Raman spectroscopy as a tool for the non-destructive identification of organic minerals in the geological record (original) (raw)
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ArcheoLogica Data, 2022
This paper reports on the preliminary results of the ongoing research on Medieval and Renaissance ceramic corpus from a cistern placed under the Incontri-Viti Palace in Volterra, Italy. The potteries found in the cistern are dated between 14 th and 16 th centuries; this period is marked by the transition between the late Middle-Ages and the Renaissance, and it is characterized by the introduction of technological and stylistic innovations in glazed ceramic productions. The work is part of a wider research program which involves the study of Volterra from the Late Antiquity to the Early Modern Age, through the detailed characterization of ceramic finds. Among samples from Incontri-Viti Palace, thirty-three fragments were selected for this investigation based on shape and decoration, including Maiolica and Graffita (or Sgraffito) productions. Micro-Raman and X-ray fluorescence analysis were carried out on both glaze and body, providing-for the first time-the non-invasive and non-destructive characterization of Maiolica and Graffita productions from Volterra. The investigation allowed the discrimination among studied productions based on glaze components and colouring agents, identifying one main compositional group credibly linked to local workshops. The analysis of ceramic paste enabled differentiating Italo Moresca among Maiolica productions for the higher tenor of Ca, which is a marker of the technological innovation optimised for obtaining a creamy coloured paste.
CHARACTERISATION OF FINE WALL AND EGGSHELL ROMAN POTTERY BY RAMAN SPECTROSCOPY
Roman pottery from Oiasso harbour (nowadays Irun, Basque Country) has been thoroughly studied by micro-Raman spectroscopy and X-ray diffraction analysis in order to identify and characterise the mineralogical composition of those samples and to get a deeper insight about technologies involved in the elaboration of ceramic artifacts. The diffraction pattern of the ceramic body shows the presence of mullite and trydimite, which suggests firing temperatures above 1100 oC, and alumina-rich raw materials. Additionally, the presence of pseudowollastonite and diopside observed by the XRD and Raman spectroscopy is explained by high firing temperatures of lime-rich raw materials. Raman microscopy has also provided further information about the heating temperature and composition of raw materials. On the one hand, the presence of rutile (TiO2) but not of anatase also suggests a strong heating process. Moreover, the presence of hematite (α-Fe2O3) and maghemite (γ-Fe2O3) instead of magnetite (Fe3O4) suggests the oxidising conditions during ceramics firing
Micro-Raman spectroscopy of ancient ceramics: a study of Frenchsigillata wares
Journal of Raman Spectroscopy, 2004
Micro-Raman spectroscopy was applied to the study of some French sigillata wares dating back to the end of the 1st century AD and coming from two important Roman ceramic production centres at La Graufesenque (Aveyron) and Glanum in Saint Rémi de Provence. The differentiation between the mineralogical composition of the reddish bright slip and the porous ceramic body underneath was accomplished, confirming the previous hypothesis by the CNRS research group at Toulouse that a different and finer clay material was used for the coating. This was primarily suggested by the highly heterogeneous body matrix mineralogy due to the presence of a large variety of minerals such as haematite, quartz, rutile and feldspar species, while the slip coating was basically made of haematite alone. The phase analysis results also gave an indication of the firing for insight into the production technology: an oxidizing atmosphere and a firing range between 850 and 1000°C could be suggested, in good accordance with the acknowledged Roman sigillata pottery production procedure. Copyright © 2004 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy, 2014
ABSTRACT Ten fragments of pots made by pietra ollare (basic and ultrabasic metamorphic rocks belonging to greenschist facies) found in the archaeological site of Crocetta di Sant'Agata Bolognese (Bologna, Italy) have been studied to characterize them and to define their provenance. The fragments, dated between the 9th and 10th century AD, show traces of blackening from fire, indicating the use of these findings as pots by fire. The extensive use of a non-destructive technique, Raman spectroscopy, in both laboratory and portable forms, for the provenance analysis of pietra ollare artifacts has been evaluated. Micro-Raman spectroscopy was used for a detailed study of the main components, to identify the secondary minerals and to study the distribution of the mineral phases in the samples. The samples show schistose texture, are fine grained and consist mainly of talc and chlorite, and subordinate carbonates, oxides and serpentine. Olivine is rare. Based on the mineralogical composition, the material can be defined as chlorite and carbonate talc-schist. Our samples of pietra ollare may be assigned to chlorite and magnesite-bearing talc-schists. The alpine areas of origin of this lithotype are Valtellina, Valchiavenna and Val Bregaglia. In particular, we can hypothesize that the origin of these findings is Valchiavenna, which had great commercial importance in the Middle Ages. Further measurements, obtained with a portable Raman spectrometer, directly on a quarry near Chiavenna, support our hypothesis. Copyright © 2013 John Wiley & Sons, Ltd.
