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Ceramic Technology How To Characterise Black Fe-Ba
Ceramic Technology How To Characterise Black Fe-Ba
https://doi.org/10.1007/s12520-020-01134-x
ORIGINAL PAPER
Received: 21 January 2020 / Accepted: 24 June 2020 / Published online: 28 July 2020
# Springer-Verlag GmbH Germany, part of Springer Nature 2020
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 repro-
ductions 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.
Keywords Magnetite and hercynite . Clay colloids . Aluminosilicate glass . Black glazed ware . Attic pottery
This article is a Topical Collection on Ceramics: Research questions and Black gloss pottery
answers
1
THETIS AUTHENTICS LTD, 4 Diagoras St., We cannot imagine anything more common and humble than
GR-11636 Athens, Greece earth. And yet, this modest material—“trivial and easy”, in
Plato’s words—was turned into veritable gold by the ancient Clay earth of strict specifications
potters of Attica, demonstrating that even the most inconse-
quential things can become precious if they are utilised to What was it that made the Attic vases so special and their
advantage. Attic vases monopolised the international markets imitation so difficult, not only by modern but also by ancient
of their time during the sixth to the fourth century BC and were would-be copiers (in mainland Greece, Asia Minor, Magna
a remarkably profitable export product. Athens steadily Graecia, Etruria and the colonies in the west), who were far
prevailed in this monopoly because, though many tried to more familiar with the ceramic art of that period than we are?
imitate the rare quality of its vases, none really succeeded We argue that the secret lies partly in the clay. The earth of
(Fig. 1). One of the great attractions of the vases was the Attica provided the potters with the appropriate raw materials
wonderful black glaze, which, as understood today, can be that enabled them to achieve not only a glaze unique in colour
classified as a ceramic—glass and a nanomaterial with un- and durability, but also a clay body of exceptional quality.1
common chemical and mechanical properties (Fig. 2a and b). However, the existence of appropriate clay deposits is not
Herodotus, the fifth century BC historian, narrates that at enough. Their optimal selective use requires a thorough un-
one time a ship loaded with merchandise set sail from derstanding of their properties acquired, in the case of Attica,
Greece and, after reaching Spain, returned home carrying through centuries of experimentation.
1000 times the value of its cargo. Even if this was an ancient The accumulated knowledge based on ethnographic and
urban myth and even though we do not know what the said archaeological data and the scientific studies referred to in
ship was carrying, we do know that Attic vases were a product the next paragraph allow us to outline the manufacturing pro-
that could command prices of that order in the markets of the cess of the decorated Athenian vases, with respect to the ma-
period. For 300 years and more, from the late sixth to the late terials used and the firing scheme.
fourth century BC, they were a par excellence luxury export
product of Athens to the then known world. The vases brought
large profits mainly to the merchants but also to their creators, Raw materials
who for the first time enjoyed a certain status and a better place
in society. Body After cleaning, mixing with water and kneading the clay,
Today, the value of high-quality vases, especially those the potters formed the vases on the wheel, which was rotated
bearing signatures or attributed to specific artists, is inestima- by foot or with the help of an assistant, a trainee or a slave.
ble not necessarily in monetary terms. They hold the same Next, the handles were affixed and then the vase was “shaved”
universal appeal for the visitors who admire them in museums on the wheel, in order to make its walls thinner (and therefore
in Greece and abroad. lighter), as well as to render the details of the shape on the rim
and the base. Following drying, the vases are decorated with
clay paint, in accordance with the style of the period (black
figure, red figure, entirely black).
Clay paint The paint for the vases was also prepared from clay.
However, for the clay paint to give the desired flawless black
glaze, the raw material had to be a soil rich in illite clay min-
erals, iron oxides and poor in calcium carbonate (Fig. 3a and
b). Concurrently, on mixing with water, it should form a col-
loidal suspension. When concentrated by evaporation of wa-
ter, this suspension gave an extremely fine “clay paint” with
which the wheel-made vases were decorated. The vases were
then fired by a very specific process and at very specific tem-
peratures in a single firing involving three-stages (iron reduc-
tion technique). The potters of ancient Athens paid great at-
tention to selecting their raw material, depending on the result
they wanted to achieve. This implies they were fully familiar
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
Fig. 1 Red-figure Attic vase with a BG coating. Eos pursues the reluctant Eridanos that crosses the site of Kerameikos, the potter’s district which takes
Tithonus, who holds a lyre, on an Attic oinochoe of the Achilles Painter, its name from the potters (r. kerameis). Riverine clay, usually grey in colour
circa 470–460 (Louvre). From Wikimedia Commons, the free media due to its organic content, is fine-grained and suitable for pottery-making. The
repository Classical Athenian cemetery is located also in the same archaeological site.
