Spectroscopic Investigation of the Coloration and Fabrication Conditions of Medieval Blue Glasses

Potash- and soda-lime-stained glasses from the 12th-13th centuries, blue-colored by cobalt, have been investigated by Mn, Fe, and Cu K-edge X-ray and optical absorption spectroscopies in order to determine the oxidation state of these elements and their impact on the blue color. Remelting these historical glasses in air at 1200 degrees C, the estimated temperature of medieval furnaces, revealed that these four glasses are more reduced before remelting. This favors Mn as weakly absorbing Mn2+, Fe as Fe2+ and Cu as colorless Cu+. Therefore Fe2+ is the second blue chromophore and copper was not intentionally used by glassmakers to obtain a blue color. A colorimetric analysis indicates that these specific melting conditions have a limited effect on the blue color of these glasses. Based on the spectroscopic determination of the redox state of Fe, Mn, and Cu, we estimate the oxygen partial pressure in medieval furnaces to be 10(-7)-10(-9) and 10(-5)bar for the potash- and soda-lime samples, respectively. The comparison with previous results enables to prove the evolution of furnace technology over centuries.