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Egyptian faience glazing by the cementation

method part 1: an investigation of the glazing
powder composition and glazing ....

Article in Journal of Archaeological Science · March 2012

DOI: 10.1016/j.jas.2011.11.013

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 Journal of Archaeological Science 39 (2012) 763e776

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Journal of Archaeological Science

journal homepage: http://www.elsevier.com/locate/jas

Egyptian faience glazing by the cementation method part 1: an investigation of

the glazing powder composition and glazing mechanism
Mehran Matin, Moujan Matin*
Research Laboratory of Shex Porcelain Co., 19th St., Kaveh Ind. Township, Saveh 39141-76314, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In cementation glazing, for various reasons, there are significant differences between the composition of
Received 10 May 2011 the glass phases present in the faience microstructure and the glazing powder composition. Further-
Received in revised form more, in this glazing method, the glazing powder should perform more functions, which are: producing
19 November 2011
a shiny and smooth glaze coating, producing a firm capsule surrounding objects entirely (to prevent
Accepted 19 November 2011
adhesion between sintered glazing mixture and the melting glaze coating), and, finally, producing
a porous and friable sintered glazing mixture for safe and easy removal of buried objects. It is obvious
Keywords:
that these functions also have significant effects on the glazing powder composition and constitution.
Egyptian faience
Cementation
Therefore, analytical data on faience glass phases are very unlikely to reflect the strict composition and
Qom technique constitution of the original glazing powder properly. Accordingly, the composition and constitution of
Glazing mechanism cementation glazing powder have remained obscure for a long time. These data are particularly crucial
Glazing powder factors for cementation replication experiments and, consequently, for our awareness of the ancient
Glazing mixture faience production. In this paper, a series of cementation replication experiments have been conducted in
Capsule an attempt to provide further clarification of these issues. In addition, as a comparative indicator for
alkali and copper vaporisation, a small piece of rock quartz was placed separately above the glazing
powder. After firing, the appearance of the faience objects and quartz pieces and the microstructures and
chemical compositions of a select group of samples, obtained using Scanning Electron Microscopy e
Energy Dispersive Spectroscopy (SEM-EDS), were investigated. The discussion has focused mainly on
issues such as the raw materials and their contribution in the glazing process, the criteria for determining
the faience glazing methods, the necessary quantity of alkalis for a successful cementation glazing, and,
particularly, the glazing mechanism.
! 2011 Elsevier Ltd. All rights reserved.

1. Introduction alkaline-lime-silica glaze, often coloured by copper, that provides it

‘Faience’ was the French term originally given to tin-glazed
majolica type earthenwares made at Faenza, in northern Italy,
during the 16th and 17th centuries. Subsequently, the meaning has
changed both in the French and English languages. In the 19th
century, European archaeologists used the misleading name of
‘Egyptian faience’ to designate ancient siliceous ceramics discov-
ered in Egypt.
Egyptian faience, described as “the first high-tech ceramic”
(Vandiver and Kingery, 1987), is basically a siliceous vitrified and
glost ceramic. Its non-clay body is composed mainly of finely
ground quartz (rock or pebble) or sand, which is coated with an
* Corresponding author. Tel.: þ98 21 88284861; fax: þ98 21 88288361.
E-mail address: moujan.matin@gmail.com (M. Matin).
with its characteristic bright blue-green hue.
Faience was first produced in the late fifth millennium BC in the
Near East and then in Egypt. Subsequently, its production spread to
Rhodes, Crete, Cyprus, Russia, Italy and central Europe, France and
Britain. In the Indus Valley, faience was only produced during
a short period, from the third millennium to the early second
millennium BC. Its production in Egypt continued until the Roman
period. Regarding the Near East, it is generally accepted that faience
was being produced there until the end of the Sassanian period
(637 AD) (Tite and Shortland, 2008: 17, 93). However, it seems that
faience production has never ceased in Iran (Persia). There are
plenty of literature documents in Persian mentioning the produc-
tion of faience (Dehkhoda, 1956e1978), for instance, in the poems
of Nassir Khusrau, Sanai, and Mowlana (Rumi) (11th, 12th and 13th
centuries AD, respectively). In the early decades of the last century,
faience was made at least in two sites located at Qom and Shushtar,
cities in the centre and southwest of Iran (Wulff, 1966). Presently