a b
Fig. 2 a The fine-grained slip used for the BG forms a dense uniform surface × 2000, BG Attic sherd, CL-35), b Clay nanoparticles in the
layer during the 3-stage ORO firing, due to the extremely low CaO con- BG layer during sintering (SEM-image SE mode, fracture surface, ×
tent; the brick-red body is porous presenting the characteristic cellular 120.000, BG sherd–modern reproduction)
micromorphology of calcareous clays (SEM-image SE mode, fracture
with the properties of ferruginous clays as demonstrated by was sealed, thus interrupting the oxygen supply and in this
the fact that the clay used for the body of the vases was dif- way decreasing the temperature. In this reducing stage,
ferent from that used for their paint (Table 1). nanocrystals of magnetite are formed in the paint layer and
the black colour emerges (body and decoration become black
The three-stage firing and dark grey at this point, Fig. 4c). In the final oxidizing
stage, the potters open the aperture in the kiln (so increasing
The firing process comprised three stages: oxidation, reduc- the temperature again), the painted and vitrified areas do not
tion and again oxidation. In the first oxidizing stage, the an- reoxidise, thus remaining black, whereas unpainted areas
cient craftsmen raised the temperature in the kiln while reoxidise and become red (Fig. 4d). This final stage of re-
allowing air to circulate in the kiln. When the desired temper- oxidation demands considerable attention to ensure that the
ature was reached and the clay paint began to sinter or vitrify temperature does not rise too much, in which case the glaze
(body and decoration are red at this point, Fig. 4a, b), the kiln may turn red again.
a
b
Fig. 3 a Natural (spontaneous) clay suspension in water in early spring- clay-water suspension and a thick clay-paint after evaporation of water c
time following rainfalls in the Panakton plateau–Skourta plain between vase decoration with the clay paint
Attica and Boeotia. b Clay suspension in the laboratory, ferruginous clay,
Black-figure (seventh–fifth century BC) and red-figure style wide audience. This is evidenced by the comprehensive article
(fifth-third century BC)2 by Naudé (1959) combining archaeological and physico-
chemical information, with references to ancient texts and
On black-figure vases, figures and decorative motifs are black colloidal chemistry. There is a vast list of articles on the char-
and the ground is the red terracotta colour of the body. The acterisation and analysis of the Attic BG spanning a period of
potters painted the figures (Figs. 4a and 5a), filling them with more than 270 years, starting with the essay by Comte de
clay paint, rendered the details by incision and added colours, Caylus in 1752 to the on-going work of the last decade in
white and purple. When fired, the areas that had been covered the framework of recent research programs (Walton et al.
with clay paint turned black, while the grey clay took on a 2015; Chaviara and Aloupi-Siotis 2016; Cianchetta et al.
warm brick-red colour. Purple (mauve) was produced from 2016; Chaviara 2018). Jones (1986) provides a detailed ac-
ochres (oxides and hydroxides of iron) mixed with clay paint, count of the studies of the Attic black gloss/glaze since the
which on firing acquired a mauvish sanguine hue. The style beginning of the twentieth century and the physicochemical
was developed originally in Corinth in the seventh century BC description of the ancient decoration technique, by then called
but it reached its apogee in Athens during the sixth century “iron reduction technique” (Noll et al. 1975).
and survived until the fifth century BC. Several chemists, archaeologists and ceramists engaged
On red-figure vases, which corresponded to a revolution in with the reproduction of the Attic BG have suggested the
the design of the period, the figures and the decorative motifs use of additives to the clay in order to produce a suspension
are reddish, reserved on the ground of black glaze that covers in water. A series of “exotic” materials such as urine, dregs of
the entire vase. Here, the outline and the details of the figures wine, blood, bone powder, wood or seaweed ashes and mod-
were painted first (Fig. 5b), and the remaining body of the ern chemicals like Calgon4 and pyrogallic acid were used
vases was painted all over so as to become black. (Schumann 1942; Winter 1959, 1978; Hofmann 1962;
Noble 1960, 1965). Most of these additives have a
An eye on the temperature deflocculating effect and enhance dispersion of the clay parti-
cles in water. Their use however influences the final chemical
The range of temperatures demanded in order to create the composition of the BG, and they are not compatible with the
black glaze is rather narrow, the best quality is achieved at consistency observed in the Attic BG (Aloupi-Siotis 2008).
