Chemo-Mineralogical Changes in Six European Monumental Stones Caused by Cyclic Isothermal Treatment at 600 °C

This experimental study analyses the extent of chemo-mineralogical changes that occur when a building stone encounters a cycling isothermal treatment at 600 °C. Four carbonate and two silicate European building stones were analysed in their fresh quarried and thermally treated conditions by means of colour measurements, in situ X-ray diffraction (XRD), and optical microscopy. Furthermore, powdered samples were characterised by Fourier-transform infrared spectroscopy, simultaneous thermal analysis, and cycling thermogravimetry (TG). The in situ XRD spectra revealed a surface-limited phase transformation of solid calcite and dolomite under isothermal conditions during the first 10 min at 600 °C and 500 °C, respectively. The onset of thermal decomposition and extent of phase transformation were governed by the microstructure of the solid samples. Inter- and intragranular microcracks are induced to varying degrees, and their incidence depended on the stone’s microstructure. Discolouration indicated a transformation of minor elements across the entire analysed sample volumes. Kaolinite was preserved even after three hours of thermal treatment at its dehydroxylation temperature due to its sheltering in confined pore spaces. Mass loss was more pronounced when cyclic treatment was employed compared to a non-periodic treatment, as determined by a TG analysis performed at same time intervals. Examining the chemo-mineralogical and microstructural changes caused by heat treatment allows us to study how and if regaining mechanical strength and restoring physical properties are possible for purposes of heritage restoration after fire damage.