0305-4403/$ e see front matter ! 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jas.2011.11.013
764 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776
the ancient production process is still employed at Qom to some
extent.
It is now generally accepted that faience can be glazed using
three different techniques, namely application, efflorescence, and
cementation (Vandiver, 1983). It should be noted that a combina-
tion of these methods might have been used for one object.
Application glazing has been the most common glazing method in
ceramic technology. In summary, it involves the application of
a glazing suspension consisting of water and ground glazing
ingredients, such as pre-fired glass and/or quartz, colorant
(frequently copper), alkali flux, and lime. The glaze slurry can be
applied to the faience body by painting, pouring, or dipping.
Application glazing was common for producing large objects such
as tiles, and it is accepted that it may be recognised by the probable
presence of brush marks, drips, and glaze running lines, as well as
by considerable variations in the glaze thickness (Tite and
Shortland, 2008: 48e49, 208). The efflorescence method is a self-
glazing technique in which soluble alkali salts (carbonates, chlo-
rides, sulphates, etc.), copper compounds, ground quartz and water
are mixed to form a paste that is often shaped by moulding. During
the drying process, as the water evaporates, the soluble salts
migrate to the surface of the object, and an efflorescence layer
(scum) develops. In the course of firing, this layer reacts with
quartz, lime, and copper to form the glaze on the surface of the
object. This method was used for the production of both small and
large artefacts. Objects made by this technique may show stand
marks on parts which were set down during the drying process.
Once again, variations in the glaze thickness are visible; the glaze is
thickest at the rims and on the outer surface, where the air flow and
drying were the most significant. The cementation method is also
a self-glazing technique. This method has been known to archae-
ologists since the 1960s, when its use was first recorded at Qom, an
old town in Iran (Wulff et al., 1968); as such, it is sometimes
referred to as the ‘Qom technique’. In this method, after the object
has been formed and dried, it is buried in a glazing mixture (the
cement) consisting of alkalis, copper compounds, calcium oxide or
hydroxide, and/or quartz. Moreover, it is generally accepted that
charcoal is one of the ingredients of the glazing mixture. During the
firing process (at about 1000 " C), a glaze layer is formed on the
faience surface as a result of different reactions between the glazing
mixture and the siliceous surface of the object. In this method, the
alkalis and copper vaporisation are crucial to the glaze formation.
After firing, the partially sintered cementation mixture can be
crumbled away from the object, which is now coated with glaze
(Figs. 1 and 2). Cementation glazing was appropriate for small
objects such as beads. It is generally accepted that this method can
be recognised by uniform glass thickness (Nicholson, 1993: 13; Tite
and Shortland, 2008: 48e49) and the absence of drying and firing
marks for small objects. However, on larger pieces a rough glaze
coating may be visible in the parts where they rested during firing.
Fig. 1. Schematic diagram illustrating cementation glazing (after firing).
Fig. 2. Faience object glazed by the cementation method.
As pointed out above, visual examinations and related macro-
scopic evidence are the first approach employed for recognising the
different glazing methods. However, these criteria may not be used
in many cases, for example when the object is a small fragment or
the glaze is weathered. In order to provide more clarity in dis-
tinguishing between different glazing methods, Tite et al. (1983)
and Tite and Bimson (1986) have argued that there are character-
istic relations between the glazing method used and the micro-
structure and composition of the fired object. Consequently, they
proposed microstructural and analytical criteria for determining
which of the glazing techniques were used for the production of
a specific artefact. On the basis of these results, it was suggested
that the macroscopic evidence should be supplemented by
microstructural and analytical evidence obtained from analytical
scanning electron microscopy (SEM). The faience microstructure
consists of three different layers, which should be distinguished in
the object. The first, external layer is the quartz-free glaze layer. The
