Colourants and opacifiers in seventh and eighth century glass investigated by spectroscopic techniques.

Glass fragments dating from the seventh and eighth century AD were excavated in the Crypta Balbi in Rome. They were studied to detect agents involved in colour development and opacification. Reflectance spectra recorded on powdered samples revealed the contribution of Fe(II), Fe(III), Mn(III), Cu(II), and Co(II) ions in determining colour hues. The effect of the Mn/Fe atomic ratio on glass colour is discussed. It is apparent that medieval glassmakers in Italy could obtain a wide range of colours by exploiting the presence of iron and manganese as contaminants of sand and flux and controlling the amount of oxygen let into the furnace. X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray analysis were used to study opaque fragments. The presence of calcium antimonate was detected in white, blue, and blue-green fragments, and elemental copper was detected in a red glass.