Effect of annealing on natural calcitic crystals—A thermostimulated luminescence (TSL) study

The quality crystals (Calcitic limestone) were selected using the UV–visible methylene blue adsorption method. The thermostimulated luminescence (TSL) glow curve characteristics of six well crystallized limestone samples were analyzed. The glow curves of unannealed sample show only one peak in the range 320–330 °C. The sample irradiated with a gamma dose of 100 Gy shows two additional peaks in the range of 113–125 °C and 242–260 °C when recorded with linear heating rate of 10 °C/s. The annealed sample also shows the same trend as that of irradiated sample. Annealing treatment above 250 °C increases the sensitivity of all TSL peaks except 320 °C. On the other hand, annealing at 750 °C caused a collapse in the TSL sensitivity. The enhancement in TSL sensitivity was found to depend on the annealing temperature and time. Annealing treatment at 650 °C for 4 h followed by quenching in air is the optimum condition for TSL sensitization. The response to gamma irradiation is linear in the range from 0.5 Gy to 104 Gy. The emission spectra of all the samples show an emission at around 610 nm but with different intensities for each TSL peak. With reference to earlier work, it may be assumed that the recombination site always involves Mn2+ ions. The observation made through infra-red (IR) and X-ray diffraction (XRD) studies with thermal treatment shows the structural changes of calcite from D3h to Cs symmetry at 750 °C. The Thermogravimetric-Differential Thermal Analysis (TG-DTA) analysis shows the calcite gets disordered at 760 °C. Hence, the collapse in the TSL sensitivity at 750 °C is due to structural change or structural disorderedness.