Thermal Process of Rock Crystal: Cause of Infrared Absorption Band at 3585 cm−1

Synthetic rock crystals often show a typical infrared (IR) absorption band at 3585 cm−1. However, the authors recently found this band in a natural rock crystal with blue coating. The origin of this IR band is controversial as yet. In this paper, the infrared spectra of several natural and synthetic rock crystal samples which were heated to 673 K and 1073 K were measured after these samples returned to room temperature. Comparing the infrared spectra of samples before and after heating, we found the absorption band at 3585 cm−1 was induced by the thermal process, which indicates that this band cannot be used as diagnostic evidence for synthetic rock crystal alone. In addition, the LiOH bands decreased while AlOH bands increased upon thermal processing. And the negative correlation between the LiOH bands and the 3585 cm−1 band was also distinct. The above results reveal that the thermal process destroyed the LiOH defects, leading to the formation of a new AlLi defect. And the isolated OH− defect inside dislocations generated upon thermal processing is considered to be the exact cause of the 3585 cm−1 band.

OH point defects in quartz – a review

Research results of the past 6 decades on the incorporation of OH point defects in quartz are summarised and evaluated in terms of their application to natural samples and processes, and a link between experimental petrology, natural archives, and model calculations is made. A strong focus is put on recent studies on quartz as a rock-forming mineral, as a geochemical and/or petrological tracer, and as a tool for provenance analysis in sediments and sedimentary rocks. The most relevant defects for natural specimens are generated by coupled substitution involving mono- and trivalent cations, the most prominent being Li+, Al3+, and B3+. OH incorporation is rather a function of the availability of trace metals and water than of pressure and temperature, though temperature indirectly influences the incorporation by the solubility of trace metals in the fluid. Pressure has a negative influence on the formation of OH defects, so the most pure quartzes are probably formed in the deep crust close to the quartz/coesite transition. Natural quartz grains from the Earth's crust have on average 10 wt ppm (weight parts per million) water (5 wt ppm median), but grains with OH defect contents corresponding to up 250 wt ppm water have been discovered in sedimentary archives, matching the concentration of quartz from high-pressure experiments <4 kbar under water-saturated conditions in granitic systems. A rough division into three classes is suggested: (1) grains with pristine igneous and/or hydrothermal origin, (2) mildly thermally annealed grains, and (3) strongly dehydrated grains. While samples derived from the currently exposed Scandinavian Shield are dominated by the third class, considerable contributions of the first two classes are found in the younger rock systems in Central Europe. OH defect contents may be used to estimate mixing ratios for sediments with different sources, provided that a sufficiently large data set exists and that the different sources can be clearly distinguished by their OH inventory. Furthermore, metamorphic overprint leads to a higher degree of equilibration of OH defects between individual grains and may thus be used as a geothermometer. Finally, OH defect retention in quartz allows for estimating timescales of volcanic processes.

OH defect contents in quartz in a granitic system at 1–5 kbar

Quartz is able to incorporate trace elements (e.g., H, Li, Al, B) depending on the formation conditions (P, T, and chemical system). Consequently, quartz can be used as a tracer for petrogenetic information of silicic plutonic bodies. In this experimental study, we provide the first data set on the OH defect incorporation in quartz from granites over a pressure/temperature range realistic for the emplacement of granitic melts in the upper crust. Piston cylinder and internally heated pressure vessel synthesis experiments were performed in a water-saturated granitic system at 1–5 kbar and 700–950 °C. Crystals from successful runs were analysed by secondary ion mass spectrometry (SIMS) and Fourier transform infrared (FTIR) spectroscopy, and their homogeneity was verified by FTIR imaging. IR absorption bands can be assigned to specific OH defects and analysed qualitatively and quantitatively and reveal that (1) the AlOH band triplet at 3310, 3378 and 3430 cm−1 is the dominating absorption feature in all spectra, (2) no simple trend of total OH defect incorporation with pressure can be observed, (3) the LiOH defect band at 3470–3480 cm−1 increases strongly in a narrow pressure interval from 4 kbar (220 µg/g H2O) to 4.5 kbar (500 µg/g H2O), and declines equally strong towards 5 kbar (180 µg/g H2O). Proton incorporation is charge balanced according to the equation H+ + A+ + P5+ = M3+ + B3+, with A+ = alkali ions and M3+ = trivalent metal ions.

Hydrothermal Synthesis and Structure Characterization of Nanocrystalline Barium Titanate Powders

Nano-sized barium titanate powders were prepared by the high-gravity reactive precipitation (HGRP)-hydrothermal method. The properties and defects of hydrothermal barium titanate crystallites were investigated by TEM, XRD and FTIR. The mean particle size of the hydrothermal barium titanate was about 70 nm with narrow particle size distribution. The crystallite phases and OH defects were focused. The results show that the powders without heat treatment were crystallized as cubic-BaTiO3 and the absence of tetragonal with increasing calcined temperature to 1100°C. The IR results exhibited the OH defect content in the crystallites was to increase the heat treatment temperature and reduced the probability of forming barium vacancies.