Silicon-Oxygen Region Infrared and Raman Analysis of Opals: The Effect of Sample Preparation and Measurement Type

An extensive infrared (IR) spectroscopy study using transmission, specular and diffuse reflectance, and attenuated total reflection (ATR) was undertaken to characterise opal-AG, opal-AN (hyalite), opal-CT and opal-C, focussing on the Si-O fingerprint region (200-1600 cm(-1)). We show that IR spectroscopy is a viable alternative to X-ray powder diffraction (XRD) as a primary means of classification of opals even when minor levels of impurities are present. Variable angle specular reflectance spectroscopy shows that the three major IR bands of opal are split into transverse optical (TO) and longitudinal optical (LO) components. Previously observed variability in powder ATR is probably linked to the very high refractive index of opals at infrared wavelengths, rather than heterogeneity or particle size effects. An alternative use of ATR using unpowdered samples provides a potential means of non-destructive delineation of play of colour opals into opal-AG or opal-CT gems. We find that there are no special structural features in the infrared spectrum that differentiate opal from silica glasses. Evidence is presented that suggests silanol environments may be responsible for the structural differences between opal-AG, opal-AN and other forms of opaline silica. Complementary studies with Raman spectroscopy, XRD and scanning electron microscopy (SEM) provide evidence of structural trends within the opal-CT type.