Ancient Ceramics Research Articles

Quantitative characterisation of damage mechanisms in ancient ceramics by quantitative X-ray powder diffraction, polarisation microscopy, confocal laser scanning microscopy and non-contact mode atomic force microscopy

Ceramic technology is civilisation’s oldest tradition and one of our most current areas of knowledge. Pottery, ceramics, and their industrial production materials have been rooted in the historical and cultural structure of a nation and civilisation for thousands of years and retain their importance today. The origin of the surveyed material in this paper relates to areas of the Elamite Period (1500 BC) in South-West IranThe main purpose of the identification is to pay attention to the textural formation of the material, which is dependent on the mineralogical chemical performance in such systems. In this investigation, the texture of damage and phase segregation was determined. The phase analyses of crystalline composition were determined by quantitative X-ray powder diffraction (QXRD) measurements with Rietveld refinement. The results were matched with microscopic methods in order to arrive at a chemical petrological conclusion. The chemical compositions of the phases and the variation of elements between boundaries and the core were obtained by correlation of QXRD and X-ray fluorescence results and verified through EDX measurements. According to XRD polarisation microscopy studies, the research materials can be divided into two groups according to their matrix structure. The first group displays a calcareous matrix, which mainly consists of CaCO3 with a minor content of SiO2. The second group consists mainly of SiO2 and other silica compositions, such as alkali-feldspars, plagioclases and pyroxene. With respect to thermodynamic stability of pyroxene, the stability area of the solid solution in such systems varies between 750 and 870°C. Here, AFM in non-contact mode was carried out. The aim of this combined method was to confirm the damage process with regard to the structural conversion in the interface between selected minerals and the matrix (quartz, plagioclase, Kali-feldspar). Thus it was ultimately possible to obtain a quantitative characterisation of the micro- and nanostructure of these historical materials. As a result of this data, it is possible to define much more precise requirements for modern methods of restoration of materials, in order to gain higher durability and rentability cycles.It is possible to explain the techniques which have been used in ancient times in terms of material science methods, with the so called ‘ceramography’. In fact, the word ceramic is of Greek origin and means potter’s earth; however the tradition is much older. Traditional ceramics are those derived from naturally occurring raw materials and include clay based products. These were the most readily available raw materials for the ancient potters. It means that pottering might be actually the human development reference. Ceramics were the first products of people who sought materials which were required to demonstrate good plasticity behaviour in forming, high durability during firing, and an aesthetically pleasing end result.

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V. A. Drebushchak, Isobaric dehydration of zeolites, Geokhimiya, N1 (1990) 124–129 (in Russian) V. A. Drebushchak and A. I. Turkin, Relationship between heat capacity and thermal expansion derived from the Lennard-Jones potential, J. Therm. Anal. Cal., 65 (2001) 745. V. A. Drebushchak, Calibration coefficient of a heat-flow DSC. Part I. Relation to the sensitivity of a thermocouple, J. Therm. Anal. Cal., 76 (2004) 941. V. A. Drebushchak, Calibration coefficient of a heat-flow DSC. Part III. Electromotive force of a thermocouple as a function of temperature. J. Therm. Anal. Cal., 90 (2007) 289. V. A. Drebushchak, L. N. Mylnikova and V. I. Molodin, Thermogravimetric investigation of ancient ceramics: metrological analysis of sampling. J. Therm. Anal. Cal., 90 (2007) 73. Recognitions

Relevance of magnetic properties for the characterisation of burnt clays and archaeological tiles

