Mineralogical study of historical bricks from the Great Palace of the Byzantine Emperors in Istanbul based on powder X-ray diffraction data

摘要

This study concerns the Quantitative Phase Analysis (QPA) of historical bricks coming from the complex of the Great Palace of the Byzantine Emperors in Istanbul. The studied samples are characterised by different chemical compositions (low and high calcium content), variable firing temperatures and different amounts of soluble salts as damage products. In the low-Ca samples, the decrease of the phyllosilicate content (from 23.4 to 6.9 wt%) is associated to the increase of the amorphous fraction (from 24 to 48%). This clear negative correlation between the phyllosilicate content and the amorphous fraction indicates that in low-Ca systems vitrification processes are overwhelming with respect to nucleation and recrystallisation processes. By contrast, high-Ca samples present newly formed Ca(Mg) silicates (diopside from 5.7 to 27.2%; anorthite from 1.4 to 8.7%) and aluminium silicates (gehlenite only in two samples, 6.2 and 7.7%) associated to the decrease of quartz (from 27.7 to 11.5%), phyllosilicate (from 6.5% until complete break down) and amorphous (from 30 to 14%) phase fractions. These findings support the role played by the CaO(MgO) content deriving from carbonates decomposition which reacts with Al2O3 and SiO2 oxides from dehydroxylated clay minerals and quartz grains. The above results have been obtained by X-ray powder diffraction data using the combined Rietveld refinement - internal standard method in order to estimate both the crystalline and the amorphous phase fractions. In addition, the coexistence of two distinct plagioclases in high-Ca samples was modelled as follows: a primary albite, which tends to incorporate Ca during the firing process as demonstrated by the increasing of gamma crystallographic angle, and a newly formed anorthite. Finally, by difference between the X-ray fluorescence data and the chemical compositions inferred by QPA, it proved possible to roughly estimate the residual chemical composition attributable to the amorphous fraction. On the basis of our data, we believe that Rietveld refinement combined with the internal standard method represent a powerful tool to better characterise complex polycrystalline and amorphous mixture as in the case of historical bricks.