Raman analysis of perrhenate and pertechnetate in alkali salts and borosilicate glasses

Sodium borosilicate glasses containing rhenium or technetium were fabricated and their vibrational spectra studied using confocal Raman microscopy. Glass spectra were interpreted relative to new high‐resolution spectra of pure crystalline NaReO₄, KReO₄, NaTcO₄, and KTcO₄ salts. Spectra of perrhenate and pertechnetate glasses exhibited sharp Raman bands, characteristic of crystalline salt species, superimposed on spectral features of the borosilicate matrix. At low concentrations of added KReO₄ or KTcO_4, the characteristic pertechnetate and perrhenate features are weak, whereas at high additions, sharp peaks from crystal field‐splitting and C_4h symmetry dominate glass spectra, clearly indicating ReO₄^? or TcO₄^? is locally coordinated with K and/or Na. Peaks indicative of both K and Na salts are evident in many Raman spectra, with the Na form being favored at high concentrations of the source chemicals, where more K⁺ is available for ion exchange with Na⁺ from the base glass. The observed ion exchange likely occurred within depolymerized channels where nonbridging oxygens create segregation from the glass network in regions containing anions such as ReO₄^? and TcO₄^? as well as excess alkali cations. Although this anion exchange provides evidence of chemical mixing in the glass, it does not prove the added salts were homogeneously incorporated in the glass. The susceptibility to ion exchange from the base glass indicates that long‐term immobilization of Tc in borosilicate glass must account for excess charge compensating alkali cations in melt glass formulations. Published 2014. This article is a U. S. Government work and is in the public domain in the USA.