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Ceramic technology: how to characterise black Fe-based glass-ceramic coatings

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Abstract

The study of the ancient black ceramic coating that decorates the surface of Classical and Hellenistic pottery from Attica and other main production centres in the Mediterranean has been the subject of more than three centuries of research. The physicochemical characterisation and analysis of the black glaze/gloss (BG) with the use of a broad spectrum of analytical techniques has gradually revealed its nature as an iron-based glass-ceramic material. At its best, it is coloured by polycrystalline nanoparticles of magnetite or mixed magnetite/hercynite spinels, dispersed in the amorphous K-aluminosilicate phase doped by Fe2+/Fe3+. We discuss the technique to produce the BGc (black glass-ceramic, hereafter), known as the “iron reduction technique”, with emphasis on the 3-stage firing under oxidising-reducing-oxidising (ORO) conditions as well as the latest analytical results through XPS, high-resolution TEM, SR-micro XRD and XANES. The discussion is based on data and research experience accumulated over the years from the application of conventional techniques (such as SEM-EDS and hhXRF) on ancient samples, laboratory reproductions and contemporary full-scale reproduction of similar artefacts. We show that the parameters affecting the quality of the BGc (sheen, colour, micromorphology) depend on the nature of the clay-slip, the application process, the ORO firing scheme and weathering mechanisms due to burial in humid terrestrial or marine environment. The proposed analytical protocol for the routine characterisation of the micromorphology and the analysis of the BGc and the ceramic body involves the use of non-destructive or minutely destructive techniques with special emphasis on the pottery sample classification and documentation.

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Notes

  1. The stratigraphical data from the excavations for the Athens METRO have revealed a rich layer of soft clayey marl on weathered Athenian schist (Marinos et al. 1997) in the area of the marsh on the banks of the River Eridanos that crosses the site of Kerameikos, the potter’s district which takes its name from the potters (r. kerameis). Riverine clay, usually grey in colour due to its organic content, is fine-grained and suitable for pottery-making. The Classical Athenian cemetery is located also in the same archaeological site.

  2. For the red figure technique see: Penthesilea bowl. Greek vase painting in practice. ATTIC BLACK: ΘΕΤΙΣ AUTHENTICS LTD. Feb 2019. https://www.youtube.com/watch?v=Be2MQTdbLdA (video with English subtitles).

  3. See for example The Potter’s Studio Handbook: A start-to-finish guide to hand-built and wheel-thrown ceramics (Muller 2007, p. 111).

  4. Calgon is sodium hexametaphosphate [NaPO3]6. The original product consisted of amorphous sodium polyphosphate, which in water would complex with ambient calcium ion and other cations, preventing formation of unwanted salts and interference by those cations with the actions of soap or other detergents. Its name suggests “calcium gone”. In the case of clay suspensions, it complexes the calcium from fine calcite particles and probably interstitial Ca2+ from clay minerals of the smectite group, by forming calcium-polyphosphates that remain in the finest fraction.

  5. It is worth noting that M. Bimson (1956) made similar observations during her experiments, but her comments remained unnoticed.

  6. Spherical bubbles which are trapped within the glassy phase witnessing the production of gases, i.e. CO2, O2, SO3 during the firing at the maximum temperature. Extensive bloating, referred to as foaming in highly fired contemporary ceramic materials (Sasmal et al. 2015), lightens the black colour of the BG to grey.

  7. The research by Aloupi (1993) formed the basis of an Attic BG production unit, operating in Athens since 2000. THETIS AUTHENTICS LTD (ATTIC BLACK).

  8. Aloupi-Siotis (2008) has reported on the technical issues and understanding that emerge through the routine full-scale reproduction and the ensuing contributions to archaeological research. The number of ORO firings performed during this period (June 2000–Dec 2019) exceeds 800.

  9. In our view, the appearance (colour and opacity) of the BG results from a fine interplay between the concentration and particle size of the Fe3O4-FeAl2O4 spinel crystals and the coloration of the transparent K-alumino-silicate glass matrix. Introduction of first-series transition metals into a silicate glass causes colouration due to coordination of oxygen donor atoms to the metal ion. Fe3+produces a week yellow colour, which is shifted toward a more intense blue colour upon reduction to Fe2+. It is expected that the exact chemical composition and the resulting structure of the base glass influences the colour obtained.

  10. As stated by Naudé (1959) “Both the terms “glaze” and “varnish” are used to describe this surface decoration, neither of which is strictly correct. It cannot be varnish as it contains no oil, and it lacks the most striking feature of glaze, namely becoming liquid when heated. The term glansverf is used in Holland. In Germany, Glasur describes the decoration, and “Lasur” the preliminary wash with which vase surfaces were sometimes prepared.”

  11. For example, see Sandu et al. (2017)

  12. For example, see Lagaly (2006)

  13. More particularly the areas indicated were Laurion, Mount Hymettus, Mesogea and Mount Parnes as well as the Panakton plateau-Skourta plain mentioned above. The BGc pottery samples produced with these clays were compatible with the ancient samples (Chaviara and Aloupi-Siotis 2016).

  14. The particle size of the separated clay fractions is estimated as equivalent spherical diameter (ESD) according to the Stokes law

    and was later tested successfully with Dynamic Light Scattering (DLS) measurements.

  15. See Chaviara and Aloupi-Siotis (2016) as opposed to Walton et al. (2015)

  16. See for example Berthold et al. (2009)

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Acknowledgments

The new data presented here are mainly part of the THETIS’ archive (THETIS AUTHENTICS LTD) and were collected in the framework of externally funded research programs (CERAMED INCO III European Commission/Framework Program for Research 2003–2006, TESS European Regional Development Fund/ General Secretariat for Research and Technology, 2008–2010) and in-house research with a view to introducing quality control criteria, improving production and reducing costs.

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    Eleni Aloupi-Siotis

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Aloupi-Siotis, E. Ceramic technology: how to characterise black Fe-based glass-ceramic coatings. Archaeol Anthropol Sci 12, 191 (2020). https://doi.org/10.1007/s12520-020-01134-x

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