Changes in Blue Color of Sapphire Compared with Oxidation State Changes

Abstract

Blue sapphire has long been treated with heat to modify its blue color and attain greater value. However, the process of modifying the blue color in sapphire remains not well understood. The color-changing mechanism has traditionally been explained using the Intervalence Charge Transfer (IVCT) (Fe2+-Ti4+ and/or Fe2+-Fe3+) theory, wherein the blue color can be diminished by heat treatment in an oxidizing environment which alters Fe2+ (FeO) to Fe3+ (Fe2O3) and decreases the occurrence of the IVCT process. However, recently, the band gap theory has been proposed, suggesting that iron (Fe) in sapphire is always in the Fe3+ state, the blue color is caused by Fe3+-Ti4+ pair and the heat treatment does not affect Fe oxidation state. Therefore, in this study, eight magmatic sapphires from four localities were investigated for changes in blue color via color analysis, changes in spectra using XANES, and changes in chemical composition using PIXE both before and after heat treatment. The color analysis reveals a slight reduction in saturation (fading of blue) and a noticeable lightening after heat treatment, which corresponds with the high content of solid inclusions or trapiche samples. XANES data analysis using the LCF technique indicated insignificant changes in Fe oxidation state from 2+ to 3+ after heat treatment across all samples. However, when comparing the XANES data with color parameter L*a*b*, it is noted that the percentage of Fe oxidation state changes does not show a positive relationship with changes in blue based on color parameter b* (blue–yellow); rather, it shows a positive relationship with parameter L* (lightness). Microscopic observations also reveal the dissolution of clouds or minute particles around planes of ilmenite needles. It could be suggested that the changes in Fe oxidation state may not be directly related to changes in blue color but could be linked to the partial dissolution of Fe-bearing inclusions.