Thermodynamic parameters of bonds in glassy materials from viscosity-temperature relationships

Doremus's model of viscosity assumes that viscous flow in amorphous materials is mediated by broken bonds (configurons). The resulting equation contains four coefficients, which are directly related to the entropies and enthalpies of formation and motion of the configurons. Thus by fitting this viscosity equation to experimental viscosity data these enthalpy and entropy terms can be obtained. The non-linear nature of the equation obtained means that the fitting process is non-trivial. A genetic algorithm based approach has been developed to fit the equation to experimental viscosity data for a number of glassy materials, including SiO2, GeO2, B2O3, anorthite, diopside, xNa2O–(1-x)SiO2, xPbO–(1-x)SiO2, soda-lime-silica glasses, salol, and α-phenyl-o-cresol. Excellent fits of the equation to the viscosity data were obtained over the entire temperature range. The fitting parameters were used to quantitatively determine the enthalpies and entropies of formation and motion of configurons in the analysed systems and the activation energies for flow at high and low temperatures as well as fragility ratios using the Doremus criterion for fragility. A direct anti-correlation between fragility ratio and configuron percolation threshold, which determines the glass transition temperature in the analysed materials, was found

Some Trends in Radioactive Waste Form Behavior Revealed in Long-Term Field Tests

Results from long-term field tests with borosilicate glass, cement and bitumen waste forms containing actual intermediate-level radioactive waste are summarized and discussed in the paper. Leaching behavior of the waste forms was evaluated by monitoring the contamination of contacting water. Measured leach rates of the three waste-form materials were in a narrow range in shallow subsurface repositories, but varied in a wide range at an open testing site owing to weathering of bitumen and cement materials. The repositories were opened after 12-year testing for visual examination, sampling and analysis. All retrieved waste forms were in good physical condition. The study has not revealed any negative changes in the waste glass. Some ageing processes were detected in cement and bitumen waste forms, which can positively (bitumen) or negatively (cement) affect physical and containment properties of these waste materials. It has been established that a significant proportion of the radioactive inventory in the bitumen waste form became associated with the bitumen phase. Phase separation of this radioactive bitumen has shown, than the asphaltene fraction is responsible for the major part of the radioactivity retained by the bitumen

Topologically disordered systems at the glass transition

The thermodynamic approach to the viscosity and fragility of amorphous oxides was used to determine the topological characteristics of the disordered network-forming systems. Instead of the disordered system of atoms we considered the congruent disordered system of interconnecting bonds. The Gibbs free energy of network-breaking defects (configurons) was found based on available viscosity data. Amorphous silica and germania were used as reference disordered systems for which we found an excellent agreement of calculated and measured glass transition temperatures. We reveal that the Hausdorff dimension of the system of bonds changes from Euclidian three-dimensional below to fractal 2.55 ± 0.05-dimensional geometry above the glass transition temperature

LONG-TERM SAFE STORAGE AND DISPOSAL OF SPENT SEALED RADIOACTIVE SOURCES IN BOREHOLE TYPE REPOSITORIES

Abstract Borehole disposal of spent sealed radioactive sources (SRS) has a number of noticeable advantages: • Effective radiating protection; • Long-term safety of disposal. • Operational safety; • Easy in operation; • Conceptually simple; • Simplicity of a design; • Easy of erection; • Practicability practically everywhere; • Low cost; • Long practice of application; • Retrievable (the new project); • Ease in improvement; Russian Federation has the leading experience in applying borehole storage/disposal method for SRS. A new immobilisation technology for sources being disposed of in underground repositories was mastered by 1986 and since then it is used in the country. This method uses all advantages of borehole type repositories supplementing them with metal encapsulation of sources. Sources being uniformly allocated in the volume of underground vessel are fixed in the metal block hence ensuring long-term safety. The dissipation of radiogenic heat from SRS is considerably improved, radiation fields are reduced, and direct contact of sources to an environment is completely eliminated. The capacity of a typical borehole storage/disposal facility is increased almost 6 times applying metal immobilisation. That has made new technology extremely favourable economically. The metal immobilisation of SRS is considered as an option in Belarus and Ukraine as well as Bulgaria. Immobilisation of sources in metal matrices can be a real solution for retrieval of SRS from inadequate repositories

Mathematical Simulation of the Gas-Particles Reaction Flows in Incineration of Metal-Containing Waste

A ''quasi-equilibrium'' approach for thermodynamic calculation of chemical composition and properties of metal-containing fuel combustion products has been developed and used as a part of the mathematical model of heterogeneous reacting flow which carry burning and/or evaporating particles. By using of this approach, the applicable mathematical model has been devised, which allows defining the change in chemical composition and thermal characteristics of combustion products along the incineration chamber. As an example, the simulation results of the reacting flow of magnesium-sodium nitrate-organic mixture are presented. The simulation results on the gas phase temperature in the flow of combustion products are in good agreement with those obtained experimentally. The proposed method of ''quasi-equilibrium'' thermodynamic calculation and mathematical model provide a real possibility for performing of numerical experiments on the basis of mathematical simulation of nonequilibrium flows of combustion products. Numerical experiments help correctly to estimate the work characteristics in the process of treatment devices design saving time and costs

Problems and Tasks of TRAINING at Courses for Enhancement of Qualification in the Radioactive Waste Management Area

Requirements to the professional competence of the personnel engaged in the area of the radioactive waste management are increased. Higher school cannot supply the branch with the qualified personnel; therefore special attention should be given to the system of staff retraining and to the increase of their qualification. In that paper the analysis of SIA ''Radon'' experience on the organization and carrying out training at courses of qualification improvement is represented. The main criterion of the analysis is the research of an education efficiency. Also here the basic directions of the training process improving are submitted as well as the requirements that should be considered when forming the teaching staff and trainees groups

Combined Quantitative X-ray Diffraction, Scanning Electron Microscopy, and Transmission Electron Microscopy Investigations of Crystal Evolution in CaO–Al2O3–SiO2–TiO2–ZrO2–Nd2O3–Na2O System

Glass-ceramics, with a specific crystalline phase assembly, can combine the advantages of glass and ceramic and avoid their disadvantages. In this study, both cubic-zirconia and zirconolite-based glass-ceramics were obtained by the crystallization of SiO2-CaO-Al2O3-TiO2-ZrO2-Nd2O3-Na2O glass. Results show that all samples underwent a phase transformation from cubic-zirconia to zirconolite when crystallized at 900, 950, and 1000 °C. The size of the cubic-zirconia crystal could be controlled by temperature and dwelling time. Both cubic-zirconia and zirconolite crystals/particles show dendrite shapes, but with different dendrite branching. The dendrite cubic-zirconia showed highly oriented growth. Scanning electron microscopy images show that the branches of the cubic-zirconia crystal had a snowflake-like appearance, while those in zirconolite were composed of many individual crystals. Rietveld quantitative analysis revealed that the maximum amount of zirconolite was ∼19 wt %. A two-stage crystallization method was used to obtain different microstructures of zirconolite-based glass-ceramic. The amount of zirconolite remained approximately 19 wt %, but the individual crystals were smaller and more homogeneously dispersed in the dendrite structure than those obtained from one-stage crystallization. This process-control feature can result in different sizes and morphologies of cubic-zirconia and zirconolite crystals to facilitate the design of glass-ceramic waste forms for nuclear wastes