The archaeomagnetism of pottery, bricks and tiles is typically employed for dating inferences, yet the magnetic properties of ancient ceramics can also be convenient for their characterisation, to evaluate the technological conditions applied for their production (temperature, atmosphere, and duration of firing), as well as to distinguish groups of sherds having different provenance. In this work, the measurement of hysteresis loops has been applied and combined with colour survey to characterise the magnetic properties of burnt clays and archaeological tiles. Four calcareous and non-calcareous clays, along with seventeen tile fragments excavated from the sites of the ancient Roman towns of Pompeii and Gravina di Puglia, in Southern Italy, are examined. The ferrimagnetic character of the clays, in general, enhances with increasing firing temperatures until vitrification processes occur (900–1000 °C) dissolving iron oxides and dispersing the colour and magnetic properties they provide. High values of saturation magnetization are observed in clays with relevant calcareous content after firing above 900 °C, which results in the formation of Ca-silicates able to delay the onset of the vitrification processes. Magnetic properties of the tiles have been evaluated in terms of the high coercivity (i.e. mainly ferrimagnetic) or low coercivity behaviour (i.e. including relevant paramagnetic and superparamagnetic contributions). Enhanced ferrimagnetic character, mostly depending on the growth in number and volume of iron oxide particles, is associated with the development of an intense reddish hue.

Application of chemical and chemometric analytical techniques to the study of ancient ceramics from Dougga (Tunisia)

In the present paper chemical characterization has been carried out on 67 shards of archaeological pottery from Dougga (North Tunisia). The analysed shards, dated to the Byzantine period (VI–VII century A.D.), belong to the three ceramic classes African Red Slip Ware, Dougga Ware and African cooking Ware. Fourteen elements have been determined by both atomic emission spectroscopy with flame as source (AES) and by using an inductively coupled plasma source (ICP-OES). The data acquired have been treated by statistical techniques in order to define grouping for the examined shards. Both unsupervised and supervised methods have been employed in order to define groups of different pottery shards. As a comparison, some samples (control group) coming from Southern Tunisia have been examined. All the statistical methods employed have evidenced how the control group, as concerns the chemical composition, is clearly distinguishable from Ain Wassel samples which are highly homogeneous. In fact because of the compositional homogeneity of the Northern Tunisia productions, it is quite difficult to establish a good classification and distribution of the samples in well defined cluster. Nevertheless supervised analysis has evidenced how, among the three classes, the African cooking Ware is the more distinguishable one confirming the archaeologists' hypothesis that Dougga Ware is an imitation of African Red Slip Ware.

Ceramic micropalaeontology: the analysis of microfossils in ancient ceramics

Abstract. Microfossils can be a common component of ancient ceramic artefacts. Their analysis in this unusual context is a little-known, yet promising, cross-disciplinary application of micropalaeontology. This article presents the first detailed assessment of the phenomenon of microfossils in ancient ceramics and demonstrates how micropalaeontology can contribute to a range of issues in archaeological ceramic analysis and the reconstruction of the human past. In describing a methodology by which micropalaeontologists and archaeologists can analyse microfossiliferous ceramics, this paper presents the foundations of an approach, which is here referred to as ‘ceramic micropalaeontology’.

Thermogravimetric investigation of ancient ceramics

Abstract Sherds from restored ancient pots taken from archaeological sites of Siberian region (Late Bronze and Early Iron Age, IX–VIII to VII–VI BC) were investigated by thermogravimetry in order to define the effects of sampling. Three types of the sampling were (1) scanning through the inner surface of a pot, (2) outer surface, core, and inner surface of thick-walled sherds, and (3) random fragments of a restored pot. The results of the measurements were shown to depend on two factors, clay paste composition and firing conditions. Redistribution between mass loss at dehydration and dehydroxylation was detected for the ancient ceramics after ‘mild’ firing. The results of the measurements are explained in terms of a temperature profile throughout the wall of a pot during the thermal treatment under firing and cooking meal. The main conclusion of the work is that the thermogravimetric measurements will be very useful for the solution of archaeological problems only if the sampling is correct.

