The blue color mechanism on sapphires from different gem deposits before and after heating under oxidizing atmosphere

Abstract

The blue color of sapphire is commonly related to the amount of Fe and Ti impurities replacing Al3+ in Al2O3 structure. Generally, the color intensity on sapphires is related to the gem deposits including the basaltic-related and metamorphic-related ones. The color of sapphires has been changed after heating under oxidizing atmosphere. However, the explanation about the color mechanism from some previous research contradicted each other and it was still wondered. For this reason, this research is focused on the role of Fe and Ti oxidation states as well as the blue color mechanism on sapphires before and after heating under oxidizing atmosphere. In this study, the sapphire samples were collected from different gem deposits including basaltic-related sapphires from Kanchanaburi province, Thailand and metamorphic-related ones from Sri Lanka before and after heating at 1100°C under oxidizing atmosphere. As a result, the blue color on sapphires before heating can be described that a hole color center assigned to Fe3+-Ti4+ mixed acceptor states inside an energy band gap that could be received an electron from the valence band for charge-balancing after excitation. After heating, the basaltic-related sapphires turned from dark blue to light blue and the metamorphic-related ones turned from light blue to colorless because the Fe3+-Ti4+ mixed acceptor states were decreased because a hole color center was filled by an electron from oxygen during the heating process instead of an electron from the valence band. Therefore, it can be concluded that the blue color mechanism on sapphires before and after heating under oxidizing atmosphere can be explained by an energy band model involving the presence or absence of Fe3+-Ti4+ mixed acceptor states as well as a hole color center inside an energy band gap.

Changes in Blue Color of Sapphire Compared with Oxidation State Changes

“…Recently, the proposed presence of Fe 3+ -Ti 4+ mixed acceptor states in the energy band gap has been proposed as the cause of the blue color in sapphire, suggesting that when blue sapphire is heat-treated in oxidizing conditions, electrons are added to holes on those mixed acceptors, the holes are filled up, and they require fewer electron transitions, resulting in the hindering/fading of the blue color. Therefore, the oxidation of Fe does not change in the process [14][15][16][17][18][19].…”