890 to 950 °C. Traditional potters, who fire in a kiln fuelled by The advent of electron microscopy and microanalysis
wood, know very well how to distinguish the suitable temper- (electron probe microanalysis—EPMA, scanning electron mi-
atures from the radiation emitted by a black body when it is croscopy combined with energy or wave-length dispersive X-
being heated.3 At 720 to 730 °C due to thermal radiation, the ray spectroscopy—SEM-EDS/WDS) combined with petro-
kiln becomes orange; at 800 °C, it begins to turn bright orange graphic (X-ray diffraction—XRD) and magnetic studies
until at 950 °C it glows, while at 1000 °C it is bright yellow. ( M ö s s b a u er an d c o n v er s i o n e l e c t r o n M ö s s b au e r
spectroscopy—CEMS spectroscopy) led to characterization
History of the studies of the BG and the ceramic body materials and revealed sig-
nificant chemical differences between the two (Pavicevic
During the nineteenth and twentieth century, the exceptional 4
Calgon is sodium hexametaphosphate [NaPO3]6. The original product
properties and the technology of the BG had already reached a consisted of amorphous sodium polyphosphate, which in water would com-
plex with ambient calcium ion and other cations, preventing formation of
2
For the red figure technique see: Penthesilea bowl. Greek vase painting in unwanted salts and interference by those cations with the actions of soap or
practice. ATTIC BLACK: ΘΕΤΙΣ AUTHENTICS LTD. Feb 2019. https:// other detergents. Its name suggests “calcium gone”. In the case of clay sus-
www.youtube.com/watch?v=Be2MQTdbLdA (video with English subtitles). pensions, it complexes the calcium from fine calcite particles and probably
3
See for example The Potter’s Studio Handbook: A start-to-finish guide to interstitial Ca2+ from clay minerals of the smectite group, by forming calcium-
hand-built and wheel-thrown ceramics (Muller 2007, p. 111). polyphosphates that remain in the finest fraction.
a b c d
Fig. 4 The 3-stage firing through images: a before firing the slip is reduced iron phases; d at the final oxidising stage, the decoration layer
brownish red on a grey clay substrate; b during the first oxidising stage which is vitrified (see Fig. 2a above), remains black as it traps the iron
the slip and the clay body become coral red and reddish, respectively, due oxides in its reduced form (i.e. Fe3O4) and the porous body turns to red
to the formation of Fe2O3; c during the reducing stage they turn to black due to oxidation and the re-formation of Fe2O3
and dark grey, respectively, due to the formation of Fe3O4 and other
1974; Longworth and Warren 1975; Tite et al. 1982). As fourth century BC black and red gloss pottery from Iasos in
shown in Table 1, the BG layer has a lower CaO content, Asia Minor (Amicone 2015) and on the Late Republican black
higher K2O and iron (here expressed as FeO) and higher gloss pottery in north-eastern Hispania consumption centres
Al2O3/SiO2. These differences in chemistry are also reflected (Madrid i Fernández and Sinner 2019).
in the SEM micrographs shown in Fig. 2a.
Besides Attica, the conscious application of the “iron re-
duction technique” is also witnessed in other production cen- State of the art of the physicochemical analysis
tres in mainland Greece (Boeotia, Euboea, Laconia and
Thessaly) and during the Hellenistic times in the Greek colo- “Iron reduction technique” lies in a simple oxidation reduction
nies, especially in Asia Minor, in Magna Grecia (Maggetti reaction involving the formation of iron oxides with different
et al. 1981; Mirti et al. 1996; Mirti and Davit 2008) and in colouration due to the different oxidation state of iron, Fe (III)
Greco-Roman settlements in Spain (Vendrell-Saz et al. 1991). and Fe (II):
With a view to improve the archaeological classification, it is
also worth referring to recent technological studies on the
a b
Fig. 5 In the Athenian vase painting, the areas to become black are filled figures are unpainted. The details are rendered with incisions in the BF
with the red clay-paint. In the Black figure (BF) style, the figures are filled style and with fine relief lines in the RF style. Both terms are conventional
with the paint and the background remains unpainted (a), while in the since the colours emerge with firing
Red-figure (RF) style, the background is filled with the red paint and the
simultaneous decrease of temperature (Aloupi 1993; Aloupi- present. Furthermore, these authors state that the atmosphere
Siotis 2008). This decrease in temperature during reduction of the second firing stage is highly reducing, with the maxi-
was theoretically postulated as occurring spontaneously in mum CO2 content being ~ 10 vol.%, and that the temperature
traditional wood firings due to incomplete combustion of the (i.e. the maximum temperature of the firing) was ~ 950 °C for
organic fuel, thus leading to lower thermal energy in the kiln.5 a very short time. The results are compatible with the firing
This is also essential in order to avoid the formation of scheme presented above.
