In-situ IR measurements of OH species in quartz at high temperatures

Abstract 

The nature of OH species in natural clear quartz was investigated by means of in-situ IR measurements over the temperature range –185 to 1000 °C. Reversible thermal behavior of OH species was examined for a sample pre-heated to 1000 °C for 1 hour. At room temperature, the IR spectrum of the quartz sample examined includes an intense absorption peak at 3379 cm^–1 which has been assigned to an OH stretching vibration associated with Al substituting for Si (OH(Al)). The major spectral changes of the OH(Al) bond involve a systematic shift of its peak position and a decrease in its integral absorbance with temperature. A quasi-linear increase of the peak position from –185 to 400 °C is interpreted to be due to the change in the vibrational frequency of OH(Al) with hydrogen bond (H bond) distance. At higher temperatures, the IR frequency shows only a slight change, indicating a small influence of the H bond. On the other hand, the gradual decrease of the integral absorbance of OH(Al) with temperature indicates a decrease of this defect’s molar absorptivity without any reduction in defect concentration. This is interpreted to result from a decrease in dipole moment of OH(Al) with temperature. A sudden shift of the vibrational frequency from 3396 to 3386 cm^–1 between 550 and 560 °C and a constant value of the integral absorbance from 535 to 570 °C were considered to be related to the change in H bond distance during the structural transformation of α-quartz to its β-form. The local environment of OH(Al) begins to change at temperatures below 570 °C, where the crystallographic α–β transition occurs.