second one is the interaction layer or ‘buffer layer’, as it is called in
ceramic technology (see e.g., Hamer and Hamer, 2004). This is the
glazeebody interface, consisting of quartz grains surrounded by
glass matrix. The third layer is the body itself, containing varying
amounts of glass phase holding together the quartz grains of the
body. On the basis of laboratory replication (Tite et al., 1983; Tite
and Bimson, 1986), it is now widely accepted that objects made
by cementation glazing tend to have thinner glaze and buffer layers
and less interparticle glass. In contrast, efflorescence glazing has
a thicker glaze and buffer layers, and the greatest amount of
interparticle glass. In the case of the application method, there is
again less interparticle glass and a thin buffer layer, but the glaze
layer tends to be much thicker. Furthermore, in recent laboratory
replications, Tite et al. (2007) have investigated the composition
profiles of glass phases, from the glaze layer through the buffer
layer to the interparticle glass in the body, for objects produced by
the efflorescence and cementation glazing methods. The investi-
gated composition profiles for glazes formed by the efflorescence
technique mostly indicated an increase in the soda content and
corresponding decrease in the potash, calcium, magnesia and
copper oxide contents from the interparticle glass (in the body)
through to the glaze layer, which reflects the preferential efflores-
cence of sodium carbonate in comparison with potassium, calcium
and magnesium carbonates, and copper oxide. In the case of
cementation glazing, a decrease in soda and copper content from
the glaze layer through the buffer layer has been observed. In
addition, the absolute percentage of potash was significantly higher
in both layers than in the original glazing powder (Tite et al., 2007;
 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776
Tite and Shortland, 2008: 51e54). The significant difference
observed in the composition profiles for copper oxide makes it
a useful criterion for distinguishing between the efflorescence and
cementation glazing methods. In this context, preferential vapor-
isation of potash during the firing of wood ashes has been reported
(Misra et al., 1993), which may be expected in cementation glazing.
Furthermore, Paynter (2001) has suggested that potash in contact
with silica is a more effective flux than soda. Therefore, in
cementation glazing, it will be preferentially taken up into the
melting glass.
In cementation glazing, the increased absorption of potash and
the reduced intake of calcium and magnesia (in comparison with
soda) reflect the fact that the composition of glass phases in faience
differs significantly from the glazing powder composition from
which they were produced. In addition, there are further known
factors at work; plant ashes as a source of alkali contain not only
alkali carbonates, lime, and magnesia, but also considerable
amounts of chlorides and sulphates. In the context of ancient glass
compositions, Rehren (2008) has argued that during the melting
process, the majority of chlorides and sulphates (present in plant
ash) form a separate salt melt, and it is only carbonates, bicar-
bonates, hydroxides, sulphites, and sulphates that are readily
incorporated into the glass melt. He states that “soda-lime-silica
glass and common chloride or sulphate-base salts form at melting
temperature a system of two immiscible melts, like oil and water”
(Rehren, 2001: 484). Furthermore, laboratory replication experi-
ments have proved that in comparison with soda, potash is
enriched in the salt melt and depleted in the glass melt, irrespective
of whether the chlorides were originally present as sodium or
potassium chloride (Rehren, 2008; Tanimoto and Rehren, 2008;
Tite and Shortland, 2008).
As pointed out by Tite et al. (2007), cementation glazing pres-
ents the advantage that a large number of small objects can be
glazed and produced economically, and is thus appropriate for the
mass production of small objects. It should be considered that in
the mass production of faience objects by the cementation method,
in actual practice, three significant features should be maintained
by the glazing powder: first, the object should be covered by a shiny
smooth glaze. Second, no adhesion should occur between the
faience glaze coating and the glazing powder. Finally, the sintering
of the glazing powder should be optimum in order to provide safe
and easy removal of the objects. Obviously, the mentioned features