bloating pores within the BG layer that affect the colouration The development of synchrotron radiation spectroscopy
of the BG. In simpler terms, intense reduction with simulta- techniques led to more accurate characterisation of the miner-
neous temperature decrease to 800–830 °C is essential for the alogy of the Fe oxides. Following an exploratory work on the
partial reduction of Fe3+ to Fe2+ to take place through the applicability of the techniques (Tang et al. 2001), a series of
formation of magnetite crystals. The temperature decrease al- trial measurements by SR-micro XRD on ancient Attic and
so prevents further reduction to Fe2+ (FeO) which would lead South Italian BG samples (Fig. 6a) were compared with mod-
to vigorous O2 release, and thus to rapid melting of the BG ern reproductions by THETIS7 and verified the presence of
and to bloating.6 Giorgetti et al. (2004), by using high- hercynite-magnetite in the Athenian, ancient and contempo-
resolution electron microscopy on BG ceramics from rary specimens. The BG from Taranto also contains haematite,
Tuscany, provided very informative TEM images of most probably due to incomplete in-depth reduction. This also
nanocrystals of hercynite and zoned hercynite/magnetite accounts for the reddish colouration in the interior of many
which are expected to form during cooling under reducing BG samples as shown in Fig. 6b, c, and d (Chaviara and
conditions, practically verifying the spontaneous temperature Aloupi-Siotis 2016).
decrease, as stated above. Gliozzo et al. (2004) provided a correlation between the
Ingo et al. (2000) through the application of X-ray photo- colouration of Etruscan BG specimens, i.e. whether bluish,
electron spectroscopy (XPS) and X-ray–induced Auger matt or with a metallic sheen, with the presence of almost
Electron Spectroscopy (XAES) on the BG of Attic samples exclusively hercynite in the first case, and the elongated mag-
from western Sardinia (a) demonstrated that the presence of netite coexisting with haematite in the latter. As stated in the
gradients in elemental (C, O, Fe, Al) variation in the top parallel article by Giorgetti et al. (2004), on the same samples,
1000 nm of the BG and estimated that Fe2+ is more abundant the varying shape of the oxide crystals can be interpreted as
than Fe3+; (b) demonstrated that the presence of iron grains the evidence that the system is out of equilibrium. Also, and
with a complex structure, constituted by discrete areas of sin- more important was the fact that gloss mineralogy at a nano-
gle phases with Fe3+, Fe2+ and Fe0; and (c) showed that these scale level can give some hints on firing conditions (partial
particles are finely dispersed in a vitreous Al–K- and Fe- pressure of O2) or temperature variation. However, accurate
enriched silicate where also Fe–C and C–C carbon atoms are estimates of temperature or exact oxidising-reducing condi-
tions are difficult to obtain since this technological process is
5
It is worth noting that M. Bimson (1956) made similar observations during rapid.
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
7
temperature. Extensive bloating, referred to as foaming in highly fired con- The research by Aloupi (1993) formed the basis of an Attic BG production
temporary ceramic materials (Sasmal et al. 2015), lightens the black colour of unit, operating in Athens since 2000. THETIS AUTHENTICS LTD (ATTIC
the BG to grey. BLACK).
The experience from the contemporary full-scale reproduc- To quantify the redox of Fe in the BG, Lühl et al. (2014)
tion of BG ceramics over the past 20 years8 has shown that the developed a new methodology based on confocal X-ray
bluish colouration is produced during highly intense reducing Absorption Near Edge Structure (XANES) and applied it to
conditions starting from Tmax 900 °C (± 10), while a greenish ancient BG sherds, laboratory reproductions with glass and
tint appears occasionally when Tmax is 950 °C (± 20). As mineral standards. The best quality Attic BG with bluish tint
stated by Aloupi-Siotis (2008), the presence of Fe2+ ions in (mid fifth century BC sherd from Kerameikos) presented the
the amorphous phase may account for the bluish colouration lowest amount of Fe3+/Fetot ~ 20% (or the highest Fe2+/Fetot)
of the K-aluminosilicate glass.9 This so-called glass redox is and was correlated with contemporary BG reproductions
correlated with colour. Reduced glasses with only Fe2+ are resulting from colloidal clay suspensions in water (using spe-
blue while the oxidised ones with only Fe3+ are yellow cific ferruginous illitic clays with grain sizes < 0.8 μm) and
(Bamford 1977). Besides the inevitable unstable conditions annealing at Tmax 890–910 °C/ORO conditions.