Medieval and Renaissance waste shafts (butti) offer a unique opportunity to study objects of common use in the past, the majority of findings that emerge from the excavation of these pits are pottery found in fragmentary condition, sherds that provide essential information on the historical periods to which the butto belongs. In the present work Micro-Raman analysis was conducted on a representative group of samples dated back from XIV to XVIII century, coming from the waste shaft pertained to the Monk’s Palace sited in Leprignano, the current Capena in the province of Rome. The aim of the study was to characterize the composition of coloured glazes pertaining to majolica sherds, through a technique that has proved to be invaluable for this purpose, according to the amount of published data in recent years. Differences in terms of structure and constituents of the decorative layers have been observed. Yellow pigments can be ascribed to the family of lead pyroantimonates, in both binary and ternary form, brown and green glazes are constituted by ions dissolved in the glass matrix, while in blue glazes cobalt olivines have been clearly identified for some samples. Polymerization index calculated on vitreous layers shows the presence of a lead-based glaze that is commonly found in majolica referable to the same age and provenance. The results obtained are in a good agreement with Piccolpasso’s treatise, “The Three Books of Potter's Art”, except for a sherd pertaining to a later Ligurian production.
2018
Medieval and Renaissance waste shafts (butti) offer a unique opportunity to study objects of common use in past times; the majority of findings that emerge from the excavation of these pits are pottery found in fragmentary condition, sherds that provide essential information on the historical periods to which the butto belongs. In the present work Micro-Raman analysis was conducted on a representative group of samples dated back from XIV to XVIII century, coming from the waste shaft pertained to the Monk’s Palace sited in Leprignano, the current Capena in the province of Rome. The aim of the study was to characterize the composition of coloured glazes pertaining to majolica sherds, through a technique that has proved to be invaluable for this purpose, according to the amount of published data in recent years. Differences in terms of structure and constituents of the decorative layers have been observed. Yellow pigments can be ascribed to the family of lead pyroantimonates, in both b...
Vibrational Spectroscopy, 2011
Non-invasive Raman microspectroscopy, FTIR, µXRD and XRF were used to identify the materials present in the black, red, and white surface decorations in elected pottery wares from two Prehispanic archae-ological sites in Northwestern (NW) Argentina (AD 900–1530). The iron manganese spinel jacobsite, MnFe2O4, was found to be the main component of two of the fired black decorations analyzed, while hematite and amorphous silicates were found to be present in the red and white fired decorations, respectively. This is the first study, to our knowledge, that firmly identifies jacobsite in black decorations in Prehispanic archaeological ceramics. In fragments recovered from one site, a carbon-based black pigment was identified while gypsum was observed in the recessed areas of decorative surface incisions. Gypsum, potassium nitrate and halite, most likely deposited during burial, were observed on the surface of some of the fragments analyzed. The results are discussed in the context of the technological processes involved and are compared to compositions previously reported for decorations in ceramic objects from NW Argentina.
On-Site Raman Analysis of Rare Ancient Ceramics : Medici Porcelain and Iznik Pottery
On site Raman analyses were performed at the Musée national de Céramique, Sèvres, France, on rare Iznik Ottoman pottery produced between ~1480 and ~1620 and Florentine Medici porcelain produced between 1575 and ~1587. Comparison is made with similar Sefavid (Persia, ~1500-1730) and Kütahya (from 1550 or more probably from 1680) pottery. In most Iznik/Kütahya fritwares; the white colour arises from an α -quartz slip, cassiterite (SnO2) opacifier being present only in some early blue-and-white Iznik fritwares (Master of the Knots and Baba Nakkas style, ca. 1510-1530). We do not have other evidence of tin oxyde intentional use as an opacifier. Intentional addition of tin oxide is likely for colour lightening in some red, blue and in clear green boles. At least two types of red glazes and two types of Cr-containing dark-green to black pigments are evidenced. Analysis of Medici Porcelain shows the material was prepared using feldspar, sand and calcium-rich glass, i.e. associating hard- a...