Alteration experiments have been performed using RTT7 and synthetic basaltic glasses in MgCl2−CaCl2 salt solution at 190°C. The duration of experiments ranged from 0.25 to 463 days. The alteration products were studied by Scanning Electron Microscope (SEM), Scanning Transmission Electron Microscope (STEM), X-ray diffraction (XRD) and Electron Spectrometry for Chemical Analysis (ESCA). For both glasses, the early alteration product is a hydrotalcite-like compound [Mg6Al2CO3(OH)16·4H2O] in which HPO42−, SO42− and Cl− substitutes for CO32−. The measured basal spacing is 7.68 Å for the hydrotalcite formed from R7T7 glass and 7.62 Å for the hydrotalcite formed from basaltic glass which reflect the high Al/Al + Mg ratios x (0.34 ≤ x ≤ 0.46). The chemical microanalyses show that the hydrotalcite is subsequently covered by a silica-rich gel which evolves into saponite after a few months. These results support the use of basaltic glasses alteration patterns in Mg-rich solution, to understand the long-term behavior of R7T7 nuclear waste glass.

Synthesis of the Li-Al-Fe layered double hydroxides was performed by the coprecipitation method at constant pH (11.0±0.2) and temperature (40±2°C). Structural features of the as-synthesized samples were investigated by X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy and Mössbauer spectroscopy. The samples consisted of well crystallized [LiFexAl2-x(OH)6]2CO3·nH2O phases with strict ordering of M+ and M3+ cations in the sheets. However, only a proportion of Al3+ could be substituted by Fe3+ ions. The excess Fe3+ cations formed a separate ferrihydrite phase. Incorporation of Fe into the hydrotalcite-like structure resulted in an increase in the a lattice parameter determined by XRD. In addition, a shift of IR absorption bands, ascribed to the stretching vibrations of interlayer CO32− anions as well as the transitional motions of oxygen in the layers, to lower frequencies was observed. The presence of Fe3+ in the octahedral sheets caused a splitting of the band assigned to the stretching vibrations of the layer OH groups. Mössbauer experiments revealed that Fe exists in the synthesized samples in two different chemical environments. A proportion of the Fe3+ cations is incorporated as isolated ions in the [LiFexAl2-x(OH)6]2CO3.nH2O crystal structure. However, Fe3+ ions forming the ferrihydrite phase are dominant in the Fe-rich materials.