in ancient kiln wood firings, the presence of zoned The very stringent criteria for the optimal maximum firing
hercynite-magnetite detected by Giorgetti et al. (2004) in the temperature (at the first oxidising stage) comply with the as-
bluish Etruscan BG sherds may signify intermediate stages of sumptions made by Giorgetti et al. (2004) above. From this
the Fe3+ to Fe2+ reduction process, with simultaneous intro- rather concise account of bibliography, we can deduce that the
duction of Fe2+ in the amorphous material. Considering the iron reduction technique and the nature of its best BG product,
complexity and the phase relationships of the Fe-Al oxides the Attic BG, have been thoroughly understood by now.
below 1000 °C (Turnock and Eugster 1962), and the inhomo-
geneity of BG material, we can understand the difficulty in
Updating terminology
obtaining decisive results on the technological process by re-
lying on the specialised microanalysis of a limited number of
At this stage, it is worth discussing the terms used to describe
samples.
the iron-based black ceramic coatings. Richter (1923) de-
scribed it as “rich black with satiny surface and of astonishing
durability”. Until the third quarter of twentieth century, when
8
Aloupi-Siotis (2008) has reported on the technical issues and understanding most of the studies were due to archaeologists, potters and
that emerge through the routine full-scale reproduction and the ensuing con-
tributions to archaeological research. The number of ORO firings performed
scholars with broader interests, the material was characterised
during this period (June 2000–Dec 2019) exceeds 800. as a black glaze.10 However, the gradually increasing involve-
9
In our view, the appearance (colour and opacity) of the BG results from a fine ment of material scientists in the field led to the need to
interplay between the concentration and particle size of the Fe3O4-FeAl2O4
spinel crystals and the coloration of the transparent K-alumino-silicate glass
10
matrix. Introduction of first-series transition metals into a silicate glass causes As stated by Naudé (1959) “Both the terms “glaze” and “varnish” are used
colouration due to coordination of oxygen donor atoms to the metal ion. to describe this surface decoration, neither of which is strictly correct. It cannot
Fe3+produces a week yellow colour, which is shifted toward a more intense be varnish as it contains no oil, and it lacks the most striking feature of glaze,
blue colour upon reduction to Fe2+. It is expected that the exact chemical namely becoming liquid when heated. The term glansverf is used in Holland.
composition and the resulting structure of the base glass influences the colour In Germany, Glasur describes the decoration, and “Lasur” the preliminary
obtained. wash with which vase surfaces were sometimes prepared.”
substitute the “glaze” with a new term, since the BG with its deposits13 with adequate ferruginous clays to produce the col-
high alumina content (~ 30%) was different from the typical loidal clay-paint and a high-quality BGc (Chaviara 2018).
alkali-silicate glasses. We note the use of Similar fine-grained red clays are abundant in the
“Oberflächenverzierung” (surface decoration) by Pavicevic Mediterranean and relatively recent geological data and aero-
(1974), “schwarzen Malschicht” (black paint layer), “black sol studies relate their origin with Saharan dust storms (Avila
coating” (Maggetti et al. 1981) and the “black high gloss sur- et al. 1997; Yaalon 1997; Muhs et al. 2010; Rodriguez-
face finish” by Tite et al. (1982). The latter established the Navarro et al. 2018). This in turn could practically explain
exclusive use of the term “gloss” which is still in use, the spread of the BGc pottery production originally in the
constraining the introduction of other more accurate terms. Greek colonies and Emporia and then in Roman settlements
As stated elsewhere (Aloupi-Siotis 2008; Lühl et al. 2014; as predecessors of the terra sigillata ware.
