XANES evidence for sulphur speciation in Mn-, Ni- and W-bearing silicate melts

Author Posting. © Elsevier B.V., 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 73 (2009): 6847-6867, doi:10.1016/j.gca.2009.08.013.S K edge XANES and Mn, W and Ni XANES and EXAFS spectra of silicate glasses synthesised at 1400° C and 1 bar with compositions in the CaO-MgO-Al2O3-SiO2-S plus MnO, NiO, or WO3 systems were used to investigate sulphur speciation in silicate glasses. S K-edge spectra comprised a composite peak with an edge between 2470 and 2471.4 eV, which was attributed to S2-, and a peak of variable height with an edge at 2480.2 to 2480.8 eV, which is consistent with the presence of S6+. The latter peak was attributed to sample oxidation during sample storage. W-rich samples produced an additional lower energy peak at 2469.8 eV that is tentatively attributed to the existence of S 3p orbitals hybridised with the W 5d states. Deconvolution of the composite peak reveals that the composite peak for Mn-bearing samples fits well to a model that combines three Lorentzians at 2473.1, 2474.9 and 2476.2 eV with an arctan edge step. The composite peak for W-bearing samples fits well to the same combination plus an additional Lorentzian at 2469.8 eV. The ratio of the proportions of the signal accounted for by peaks at 2473.1eV and 2476.2eV correlates with Mn:Ca molar ratios, but not with W:Ca ratios. Spectra from Ni-bearing samples were qualitatively similar but S levels were too low to allow robust quantification of peak components. Some part of the signal accounted for by the 2473.1 eV peak was therefore taken to record the formation of Mn-S melt species, while the 2469.8 peak is interpreted to record the formation of W-S melt species. The 2474.9 eV and 2476.2 eV peaks were taken to be dominated by Ca-S and Mg-S interactions. However, a 1:1 relationship between peak components and specific energy transitions is not proposed. This interpretation is consistent with known features of the lower parts of the conduction band in monosulphide minerals and indicates a similarity between sulphur species in the melts and the monosulphides. S XANES spectra cannot be reproduced by a combination of the spectra of the component element monosulphides. Mn-, W- and Ni- XANES and EXAFS for synthetic glasses without sulphide exsolution did not show any sensitivity to the presence of sulphur, which is unsurprising as S:O ratios were sufficiently low that metals would be mostly co-ordinated by O. Mn EXAFS spectra were consistent with divalent Mn in 5 co-ordinated Mn-O melt species. W spectra were consistent with tetrahedrally co-ordinated hexavalent W, most likely in scheelite-like melt species, and Ni spectra were consistent with [4] co-ordinated divalent Ni. These results indicate lower coordinations for bothWand Ni than those inferred by some previous workers. Cation coordination may reflect the proportion of non-bridging oxygens, which is lower in the Ca-rich and Al-poor samples investigated here than for previous studies.This work was performed with 814 support from the Australian Synchrotron Research Program (ASRP), which is funded by the 815 Commonwealth of Australia under the Major National Research Facilities Program

Modelling the sulfate capacity of simulated radioactive waste borosilicate glasses

The capacity of simulated high-level radioactive waste borosilicate glasses to incorporate sulfate has been studied as a function of glass composition. Combined Raman, 57Fe Mössbauer and literature evidence supports the attribution of coordination numbers and oxidation states of constituent cations for the purposes of modelling, and results confirm the validity of correlating sulfate incorporation in multicomponent borosilicate radioactive waste glasses with different models. A strong compositional dependency is observed and this can be described by an inverse linear relationship between incorporated sulfate (mol% SO42−) and total cation field strength index of the glass, Σ(z/a2), with a high goodness-of-fit (R2 ≈ 0.950). Similar relationships are also obtained if theoretical optical basicity, Λth (R2 ≈ 0.930) or non-bridging oxygen per tetrahedron ratio, NBO/T (R2 ≈ 0.919), are used. Results support the application of these models, and in particular Σ(z/a2), as predictive tools to aid the development of new glass compositions with enhanced sulfate capacities

Structure of Rhenium-Containing Sodium Borosilicate Glass

A series of sodium borosilicate glasses were synthesized with KReO4 or Re2O7, to 10,000ppm (1mass%) target Re, to assess effects of large concentrations of rhenium on glass structure and fto estimate solubility of 99Tc, a radioactive component in low active waste nuclear glasses. Rhenium was used as a surrogate for 99Tc for laboratory testing, due to similarities in chemistry, ionic size, and redox. Magic angle spinning nuclear magnetic resonance, Fourier transform infrared spectroscopy, and Raman spectroscopy were performed to characterize the glasses. Si was coordinated in Q2 and Q3 units, Al was four-coordinated, and B was mostly three-coordinated. The rhenium additions did not have significant effects on the glass structure up to approximately 3000ppm Re by mass, the maximum concentration that remained dissolved in glass. Rhenium likely exists in isolated ReO4 anions in the interstices of the glass network, as evidenced by polarized Raman spectrum of the Re glass in the absence of sulfate. Analogous to SO4 2 in similar glasses, ReO4 is a network modifier and above solubility forms alkali salt phases on the surface and in the bulk. Comparisons of phase separation and crystallization in MoO4 2 containing borosilicate glasses can also be made to ReO4 containing glasses

Composition-structure-property effects of antimony in soda-lime-silica glasses

Float glass-type SiO 2-Na 2O-CaO glasses with 0 – 10 mol% Sb2O3 were melted and their compositional, structural, thermal and optical properties characterised. All glasses were X-ray amorphous and increasing Sb2O3 content progressively decreased glass transition temperature (Tg) and dilatometric softening point (T d), despite increases in Al2O3 content from greater crucible corrosion. 121Sb Mössbauer spectroscopy confirmed that Sb was predominantly incorporated as Sb 3+ (Sb 3+/ΣSb ~ 0.9) and Raman spectroscopy showed that Sb substantially decreased average (Si, Al)-O Qn speciation. Both techniques confirmed that Sb3+ ions were incorporated in trigonal pyramidal [:SbO 3] polyhedra. XRF and Raman spectroscopies confirmed that SO 3 content decreased with increasing Sb2O3 content. TGA analysis showed, as a linear function of Sb2O3 content, mass gain commencing at 700°C, reaching a maximum at 1175°C, then mass loss above 1175°C, consistent with oxidation (Sb3+ → Sb5+) then reduction (Sb5+ → Sb3+). The TGA samples were shown to have attained or approached Sb redox equilibrium during measurement. Optical absorption spectroscopy (UV-Vis-nIR) showed red-shifts of the UV absorption edge with increasing Sb 2O 3 content, consistent with increasing intensity of far-UV absorption bands from Sb3+ and Sb5+ s→p transitions. UV-Vis-nIR fluorescence spectroscopy evidenced a broad luminescence band centred at ~25,000 cm−1, attributed to the 3P 1→ 1S 0 transition of Sb 3+, which is Stokes shifted by ~15,000 cm −1 from the 1S0→ 3P1 absorption at ~40,000 cm−1. The most intense emission occurred at 0.5 mol% Sb 2O3, with concentration quenching reducing luminescence intensities at higher Sb 2O3 contents. Additions of Sb2O3 to float-type soda-lime-silica glasses could thus enable lower melting energies and/or new solar energy applications