Intermediate structures in radiation damaged titanite (CaTiSiO ₅): A Raman spectroscopic study

Effects of radiation damage and thermal annealing on the crystal structure of natural titanite (CaTiSiO₅) were studied using Raman spectroscopy. The results show that well crystallized natural titanites generally have the P2₁/a structure at the unit cell level, in contrast to the A2/a symmetry reported previously. Radiation caused by naturally incorporated impurities (such as U and Th) leads to structural damage and amorphization in titanite, as evidenced by a significant loss of band intensity, spectral broadening and frequency shifts. Additional bands (e.g. near 574 and 650 cm ^-1) occur in weakly or partially metamict titanite due to the formation of an intermediate phase (with the A2/a symmetry). Raman spectra of titanite thermal glasses showed features different from those of metamict titanite, especially in the Ti-O and Si-O stretching regions. The effect of thermal annealing is strongly affected by the initial degrees of damage that the sample experienced. Weakly damaged titanite samples showed that annealing leads to a structural recovery, and the spectral patterns of these recovered crystals are consistent with the P2₁/a symmetry. Highly damaged titanite starts to recrystallize into an A2/a phase near 700-800 K, and additional structural modification occurs when annealed at 1300-1400 K, which involves significant change in broad Ti-O features. However, in terms of bandwidths, the metamict samples are far from fully recovered even on being annealed at 1300-1400 K.