Chaviara and Aloupi-Siotis 2016), the term “gloss” is inade- Figure 7b depicts the radical changes in chemical com-
quate since it only refers to the macroscopic appearance of the position for different fractions in the clay-water suspen-
coating, i.e. its surface sheen, as in varnishes and other glossy sion for a ferruginous clay from Crete (Kalami) expressed
surface finishes of any material. The development of modern in ratios for Al2O3/SiO2, K2O/(Al2O3+SiO2) and Fe2O3/
glass-ceramic nanomaterials since the 1990s, combined with (Al2O3+SiO2). We note that the main changes take place
the on-going increasing interest on the magnetic properties of during the first stage of refinement, with the removal of
Fe-based glass-ceramics,11 require the adoption of a new term quartz and other non- plastic inclusions (at particle size
for which we suggest the term Black Glass-ceramic (BGc) or <3 μm, expressed as ESD14). The Al2O3/SiO2 ratio in-
Fe-BGc. creases continuously demonstrating enrichment of the col-
loidal suspensions in clay minerals and the same applies
to Fe2O3/(Al2O3+SiO2), due to the ultra-fine particle size
of the original Fe oxides/hydroxides contained in the clay
Replication of the BGc—materials deposit. We also note that the K2O/(Al2O3+SiO2) ratio
and treatment reaches a plateau at ESD < 3 μm as expressed by the
K2O content that is 4.8–5.1%. These results show that
Choice of adequate clay and refinement the K2O content of the Attic BGc, as shown in Table 1,
can be achieved through suspension in water without the
Considering the parameters that influence the colloidal clay need of potassium-containing additives. The K2O content
suspension in water12 starting with the pH, the ambient tem- measured through microanalysis is further discussed in
perature, the chemical and mineralogical composition of the the next paragraph.
clay, the density and viscosity of the clay-water system where
even the vessel-container itself plays a role, it is reasonable to
question how the ancients were able to cope with this task.
The easiest way for the ancient craftspeople to achieve the fine Examination protocol
clay-paint, which would transform to the high-quality BGc,
was to localise the adequate clay deposits by using simple The quest to reconstruct the ancient BGc process based on
selection criteria, such as focused observation of spontaneous a set of ancient artefacts (also referred to as “reverse en-
dispersion in natural water-pools, followed by gineering” in engineering science) is by now essentially
experimentation. complete. This allows us to develop a scheme addressing
The scatter diagram of Fig. 7a shows the Fe2O3 vs CaO finer details of the process involving local resources and
contents for two adjacent ferruginous clay deposits from the practices which might shed light on issues of archaeolog-
area of Panakton (Skourta) in Attica. The ochre-yellow clay ical interest. Such a scheme is given in Fig. 8 where the
presents very low chemical variation with respect to the CaO macroscopic characteristics of the BGc, sheen and colour
content as opposed to the second clay, coloured red, where the relate to three detectable features of the BGc, namely its
CaO varies from 1 to 11%. The ochre-yellow deposit, contrary micromorphology, chemistry and mineralogy. This physi-
to the red, presents spontaneous dispersion in rainwater in cochemical information is in turn related to intrinsic
spring months (Fig. 3b), and for this reason, it was natural to
13
be considered as a good candidate for the BG production More particularly the areas indicated were Laurion, Mount Hymettus,
Mesogea and Mount Parnes as well as the Panakton plateau-Skourta plain
(Aloupi-Siotis 2008). Recent analytical work on a significant mentioned above. The BGc pottery samples produced with these clays were
number of ferruginous clays in Attica brought to light new 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
11
For example, see Sandu et al. (2017) and was later tested successfully with Dynamic Light Scattering (DLS)
12
For example, see Lagaly (2006) measurements.
properties of the clay material used for the clay paint, its Note on post-production alterations
degree of refinement (i.e. the particle size of the clay
suspension), the possible use of additives to enhance clay In order to draw conclusions concerning intrinsic material
dispersion in water and the application process. In addi- properties and ancient practices, we must take into account
tion, all these features depend on details of the 3-stage plausible post-production alterations due to usage, burial,
ORO firing such as the maximum temperature and the cleaning and storage conditions following discovery of the
duration and intensity of each stage. artefacts. We have already referred to the durability of the
Attic BGc layer as demonstrated by its resistance to most the BGc characteristics, concerning (a) the colour, which
chemicals. Nevertheless, alterations may be caused by long can be mixed red-black/misfired, black, bluish black, grey
exposure to weak acids, for example contact with vinegar for metallic, greenish, brown etc., (b) the sheen of the surface
years may lead to surface iridescence. Though BGc is not either glossy or matt, and (c) signs of weathering, i.e.
usually affected by a dry environment retaining the original cracks, pits, layering, iridescence. Colour Measurements
surface sheen, mild corrosion has been observed in BGc (see Mirti et al. 2006) can be particularly useful as they
sherds form an inland soil causing depletion of Si and K and provide an objective representation and classification of
thin layering phenomena on the external surface of the BGc the sample. The same might apply to light reflectance
(Maniatis et al. 1993; Mirti et al. 2006). In humid conditions measurements to evaluate the surface evenness and sheen
and more importantly in wet seawater exposure, these alter- (diffuse and specular reflection).