Physico-chemical and mineralogical study of ceramic findings from Mary City – Turkmenistan

Abstract Eight findings of ancient ceramics (IX–X century) from Merv (currently Mary City – Turkmenistan) were sampled and studied from a scientific point of view, in order to classify them on the basis of their materic and technological content. They have been collected in a place 70 km far from the Iranian border, on the ancient Silk Route and hence, in connection with Turkey, Afghanistan and Indo Valley. Different physico-chemical and analytical methodologies have been used for a detailed study of the mineralogical composition and the texture of the ceramic body, the material employed for coatings (slips, glazes and enamels) and decorations (chromophores and pigments). Optical (OM) and Scanning Electron Microscopy (SEM–EDS or WDS) measurements, carried out on thin and cross-sections, allowed an evaluation of the state of conservation of the findings, together with the presence of neo-formation phases (i.e. phosphates). These ceramics were characterized on the basis of the employed raw materials and the production technology, verifying and ascertaining differences and analogies. Finally, we have evaluated whether an exhaustive scientific description and characterization of these findings can be useful for proposing a historical contextualization.

Preliminary dating results for ancient ceramics from Romania by means of thermoluminescence

The preliminary results from dating two types of ancient ceramic from Romania by means of thermoluminescence are presented. The measurements are the first TL dating in a Romanian laboratory. Pottery collected from two Eneolithical sites (Petresti culture) and two types of Roman ceramic were investigated using the quartz inclusion technique and an additive dose procedure. The annual dose was estimated using instrumental neutron activation and the calculated values ranged between 2.7 and 3.7 mGy per annum. The analysis yielded reproductible growth curves and the ages obtained range between 5321 ± 257 and 5850 ± 509 y in good agreement with the dates assigned by archaeologists (5000–6000 y) for the Neolithic samples. The ages for the Roman samples, 1790 ± 125 and 1850 ± 170 y were also consistent with their known ages.

Thermal and mineralogical contribution to the ancient ceramics and natural clays characterization

In the present work 39 ancient ceramic sherds from the archaeological excavation of Abdera, North-Eastern Greece, dating to 7th century B.C., and 11 local raw clay bricks, fired at temperatures ranging from 500 to 1000°C, were characterized by ICP-AES, powder X-ray diffraction (PXRD) and thermal analysis (TG-DTA) techniques. It has been found that the mineralogical composition of the most studied sherds is quartz, feldspars and micas, which is in agreement with the composition of the local bricks. Chlorite is also present in a few samples, while there is one completely different sherd, which belongs to the Ca-rich clays. From the simultaneous TG/DTG and DTA data, under nitrogen atmosphere in the temperature ranges ambient to 1000°C, we comment on the possible firing temperature and distinguish between samples of different origin. The existence of muscovite or illite in most of the samples denotes that the firing temperature was lower than 950°C, while the existence of chlorite means that the firing process in these samples stopped before 700°C. A very different thermogram gave the Ca-rich ceramic sherd, due to the existence of calcite, denoting that the firing temperature was about 700°C.

Development and optimisation of a portable micro-XRF method for in situ multi-element analysis of ancient ceramics

Non-destructive analysis of cultural objects by micro-XRF spectrometry is an advantageous multi-element technique that has rapidly developed during the past few years. Portable instruments contribute significantly to the in situ analysis of valuable cultural objects, which cannot be transported to the laboratory. Ancient ceramics are the most common archaeological findings and they carry a significant historical content. Their analysis often presents certain particularities due to surface irregularities and heterogeneity problems. In the present work, the analytical characteristics (beam spot size, geometry effect and detection limits) of a compact and portable micro-XRF instrument with a monocapillary lens are presented in details. The standard reference materials SARM 69, SRM 620, NCS DC 73332 and the reference materials AWI-1 and PRI-1 were analysed for the determination of the detection limits (DL's) and the evaluation of the accuracy of the micro-XRF. Emphasis is given on the critical parameters, which should be monitored during measurements and influence the final results in the analysis of ancient ceramics. A quantitative analysis of ancient ceramic samples from Abdera (North Greece) is also presented.

Compositional analysis of Hispanic Terra Sigillata by laser-induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) has been applied for the analysis of Roman pottery Hispanic Terra Sigillata dating back to the 1st–5th century A.C. from two important ceramic production centers in Spain. For each sample, several examinations were performed on slip and body providing data necessary to draw depth profiles of the contents of various elements. In all the cases investigated, the amount of some elements such as calcium and iron and the presence of other ones such as silicon and aluminum showed the differences existing between slip and body in these ancient ceramics in relation with their region and period of production. In addition, complementary analyses were carried out with scanning electron microscopy linked with energy dispersive X-ray microanalysis (SEM/EDX) to measure the thickness of slip and to obtain verification of chemical results.

