolation and an ‘ordered’ fraction equal to the critical threshold Φc = 0.15 ± 0.01 from Tg to Tn+