are affected by different factors in the production process, such as
the ingredients’ particle size, the firing schedule, and, particularly,
the glazing powder composition. All these factors should be care-
fully considered in the laboratory replication experiments; other-
wise, any results based on replication experiments may lead to
misinterpretations. Therefore the attainment of these three
features should be regarded as a criterion for a successful cemen-
tation glazing replication.
In summary, the composition and constitution of glazing
powder in cementation method have remained obscure for a long
time. Because of the reasons mentioned above, the analytical data
on faience glass phases are very unlikely to reflect the exact
composition and constitution of the original glazing powder. About
half a century ago, in their seminal study, Wulff et al. (1968: 107)
stated that “systematic composition of the glaze powder from
these materials [pure materials] may eventually show which of the
components of the glazing powder are essential and which are only
incidental”. Therefore, this paper aims to improve present aware-
ness about the cementation glazing process, its technology, and
other relevant issues. To this purpose, hundreds of cementation
glazing replication experiments (not published) have been con-
ducted by the authors, of which a select group is discussed in
this paper.
765
In part 1 of our study (the present paper), the replication
experiments have been conducted mainly by using synthetic
chemicals in order to provide the background information and
a basis for the second paper (part 2). The replication experiments
will again be conducted in part 2, but using predominantly natural
raw materials in order to obtain a more realistic view of ancient
faience production. In this respect, part 2 will mainly focus on
a probable alkaline flux source that had been widely available to
ancient faience makers.
2. Experimental procedure
Replication experiments by the cementation method were
undertaken with nine glazing powder recipes. After firing, the
resulting objects and partially sintered glazing powders were
observed by the naked eye and/or with a low power binocular
microscope, and macroscopic evidence were reported. Further-
more, investigations on some selected objects were carried out
using SEM images (BSE mode) and SEM-EDS analyses.
2.1. Raw materials
Sand was used as a silica source for both faience bodies and
glazing powders. The particle size distribution and chemical
compositions of the raw materials are provided in Tables 1 and 2,
respectively.
2.2. Faience bodies
Recipes of faience bodies and their calculated chemical
compositions are provided in Tables 3 and 4. Fine silica was used in
all samples except B2, in which coarse silica was used. As a binder
and plasticiser, 5% Serish was used in all the recipes. Serish is the
Persian name for the powdered root tuber of Asphodelus sphaer-
ocarpus, whose aqueous solution was commonly used as an adhe-
sive in many traditional crafts in Persia, such as bookbinding and
textile crafts (Wulff, 1966). In addition, its usage in the faience body
mixtures of the last century has been pointed out by Yaghobi
(2002). The ash content of Serish is only about 5% at 900 " C. For
better homogenisation, the resulting powder mixtures, which
consisted of sand, Serish, etc., were sieved twice (30 mesh, 590
microns). By adding about 30 wt% water to each mixture, a paste
was created, which was wedged and kneaded for a few minutes
without any further ‘aging’ of the body paste. The pastes were then
formed in two plastic (epoxy resin) moulds. The consequent shapes
were tabular discs of 40 mm in diameter that were made in two
thicknesses, 7.5 mm and 12 mm, for each body sample. The disc-
shaped faience bodies were then left to dry at room temperature
for 48 h. The analytical data on the composition of the quartz
pebbles and sands that had been used in ancient faience production
describes an alumina content of up to about 3.5 wt% (e.g., Tite and
Shortland, 2008: 38). Wulff et al. (1968: 100) have reported 5 wt%
Al2O3 and 1% Na2O in the faience body (before firing). Hence, to
replicate the aforementioned contaminant, 10 wt% feldspar and
5 wt% kaolin were added to the BR and B3 recipes, respectively.
Table 1
Particle size distribution of raw materials (microns, wt%).
Raw materials Less than 44 44e88 88e149 149e250
Silica sand (fine) 40 60 e e
Silica sand (coarse) 10 20 25 45
Feldspar 40 60 e e
Calcium carbonate 100 e e e
766 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776