Chemical Characterization and Comparison of Ceramic Samples from Ramnous and Laurion

Instrumental neutron activation analysis is, up to now, one of the most important analytical methods for the investigation of the chemical composition of ancient ceramics. At the reactor of the NCSR “Demokritos”, 21 ceramic fragments of the area of ancient Ramnous and 23 pieces from ancient Laurion were examined. The ceramic fragments were mainly from utilitarian vessels, which belonged to the fourth and third century BC. All pieces were without any decoration, aside from some black colours on one side. From all samples, data could be obtained for the elements As, Eu, La, Th, U, Sb, and Zn. The statistical evaluation of the mean values of these elements, as well as the correlation coefficients for the corresponding element combinations, showed that the fragments from ancient Ramnous were different from those of ancient Laurion. Cluster and factor analysis demonstrated that the samples from both places are separated into two independent groups. However, the separation is not very good, as the groups remain close together. The reason might be that the geological raw materials in such a closed area do not differ too much in its chemical composition profiles. Nevertheless, the results indicated that the utilitarian ceramics were obviously not objects for trade between these two regions, but remained items of local production.

Comparison of a portable micro-X-ray fluorescence spectrometry with inductively coupled plasma atomic emission spectrometry for the ancient ceramics analysis

Two multielement instrumental methods of analysis, micro X-ray fluorescence spectrometry (micro-XRF) and inductively coupled plasma atomic emission spectrometry (ICP-AES) were applied for the analysis of 7th and 5th century B.C. ancient ceramic sherds in order to evaluate the above two methods and to assess the potential to use the current compact and portable micro-XRF instrument for the in situ analysis of ancient ceramics. The distinguishing factor of interest is that micro-XRF spectrometry offers the possibility of a nondestructive analysis, an aspect of primary importance in the compositional analysis of cultural objects. Micro-XRF measurements were performed firstly directly on the ceramic sherds with no special pretreatment apart from surface cleaning (micro-XRF on sherds) and secondly on pressed pellet disks which were prepared for each ceramic sherd (micro-XRF on pellet). For the ICP-AES determination of elements, test solutions were prepared by the application of a microwave-assisted decomposition procedure in closed high-pressure PFA vessels. Also, the standard reference material SARM 69 was used for the efficiency calibration of the micro-XRF instrument and was analysed by both methods. In order to verify the calibration, the standard reference materials NCS DC 73332 and SRM620 as well as the reference materials AWI-1 and PRI-1 were analysed by micro-XRF. Elemental concentrations determined by the three analytical procedures (ICP-AES, micro-XRF on sherds and micro-XRF on pellets) were statistically treated by correlation analysis and Student's t-test (at the 95% confidence level).

Pliocene clays from Aegina (Greece): Reference material for chemical provenance studies on bronze age pottery from the Island

AbstractNormally, the use of clays as reference materials in chemical provenance studies of ancient ceramics is complicated due to the original clay paste processing. The primary mixing and/or refining of raw materials during pottery production makes a straightforward comparison of archaeological ceramics with extant geological materials difficult if not impossible in many cases. However, in the case of Pliocene clays from Aegina (Greece), which were examined chemically and mineralogically and compared with Bronze Age pottery produced on the island, a successful exception can be presented. The chemical composition of a large group of Aeginetan pottery resembles the chemical composition of clays from a deposit in close vicinity to the main Bronze Age settlement of the island. Clays from specific outcrops exhibit considerable chemical and mineralogical homogeneity, and the suitability of those clays for pottery production apparently made substantial clay paste processing unnecessary. © 2004 Wiley Periodicals, Inc.

Micro‐Raman spectroscopy of ancient ceramics: a study of French sigillata wares

AbstractMicro‐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.

