The Effects of Alkaline Earth Metals on the Structure of Sodium Borosilicate Glasses: 11B and 29Si NMR Study

The effect of substitution of alkaline earth metals for sodium on the structure of alkali borosilicate glasses had been studied using the solid-state 11B and 29Si NMR spectroscopy. NMR spectra enable to evaluate the relative mole fractions of different silicon and boron structural units in studied samples. The obtained results demonstrate that alkaline earth metals increase the polymerization degree of the silicon structural units at the expense of de-polymerization of the boron units. The reason for these changes is preferential coordination of sodium and alkaline earth metals to the boron units, that increases strongly for the studied alkaline earth metals.

Evolution of cations speciation during the initial leaching stage of alkali-borosilicate-glasses

Alkali-borosilicate glasses (ABS) are used as host immobilization matrices for different radioactive waste streams and are characterized by their ability to incorporate a wide variety of metal oxides with respectively high waste loadings. The vitreous wasteform is also characterized by very good physical and chemical durability. The durability of three ABS compositions were analyzed by investigating their leaching behavior using the MCC1 test protocol and these data were used to investigate the waste components retention in the altered layer and the evolution of the interfacial water composition during the test. The results indicated that the Mg species evolution is exceptional with respect to other alkaline elements and dependent on glass matrix composition and leaching progress, while transition elements speciation is fairly constant throughout leaching process and independent on glass compositions. Si and B species are changing during leaching process and are affected by waste composition. For modified wasteform sample, evolution of Mg, Si and B species is respectively constant, whereas at highest waste loading, these elements have fairly constant speciation evolution within the first 2 weeks of leaching.

FERROELECTRIC NANOCOMPOSITES WITH GOVERNED INTERFACE ON BASE OF MAGNETIC POROUS GLASSES

Two-phase (nonporous) magnetic alkali borosilicate glasses have been produced by induction melting. Their macroscopic properties and crystal structure have been studied and it is shown that in the silica skeleton there are the agglomerates of Fe3O4. These agglomerates are formed by monodomain nanoparticles of magnetite and demonstrate the superparamagnetic properties. After special thermal treatment (liquation process) and chemical etching the nanoporous matrices with random dendrite pore structure and magnetic properties have been produced. The channels (porous space) were filled by ferroelectric materials KH2PO4 (KDP), KH2PO4+(NH4)H2PO4 (KDP-ADP or KADP), and NaNO2 and the effect of applied magnetic fields on phase transitions in these nanocomposite have been studied. It has also been established that a restricted geometry changed essentially the phase diagram of KADP.

An Assessment of Initial Leaching Characteristics of Alkali-Borosilicate Glasses for Nuclear Waste Immobilization

Initial leaching characteristics of simulated nuclear waste immobilized in three alkali- borosilicate glasses (ABS-waste) were studied. The effects of matrix composition on the containment performance and degradation resistance measures were evaluated. Normalized release rates are in conformance with data reported in the literature. High Li and Mg loadings lead to the highest initial de-polymerization of sample ABS-waste (17) and contributed to its thermodynamic instability. Ca stabilizes non-bridging oxygen (NBO) and reduces the thermodynamic instability of the modified matrix. An exponential temporal change in the alteration thickness was noted for samples ABS-waste (17) and Modified Alkali-Borosilicate (MABS)-waste (20), whereas a linear temporal change was noted for sample ABS-waste (25). Leaching processes that contribute to the fractional release of all studied elements within the initial stage of glass corrosion were quantified and the main controlling leach process for each element was identified. As the waste loading increases, the contribution of the dissolution process to the overall fractional release of structural elements decreases by 43.44, 5.05, 38.07, and 52.99% for Si, B, Na, and Li respectively, and the presence of modifiers reduces this contribution for all the studied metalloids. The dissolution process plays an important role in controlling the release of Li and Cs, and this role is reduced by increasing the waste loading.