Non-invasive Analyses of Ancient Ceramics Colorants

Minerals, 2024

Throughout history, ceramics have been the most abundant artifacts in archaeological discoveries. Within the Neolithic period in present-day Bulgaria, skilled artisans applied additional materials to decorate their pottery, evolving in composition and application techniques such as painting or incrustation. This study is focused on the investigation of white pigments used in decorating Early and Late Neolithic pottery from Madzherito, Kaloyanovets, and Hadzhidimitrovo-archaeological sites located in the Thracian Valley, Central South Bulgaria, affiliated with the cultural groups of Karanovo I and IV. Thirteen ceramic sherds were investigated through archaeometric techniques, including Fourier-transformed infrared spectroscopy in attenuated total reflection mode (ATR-FTIR) and laser-induced breakdown spectroscopy (LIBS). LIBS data underwent further analysis using principal component analysis (PCA). The results revealed that calcite, enriched with diverse fillers like quartz, clays, feldspars, and metal oxides, was the primary raw material for white decoration throughout the entire period. Talc emerged as an addition to calcite in the paint of two Early Neolithic sherds. The presence of hydroxyapatite and kaolinite in Late Neolithic pottery was also observed. The inclusion of supplementary ingredients in the primary formula for crafting white decorations signifies either the emergence of novel trends in manufacturing techniques or serves as evidence of vessels imported from adjacent territories.

geology.uaic.ro

Vessels: inside and outside. Proceedings of the conference EMAC'07 9th european meeting on ancient ceramics., 2009

Detailed infrared (FTIR) and Raman (FT-Raman) spectroscopic investigations were performed on raw pigment materials and painted ceramic fragments from the excavation of Szombathely-Oladi plató. In the raw yellow and red pigments we can identify limonite and hematite as colouring minerals, respectively. A special raw red pigment was found to be of purified hematite. On the ceramic fragments decorated with red, however, the paint-layer proved to be made of cinnabar (HgS) mixed with high-purity kaolin. The use of cinnabar in the Late Neolithic period was firstly established on painted ceramics belonging to the Early Lengyel Culture.

Archeometriai Műhely, 2013

Scanning electron microscopic (SEM-EDS), Raman (FT-Raman) and infrared (FT-IR) spectroscopic investigations were performed on raw pigment materials and polichrome painted ceramic fragments from the excavation of Szombathely-Oladi plató and Gór-Kápolnadomb.. In the raw yellow and red pigments we could identify goethite and hematite as colouring minerals, respectively. A special raw red pigment was found to be of ‘pure’ hematite. On the ceramic fragments decorated with red, the paint layer proved to be made of cinnabar (HgS) mixed with high-purity kaolin. The white decoration proved to be pure, homogeneous calcite. To our knowledge, this is the first evidence of the use of cinnabar (HgS) for decorated pottery in Late Neolithic period in the region of Hungary. The use of cinnabar as painting material proved though to be rare among our samples from both archaeological sites

A major role in Russian investigations of Upper Paleolithic pigment and ceramics belongs to N. D. Praslov. The cultural deposits of Kostienki‐1 site yielded approximately 400 ceramics fragments of different size. The final result was the defining of a possible temperature range for firing the studied samples, from 500 to 860–940 °C. The pigments from the site of Kostienki‐1 present a rich palette of colors and were used in ornamentation of dwellings and single inventory categories.

Journal of Raman Spectroscopy, 2012

This investigation is focused on the identification in ceramic artworks of certain nonstandard yellow/orange pigments whose composition is based, fundamentally, on lead, tin, and antimony oxides with or without silica. In this work, a comparative study (temporal and geographical) of the employment of these yellow pigments in different production centers, from Italy (Pesaro and Montelupo) and Spain (Talavera de la Reina), during the Renaissance and Baroque epochs has been proposed. For this purpose, special very ancient yellow pigments were acquired from the Stazione Sperimentale del Vetro, Murano-Venezia (Italy). These reference pigments have been produced following strict and rigorous manufacturing recipes corresponding to Venezian fabrication processes for the 16th and 17th centuries. On the other hand, the portable characteristic of a new optical fiber Raman system has allowed us the access into the Museo de Cerámica de Barcelona in order to investigate the composition of the yellow and orange colors of an important ceramic collection belonging to this museum. The results are in good agreement with the ones obtained by other authors who have investigated the same topic. It is notable, first, the excellent performances that this portable Raman system offers in the direct and non-invasive analysis of ceramic artworks and, second, the coincidences of the molecular results among these yellow pigments. This fact confirms that these pigments were commonly used either in Italian and Spanish ceramic objects during both Renaissance and Baroque epochs.

Laser …, 2006

In the field of cultural heritage, the study of the materials used by the artist is useful both for the knowledge of the artwork and for conservation and restoring interventions. In this communication, we present results of some decorations analysis obtained by the use of two complementary laser techniques: micro-LIBS and micro-Raman spectroscopy. With both techniques it is possible to operate in a practically nondestructive way on the artwork itself, without sampling or pretreatment. Micro-Raman spectroscopy gives information on the molecular structure of the pigments used, while micro-LIBS can give quantitative information about the elemental composition of the same materials. In this paper, qualitative results are reported obtained on the study of some Neolithic potteries coming from the archaeological site of Trasano (Matera); the fragments show decorations in different colors, red, black, and white. The aim of the study was detecting whether the colored decorations were made by using added pigments or came from the manufacturing process.

Optics and Spectroscopy, 2020

Using IR reflectance spectroscopy, we studied the structural and chemical composition of the colored layer located on the surface of a female figurine made of a mammoth tusk from the East Gravettian site of Kostenki 1, layer I, aged 23000-21000 years. The site is located in the Kostenki village of the Khokholsky district of the Voronezh oblast of Russia. The figurine was at the bottom of the storage pit; there are the remains of red paint on it. The paint layer on the figure consists of alumina and gypsum; the coloring pigments are mainly iron oxides. The data obtained suggest that the technology used by the Paleolithic artist when painting the figurine of the Paleolithic Venus included the stage of preliminary preparation of the surface, that is, priming the treated surface with gypsum.

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...