ations are more pronounced. In Fig. 9, we can see the effect of Digital photography using direct natural light or artificial
seawater and of humid terrestrial environment (island soil) in side lighting may also reveal some technical information on
the BGc chemistry and micromorphology on Attic sherds. The the BGc. Chaviara and Aloupi-Siotis (2016) have reported on
chart of Fig. 9a presents the changes in % for Si, K, Mg and Fe the presence of star-like microcracks on the surface of some
which are compatible with the chemical alteration observed in ancient BGc which were correlated with the use of clays from
ceramic fabrics from marine and terrestrial environment the Panakton plateau clay deposits.
(Pradell et al. 1996; Picon 1991). In the OM images of
Fig. 9b–d, we can observe the formation of pits and cracks
on the BGc sherd coming from the sea and the change in Non-destructive analysis of a large number of sherds
colour due to the partial dissolution of the top black layer and whole artefacts
when it presents an in-depth discolouration. A well-vitrified
BGc ancient sample from a humid environment will present With the use of hand-held X-ray Fluorescence (hhXRF)
severe cracking on the surface and in depth. These alterations and other portable XRF (p-XRF) instruments either in-situ
are visible macroscopically or under the stereoscope and con- or in the laboratory and of benchtop milli-XRF systems,
stitute an indication that the detected Si and K might be lower we can analyse quickly a significant number of BGc sam-
than the original and the Mg and Fe higher. ples non-destructively. BGc pottery is particularly suitable
for surface analysis due to the generally dense, even and
measurable thickness of the BGc layer (usually 20–
Macroscopic examination, documentation 35 μm), and after proper selection of suitable sherds, we
can obtain reliable quantitative results for the major and
It is suggested that the first stage of the research work minor elements from Al to Fe. Semi-quantitative results
should consist of the in-situ examination of a large num- can provide information on the raw materials used, espe-
ber of sherds, if possible with the use of a stereomicro- cially with respect to trace elements composition of the
scope, in order to have a first classification according to BGc (Mn, Co, Cu, Zn, Ga, Pb, As). An example of a
g
d
successful hhXRF application was provided through the In the scatter diagram of Fig. 10, non-destructive XRF
detection of increased Zn in the BG layer of certain Attic measurements on the BGc layer of ancient and modern
BG pottery sherds from the sixth to the fifth century BC. reproductions are compared with SED-EDS data from
The comparative analysis of ancient and modern BG re- the analysis of Attic BG sherds with a view to establish
productions from Attica clay deposits has correlated the a calibrated methodology. The BGc reproductions pre-
presence of Zn with the use of clay deposits from the area senting a correlation in K/Si to Fe/Si ratio (ellipse in
of Laurion in SE Attica.15 We must note, however, that Fig. 10), in other words a proportional increase in the
contribution from the ceramic body is unavoidable even two ratios, have been produced with clay dispersion in
with specially designed analytical set-ups, and for this water without additives, and they are compatible with
reason, the analysis of the BGc layer must be combined most ancient BG samples. The rest of the contemporary
with differential measurements of the clay body. samples (red dots in Fig. 10) have been produced with
gradually increasing addition of potash, and this is also
plausible for the geometric sherd (PrG-Att) that contains
9.3% of K2O. Two ancient sherds with higher Fe/Si (CL-
15
See Chaviara and Aloupi-Siotis (2016) as opposed to Walton et al. (2015)
Fig. 10 Scatter diagram of K/Si vs Fe/Si based on quantitative nd-XRF increased K/Si relates to potash addition. The proto Geometric sherd
analysis of the BGc layer on 25 Attic sherds (blue dots) and 22 contem- (PrG-Att) has a high K2O content (~ 9%) and has been undoubtedly
porary reproductions produced from clay-water suspensions (red and produced with addition of potash. The two ancient sherds on the right
grey dots); SEM-EDS results of the BGc from other ancient sherds (yel- (CL-11, CL-24a) present signs of weathering, and thus, the increased Fe/
low dots) are included for comparison. The products of natural suspen- Si is rather phenomenal attributed to depletion of Si
sions in water present a proportional increase of K to Fe (ellipse), while
11, CL-24a) present signs of weathering, and thus, the micromorphology (Maniatis and Tite 1981; Maniatis et al.