Table 2 Table 4
Chemical composition of raw materials (wt%). Calculated chemical composition of faience bodies (wt%).

Raw materials SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O L.O.I Code SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O
Silica sand 95.66 1.68 0.17 0.05 0.7 0.01 0.03 0.45 0.73 BR 94.5 3.06 0.17 0.07 0.78 0.01 0.45 0.96
Feldspar 71.69 15.1 0.25 0.34 1.4 0.01 4.1 5.01 1.9 B1 & B2 96.87 1.7 0.17 0.05 0.71 0.01 0.03 0.46
Calcium 1.54 0.11 0.11 0.01 54.3 0.75 0.2 0.03 42.8 B3 95 3.49 0.2 0.06 0.71 0.02 0.49 0.03
carbonate
Kaolin 47.1 36.7 0.85 0.17 0.36 0.25 0.03 1.02 12.9

glazed faiences when crumbled (Fig. 6). No adhesion of the glazing

2.3. Glazing and firing
The raw materials used in the glazing powders were silica sand
(fine and coarse), calcium carbonate and hydroxide, alkali carbon-
ates, potassium nitrate, common salt, copper oxide, and charcoal.
The particle size of sand and calcium carbonate and their compo-
sition are provided in Tables 1 and 2, respectively. The grain size of
charcoal was less than 0.25 mm. The calcium hydroxide was
produced by calcination of calcium carbonate at 980 " C. The
calcined lime was then moistened and left to dry for 15 days at
room temperature.
The compositions of glazing powders are summarised in Table 5.
The ingredients of glazing mixtures were weighed and mixed, and
the resulting powders were sieved twice (30 mesh) and placed into
unglazed porcelain containers with a stood prop in their centre
(Fig. 3). Then the faience bodies were buried alongside each other
in the middle height of the glazing powder and around the prop. A
piece of rock quartz was placed on top of the prop as a relative
indicator for alkalis and copper vaporisation, and, finally, every-
thing was covered by a container lid. An orifice of 25 mm in
diameter had been made in the centre of the container lid, to model
the kiln chimney (similar to actual mass production firing). All
samples were fired in such lidded containers; however, the GP5
sample was fired in containers both with and without a lid (to
ensure oxidation firing in the latter case). Firing was carried out in
an electric kiln, according to the firing schedule shown in Fig. 4
(980 " C maximum temperature).
3. Results
3.1. GPR
Based on the authors’ previous replication experiments (not
published), the GPR and BR samples have been our criterion and
reference for the glazing powder and faience body compositions,
respectively. As expected, the resulting faience was covered by
a rich shiny turquoise blue glaze (Fig. 5c). However, all disc-shaped
objects showed uneven and rough glaze coating on the central parts
of their underside, where they were rested during firing. The glaze
coating was smooth and perfect on bodies BR and B3, but wavy and
uneven on B1 and particularly B2. Furthermore, on the glaze coating
of some objects (different bodies), small crystals were observed in
the glaze matrix. Optimum sintering was exhibited by the glazing
powder; it crumbled easily when pressed by hand. A capsule or
cocoon was formed completely around the objects, which released
powder to the objects was observed. The faience body made with
the B2 composition, about 6.5 mm in thickness, was entirely
translucent (Fig. 7; relevant analytical data and SEM images are
shown in Table 8 and Fig. 9 and will be investigated later in Section
4); however, the thicker sample, about 11 mm in thickness, was not
translucent. Glaze runs and drip marks around the thick objects
were extensively observed, particularly on the objects whose
position was not exactly horizontal during firing. Similarly, the rock
quartz on the prop was covered entirely by a blue glaze exhibiting
runs and drips (Fig. 8a). Colonies of needle-like crystals were
observed on the thicker patches of quartz glaze coating (Fig. 8b).
3.2. GP1
Faience objects glazed by GP1 were covered by a shiny coating.
However, the colour they exhibited was mostly white, and only
blue in patches (Fig. 5a). The quartz piece was entirely white and
unglazed. The glaze coating was even and smooth on the BR and B3
samples, but wavy and uneven on the B1 and B2 samples. The
reverse sides of the objects, where they were rested during firing,
are almost unglazed, particularly on the central parts.
3.3. GP2
All faience bodies which were glazed by GP2 exhibited a rich but
very uneven coating, including many holes penetrated to the
faience bodies. The glaze colour was not turquoise blue but
greenish navy blue (Fig. 5b). The quartz piece was entirely covered
by glaze coating of the same colour. The sintered glazing powder
was more porous than GPR and GP1. However, adhesion of the
glazing powder to the glaze coating, regardless of body types, was
observed. The underside of objects, where they were rested during
firing, was covered by a rich glaze and there was no considerable
difference between the underside and upside glaze coatings.
Runners and drips were extensively observed on the coating of the
quartz piece. The appearances of the GPR, GP1 and GP2 products
are summarised in Table 6.
3.4. GP3
The observations were the same as for GPR, except for two
cases; firstly, the sintered glazing powder was too dense for an easy
removal of the objects. Secondly, there were patches of glazing
powder stuck on the glaze coating.
3.5. GP4, GP5

