The SON68 inactive “R7T7” composition is the French reference glass for the LWR nuclear waste glass. Vapor phase alteration was used to accelerate the reaction progress of glass corrosion and to develop the characteristic suite of secondary, alteration phases. Extensive solid-state characterization (AEM/SEM/HRTEM) was completed on six inactive R7T7 waste glasses which were altered in the presence of saturated water vapor (200 °C) for 91, 241, 908, 1000, 1013, and 1021 days. The AEM samples were examined in cross-section (lattice-fringe imaging, microdiffraction, and quantitative thin-film EDS analysis). The glass monoliths were invariably covered with a thin altered rind. The layer became thicker with time: 0.5μm for 22 days; 4 μm for 91 days; 6 μm for 241 days; 10 μm for 908 days; 26 μm for 1013 days; and <35μm for 1021 days. The composite alteration layer of the SON68 samples is at least four time less thick than that of the SRL 131 glass composition.
Six distinctive zones, based on phase chemistry and microstructure, were distinguished within the well-developed surface layers. Numerous crystalline phases such as analcime, tobermorite, apatite, and weeksite were identified on the surfaces of the reacted glasses as precipitates. Two crystalline phases, Ag2TeO3 and (Ca,Sr)Mo3O9(OH)2, were found within the inner zones of surface layers, and they must have nucleated in situ, indicating that Ag, Te, Sr, and Mo can be retained within the surface layer. The majority of the surface layer volume is composed of two morphologically and chemically different structures: one consists of well-crystallized fibrous smectite aggregates occurring along with cavities, the A-domain; and the other consists of poorlycrystallized regions containing needle-like smectite (montmorillonite) crystallites, a silica-rich amorphous matrix, and possibly ZrO2 particles, the B-domain. The retention of rare-earths and Zr mostly occurred within B-domains and that of transition elements, such as Zn, Cr, Ni, and Mn, in A-domains. The recrystallization of poorly-crystallized B-domains into well-crystallized Adomains may influence the long-term behavior of rare-earths, Zr, and transition elements. The mechanism of surface layer formation during vapor phase alteration is discussed based on the cross-sectional AEM studies of surface layers of the SON68 waste glasses.