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Dear Colleagues,
Raman spectroscopy provides vibrational fingerprints of chemical compounds, enabling their identification via a comparison with reference spectra. This analytical tool has high potential not only in the identification of minerals from natural sources but also for studying the complex microstructure and mineral distribution of both ancient and modern man-made materials, ranging from, e.g., historical ceramics and mortars to modern solar cell materials. In addition to the chemical identity of minerals, Raman spectra are affected by crystal orientations, substoichiometric to stoichiometric compositional changes (e.g., in solid solution series), traces of foreign ions, stress, strain, and crystallinity, enabling a comprehensive physicochemical characterisation of minerals. This Special Issue includes method developments and applications in the field of modern Raman spectroscopy of minerals in a broad sense, from natural mineral deposits to inorganic phases in materials; covers both spectroscopic and imaging studies; and provides a platform for discussing the possibilities and limits of the technique in the context of the existing analytical arsenal.
Thomas Schmid
Petra Dariz
Raman spectroscopy provides vibrational fingerprints of chemical compounds enabling their unambiguous identification. The assignment of Raman spectra to minerals is straightforward, if appropriate reference data is accessible. Modern couplings of Raman spectroscopy with microscopy (Raman microspectroscopy) merge the high structural specificity with down to sub-micrometre spatial resolution. This analytical tool has high potential not only in the identification of minerals from natural sources but also for studying the complex microstructure and mineral distribution of both ancient and modern man-made materials. In addition to the chemical identity of minerals, Raman spectra are affected by crystal orientations (varying relative Raman band intensities); (sub)stoichiometric compositional changes (e.g., in solid solution series), traces of foreign ions, strain (the latter three shifting Raman bands); and crystallinity (changing Raman band widths), enabling a comprehensive physico-chemical characterisation of minerals. Thus, Raman spectroscopy – including its in situ measurement capabilities – provides possibilities to study mineral paragenesis in both, natural and man-made samples at the micrometre scale. While in 1928 the first experimental evidence for inelastic light scattering was provided by C. V. Raman and K. S. Krishnan by using sunlight for excitation, filters for selecting the inelastically scattered light, and their eyes for detection (later, photographic plates for acquisition of spectra were employed), modern Raman spectrometers make use of laser excitation, dispersive spectrographs and charge coupled device (CCD) detection. This Special Issue includes technological developments and applications in the field of modern Raman spectroscopy of minerals in a broad sense, from natural mineral deposits and archaeological objects to inorganic phases in man-made materials. The studied minerals include fossil resins, typical rock-forming minerals (calcite, quartz, forsterite), iron-sulphur species (e.g., mackinawite), a range of sulphates (gypsum, bassanite, anhydrite III, anhydrite II, celestine, barite, ternesite), as well as silicate minerals like garnets (e.g., almandine).
Raman band widths of anhydrite II reveal the burning history of high‐fired medieval gypsum mortars
(2019)
An interdisciplinary collaboration between art technology and analytical sciences yielded an approach based on Raman microspectroscopy for the determination of the burning temperatures applied during the production process of high-fired medieval gypsum mortars. Analytical challenges and applications of the approach to examples from the cultural heritage of South Tyrol are presented.
Raman band widths of anhydrite II reveal the burning history of high-fired medieval gypsum mortars
(2019)
The use of high-fired gypsum as binder for masonry and joint mortars or stuccowork in Central Europe in the Early and High Middle Ages was a regional specific as it depended on local gypsum deposits. The calcination technology possible at the time resulted in an assemblage of calcium sulphate phases dehydrated to different degrees and partly thermally damaged accessory minerals of the raw gypsum. Because of the absence of medieval textbooks, the observation of high-temperature, low-pressure mineral transformations and the correlation of phases coexisting in not hydrated binder relicts in the gypsum matrix to the mineralogy of the raw material and the burning conditions constitute the only source to the historical technological know-how.
The CaSO4–H2O system consists of five crystalline phases, which can be discriminated by structural analysis methods, such as Raman spectroscopy, due to obvious differences in their spectroscopic data: gypsum (CaSO4 ⋅ 2 H2O), bassanite (hemihydrate, CaSO4 ⋅ ½ H2O), anhydrite III (CaSO4), anhydrite II (CaSO4), and anhydrite I (CaSO4). Only recently, it was possible to demonstrate that small spectroscopic variations exist also within the relatively large stability range of anhydrite II from approx. 180°C to 1180°C: all Raman bands narrow with increasing burning temperature applied in the synthesis from gypsum powder. The determination of band widths of down to 3 cm-1 and differences between them of a few tenths of a wavenumber is not a trivial task. Thus, this contribution discusses peak fitting and strategies for correction of instrument-dependent band broadening.
Raman maps of polished thin sections of gypsum mortars provide access to the burning histories of individual remnant thermal anhydrite grains and enable the discrimination of natural anhydrite originating from the gypsum deposit. This novel analytical method was applied to samples from medieval South Tyrolean stucco decorations and sculptures. Beyond that, Raman microspectroscopy was employed for following pyrometamorphic reactions in natural impurities of the raw material. In the presented examples mineral thermometry indicates process temperatures above 800°C: the breakdown of magnesium-rich chlorite led to the formation of forsterite Mg2SiO4, while the thermal decomposition of dolomite CaMg(CO3)2 yielded – after hydration and carbonation – magnesite MgCO3, CaCO3 polymorphs and magnesian calcite. Lower burning temperatures, which leave the accessory minerals in their pristine form, can be traced by measuring the spectra of anhydrite crystalites in grains of firing products and evaluating Raman band widths. Throughout the applications of this analytical method so far, calcination temperatures ranging from approx. 600°C to 900°C were determined.
The use of high-fired gypsum as binder for masonry and joint mortars or stuccowork in Central Europe in the Early and High Middle Ages was a regional specific as it depended on local gypsum deposits. The calcination technology possible at the time resulted in an assemblage of calcium sulphate phases dehydrated to different degrees and partly thermally damaged accessory minerals of the raw gypsum. Not hydrated clusters of firing products preserved in the binder matrix are a typical feature of such mortars. A novel Raman microspectroscopic approach, providing access to the burning history of individual anhydrite grains, was applied to samples from medieval South Tyrolean stucco decorations and sculptures. Beyond that, Raman microspectroscopy was employed for tracing and visualising pyrometamorphic reactions in natural impurities of the kiln run. In the discussed examples mineral thermometry indicates process temperatures above 800°C: the breakdown of magnesium-rich chlorite led to the formation of forsterite Mg2SiO4, while the thermal decomposition of dolomite CaMg(CO3)2 to periclase MgO and lime CaO yielded – after hydration and carbonation – magnesite MgCO3, CaCO3 polymorphs and magnesian calcite. Hydration of periclase in the mixed gypsum paste containing sulphate ions also resulted in magnesium sulphate hydrates, here identified in the form of hexahydrite MgSO4·6H2O. Lower burning temperatures left the accessory minerals in their pristine form, but can be traced by measuring the spectra of individual anhydrite crystals in grains of firing products and evaluating Raman band widths. Throughout the present study, calcination temperatures ranging from approx. 600°C to 900°C were determined.