Table 3 Macroscopic evidence observed on the objects glazed by GP4 and

The recipes of faience bodies (wt%).
GP5 (fired in the containers without lid e oxidation firing) were the
Code BR B1 B2 B3 same as for GPR products. However, it seems that the sintered
Fine silica sand 85 95 e 90 glazing powder was slightly porous and friable. In contrast, the
Coarse silica sand e e 95 e objects produced by GP5 in the lidded container indicated an
Feldspar 10 e e e unsuccessful glazing process; the glazing powder was found
Kaolin e e e 5
Serish 5 5 5 5
adhering entirely to the glazed objects; in addition, almost no blue
colour was observed on the objects, and small red patches (known as
 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776 767

Table 5
Composition of glazing powders used for replication experiments.

Experiment Calculated composition of glazing powder base (wt%) Additivesb (g)

code
SiO2 {f} SiO2 {c} CaO {ch} CaO {cc} Na2O {s} K2O {pc} K2O {pn} CuO Al2O3 MgO Fe2O3 TiO2 NaCl Charcoal Na2O {s} K2O {pc}
GPR 29.15 e 59.31 e 3.71 2.44 e 3.34 0.62 1.33 0.07 0.03 4 e e e
GP1 29.15 e 59.31 e 3.71 2.44 e 3.34 0.62 1.33 0.07 0.03 e e e e
GP2 29.15 e 59.31 e 0.36a 0.22a e 3.34 0.62 1.33 0.07 0.03 10c e e e
GP3 29.15 e e 59.31 3.71 2.44 e 3.34 0.62 1.33 0.07 0.03 4 e e e
GP4 29.15 e 59.31 e 3.71 2.44 e 3.34 0.62 1.33 0.07 0.03 4 5 e e
GP5 29.15 e 59.31 e 3.71 2.44 e 3.34 0.62 1.33 0.07 0.03 4 10 e e
GP6 29.15 e 59.31 e 3.71 2.44 e 3.34 0.62 1.33 0.07 0.03 4 e 1.5 1.5
GP7 e 29.15 59.31 e 3.71 2.44 e 3.34 0.62 1.33 0.07 0.03 4 e e e
GP8 29.15 e 59.31 e 3.71 e 2.44 3.34 0.62 1.33 0.07 0.03 4 e e e

{f}: Supplied by fine silica sand as the main source.

{c}: Supplied by coarse silica sand as the main source.
{ch}: Supplied by calcium hydrate as the main source.
{cc}: Supplied by calcium carbonate as the main source.
{s}: Supplied by sodium carbonate as the main source.
{pc}: Supplied by potassium carbonate as the main source.
{pn}: Supplied by potassium nitrate as the main source.
a
Supplied by other ingredients and not by direct use of alkaline carbonates.
b
(g): added to 100 g of glazing powder base.
c
(g): added to 94.43 g of glazing powder.

