Abstract:
The main objectives of this study were to investigate conditions for stable and metastable liquid immiscibility in dry borosilicate synthetic systems and to evaluate effects of temperature and bulk melt composition on two-liquid element partitioning and boron speciation. To distinguish between the stable immiscibility and quench heterogeneity, we used high-temperature centrifuge phase separation. For the case of stable liquid immiscibility, silica-rich (LS) and borate-rich (LB) conjugate liquids formed two distinct layers separated by a sharp meniscus. The liquids were quenched into glasses, which were analysed by electron microprobe. Some of the glasses were also studied by Raman spectroscopy. We used several synthetic mixtures along the danburite-anorthite (CaB2Si2O8-CaAl2Si2O8) and danburite-reedmergnerite (CaB2Si2O8-NaBSi3O8) joins. In addition, we studied four complex, six-component, Mg-bearing compositions with variable Na2O and Al2O3 contents. The experiments show that the width of the LS-LB miscibility gap decreases more rapidly with the B-Al substitution (in the danburite-anorthite join) than with the Ca-Na substitution, implying that interactions between network-forming elements have a greater effect on borate-silicate unmixing than the nature of network-modifying cations. Ca and Mg partition strongly to the depolymerised borate-rich liquid with LB-LS partition coefficients of ∼40 and higher. On the other hand, two-liquid partition coefficients of Na and Al in most cases are close to 1 and show complex variations with temperature and bulk melt composition. Raman spectra of LB glasses quenched at different temperatures suggest that the proportion of trigonal boron in bulk boron content decreases with decreasing temperature. The change in boron speciation appears to affect Al and Na two-liquid partitioning in such a way that at low temperatures, the latter element becomes more compatible with LS.