increased Fe/Si can be attributed to depletion of Si. 1981; Maniatis et al. 1983; Aloupi 1993). In addition, labora-
Similarly, it is expected that the application of newly de- tory ORO refirings of specimens from the lowest fired sherds
veloped non-destructive micro XRD set-ups16 on BGc sam- can establish a reference sequence. The BGc micromorphology
ples for the identification of hercynite/magnetite ratios, the can be characterised as:
possible presence of haematite and other characteristic phases,
as well as the quantity of the amorphous phase, will provide & Broken or dense, according to the particle size of the clay
information on the firing and allow the classification of the paint used, the finer the particle size, the denser the coating
BGc material with mineralogical criteria. layer
& Grainy, flaky, particles, smooth glass corresponding to a
Sampling and “destructive” analysis non-vitrified, sintered, glassy/vitrified state, respectively,
and this in turn to T < 850 °C and mostly oxidising condi-
Sampling involves a selection of sherds that are representative tions, 860–870 °C, 890–910 °C, 930–950 °C, respectively
of the assemblage with dimensions at least 4 × 5 cm, so as to & Molten (980–1000 °C), diffuse (1000–1050 °C)
proceed with the preparation of small freshly fractured speci- & The presence of bloating pores, always in vitrified paint layers
mens (0.3–1 cm) and of polished sections. Two or three larger (900–950 °C) signifies a short first oxidising stage and intense
sherds might be selected for laboratory refirings and the re- reducing conditions in the second stage of the ORO firing
maining from each sherd kept as reference material for future & Uniform (U) corresponding to even BGc thickness; the
analysis. The analysis involves: layer tending to separate from the body, signifies a long
duration of the first oxidizing stage
1. Examination of the freshly fractured specimens in the
SEM-EDS at the Secondary Electron (SE) mode. Examples on the above empirical characterisation of the
Fe-based BGcs on prehistoric and geometric pottery from
It allows the characterisation of the BGc and body micro- the Aegean are provided by Aloupi and Maniatis (1990) and
morphology at × 2000 and higher magnification and, this in Aloupi and Kourou (2006) and additional data are given in
turn, the empirical estimation of the Firing Temperature Online Resource 1.
Range (eFTR) based on the body and the BGc
2. Examination of polished sections in the Optical
16
See for example Berthold et al. (2009) Microscope (OM)
The in-depth colouration of the BGc provides information As shown in this, paper the presence of a black Fe-based
on the ORO firing scheme: glass-ceramic coating involves the combination of two differ-
ent clay materials, one “calcareous” (body) and one “non cal-
& Uniform black colouration throughout the BGc layer rep- careous” (surface coating). It also bears a wealth of technical
resents slow and controlled firing conditions and technological information, on the raw materials used and
& Red zoning in the interior witnesses a prolonged first their treatment, and allows a more accurate description of the
oxidising stage and short reduction firing scheme.
Considering the usual sampling constraints when dealing
3. Examination of polished sections in the SEM-EDS/WDS with decorated pottery, the suggested examination protocol
at the Back Scattered Electron mode (BSE). It involves: combines non-invasive analytical techniques such as Optical
Microscopy, nd-XRF and nd-XRD, with minutely destructive
& Characterisation of the particle size and occasional scanning electron microscopy (SEM-EDS). TEM and more
detection of characteristic minerals from the parent specialised synchrotron radiation techniques can resolve fo-
clay, such as fine mica platelets, fine iron oxides and cused or dichotomic questions. Such analytical protocols fo-
Fe-Ti ilmenite inclusions cusing on the surface coating(s) should complement the usual
& Quantification of the bloating pores contained in the analytical approach for the clay body involving bulk tech-
BGc layer, frequency and size distribution niques such as X-ray fluorescence (XRF) or inductively
& Chemical analysis of the BGc layer and the ceramic coupled plasma mass spectrometry (ICP) or neutron activation
body. The major and minor elements expressed as (NA), for the determination of its chemical composition.
oxides provide information on the raw clay used, the
degree of treatment, and the possible use of dispersing Acknowledgments The new data presented here are mainly part of the
THETIS’ archive (THETIS AUTHENTICS LTD) and were collected in
agents; soda, potash, natron and phosphates might be
the framework of externally funded research programs (CERAMED
detected through increased Na2O, K2O and P2O5. The INCO III European Commission/Framework Program for Research
ratios Al2O3/SiO2 and the Fe2O3/(Al2O3+SiO2) can 2003–2006, TESS European Regional Development Fund/ General
be used as discriminating parameters in handling Secretariat for Research and Technology, 2008–2010) and in-house re-
search with a view to introducing quality control criteria, improving pro-
large data sets (data in Online Resource 2).
duction and reducing costs.
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