Raman spectrometry, a unique tool to analyze and classify ancient ceramics and glasses

Raman micro/macro spectroscopy allows a non-destructive remote analysis: body and glaze, crystalline and amorphous phases can be identified, including the nanosized pigments coloring the glaze. Last-generation instruments are portable, which allows examination in museums, on archaeological sites, etc. This paper gives an overview of the potential of the Raman-spectrometry technique to analyze ancient ceramics and glasses. Selected glasses as well as glazes of various porcelains, celadons, faiences and potteries, representative of the different production technologies used in the Ancient, European, Mediterranean, Islamic and Asian worlds, were studied. Their identification is based on the study of the Raman fingerprint of crystalline and glassy phases. Raman parameters allow for the classification as a function of composition and/or processing temperature. Special attention is given to the spectra of amorphous and coloring phases (pigments).

Technological study of ancient ceramics produced in Casteldurante (central Italy) during the Renaissance

In order to recover the ancient tradition concerning the materials used for the decoration, majolica shards produced during the Renaissance period in Casteldurante, a famous centre for ceramic production in Italy (Marche), have been examined. In the present study, pigments used for the decorations have been investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES), scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) and diffuse-reflectance UV-Vis spectroscopy. Ochre, lead antimonate yellow, copper-based pigment and smalt have been used as colourants to obtain respectively yellow-orange, yellow, green and blue decorations in accordance with what is reported by the ancient recipes.

The Characterization of Ancient Ceramics from Hasankeyf (Turkey )

The Characterization of Ancient Ceramics from Hasankeyf (Turkey )

Red clays from Central and Eastern Crete: geochemical and mineralogical properties in view of provenance studies on ancient ceramics

The existing geochemical diversity of clay deposits consists the underlying assumption for the determination of provenance of archaeological ceramics on the basis of their chemical composition. This assumption was tested on Quarternary red clayey alluviums from Central and Eastern Crete (Greece), an area rich in archaeological pottery and very popular for ceramics provenance studies. This type of clay has been used for pottery production on the island since the antiquity and it is still in use by traditional workshops. Altogether, 17 samples of clayey raw materials were collected from 7 different locations in Central and Eastern Crete, and characterised by chemistry, mineralogy and petrography. The study was focussed on the internal variability within deposits and the diversity among different deposits. It was possible to distinguish all seven deposits from each other on the basis of their chemical composition, taking into account the available mineralogical and petrographical information, although some deposits presented compositional relations. Compared to Neogene clay deposits in the same area, the variability among the examined red clayey deposits was clearly higher and exceeded by far the intra-deposit variability.

RAMAN μ-SPECTROMETRY, A UNIQUE TOOL FOR ON-SITE ANALYSIS AND IDENTIFICATION OF ANCIENT CERAMICS AND GLASSES

ABSTRACTRaman micro-spectroscopy allows remote, non-destructive analysis of materials. Our laboratory was among the first to apply this technique to frescoes, oil and parchment painting. For five years we have focused our efforts on horn, ivory, tortoise shell and ancient ceramics and glasses. Crystalline and amorphous phases can be identified in both body and surface layer, including the glaze/glass-coloring nanosized pigments (e.g. in lustre ware, the first nano-optic device). Recent generation instruments are portable, which allows for on-site examination, for example, in a museum. In nanostructured, nanocrystalline/amorphous silicate glasses, glazes and most of their pigments, Raman parameters and their multivariable analysis are used to recognize compositions as well as to classify them as a function of their processing. This overview addresses the procedure, choice of the exciting radiation, control of the Raman resonance, data processing and extraction of relevant parameters such as the index of polymerization and different signatures that may be characteristic of specific glazes and pigments. Didactic examples are chosen among pottery that representative of the different production technologies used in the Roman, European (Medici, Meissen, Chantilly, Mennecy, Saint-Cloud, Sèvres), Islamic (Iznik, Kütahya, Safavid) and Asian (Vietnam) worlds.