‘copper red’ in ceramic technology) were noted instead, reflecting
the reduction atmosphere during firing. Similarly, the quartz piece
was glazed more or less by a white coating with small red patches.
3.6. GP6, GP7, GP8
The objects glazed by GP6 exhibited lighter blue glazes (in
comparison with GPR products). In addition, the same colour was
observed on the quartz piece coating. Other observations were the
same as for GPR products.
The GP7 sintered glazing powder was more porous and friable.
Furthermore, patches of adhering powder were observed on the
glazed objects regardless of body type. The other results were once
again the same as for GPR products.
The evidence visible on GP8 products was the same as for GPR
products and no considerable difference was observed between
them.
4. Discussion
4.1. Necessary quantity of alkali oxides in the glazing powder
composition
In the replication experiments mentioned above, the Na2O/K2O
ratio in the glazing powder composition was approximately 3 in all
cases. The effect of the Na2O/K2O ratio, in a range of 0.1e10, on the
appearance of the faience had been investigated in the authors’
previous replication experiments (not published), and no marked
differences in appearance were registered. However, the colour of
faience glazes which were produced with a lower Na2O/K2O ratio
slightly tended to pale blue. Moreover, the GPR replication
demonstrated that in the glazing powder composition, only about
5e6 wt% of alkali oxides (supplied by carbonates) are required for
a successful cementation glazing. The practical importance of these
data lies in the fact that such a low amount of necessary alkalis
provides a wider range of options for selecting the sources of
alkaline fluxes. Thus, these data open a new window into studying
the possible alkali flux sources in ancient faience production. This
issue will be discussed in more detail in part 2 of the present study.
4.2. Calcium carbonate or calcium hydroxide?
‘Lime’ is a general term that connotes calcium containing inor-
ganic materials in which calcium carbonate, oxide, and hydroxide
predominate. The broad use of this term in the scientific literature
on faience has been a source of much confusion in glazing tech-
nology. In the GPR experiment, a successful cementation glazing
was conducted using calcium hydroxide. In contrast, in the GP3
experiment, calcium carbonate has been the source of CaO.
Consequently, as mentioned in Section 3, adhesion of glazing
powder to the object coatings was observed. Furthermore, the
sintered glazing powder was too dense for a safe and easy removal
of objects. These replication experiments demonstrate that for

Fig. 3. Setting of faience and quartz objects for firing. Fig. 4. Firing schedule for faience and quartz objects fired in an electric kiln.
768 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776

Fig. 5. Faience objects made with BR body paste and glazed by GP1 (5a), GP2 (5b), and
GPR (5c) glazing powders.
Fig. 7. Translucent replica of faience object (about 6.5 mm in thickness) made by GPR
glazing mixture and B2 body paste.
a successful cementation glazing, in actual mass production,
calcium carbonate cannot be used as a CaO source.
contribution of potassium nitrates in the cementation glazing
process. This issue will also be discussed in more detail in part 2 of
4.3. Charcoal
this study.
It seems that the use of charcoal as a raw material in cemen-
tation glazing has been first noted in the observations of Wulff et al. 4.5. Uniformity of the glaze thickness
(1968). In the GP5 experiments (fired in the lidded container), it
was observed that the reduction atmosphere has a destructive As pointed out in Section 1, the presence of a uniform glaze
influence on the glazing process, particularly in terms of furnishing thickness has been generally accepted as a characteristic of
the glaze coating with copper blue. In cementation glazing, copper cementation glazing. However, significant variations in glaze
vaporisation with contribution of chlorides is the determining thickness were observed on the objects produced by successful
factor in the production of copper blue hues on the glaze coating
(this topic will be discussed later, in Sections 4.7 and 4.8). The blue
Table 6
hue in glaze coating is caused by Cu2þ ions. In a reduction atmo-
Coating appearance on the objects made by GPR, GP1 and GP2 glazing powders.
sphere, according to the amount of available oxygen, reddish brown
hues caused by Cuþ or the bright red resulting from copper metal Body GPR GP1 GP2
(in heavy reduction conditions) can become visible, as has been Quartz - Smooth shiny - Unglazed - Smooth shiny
seen on the GP5 sample. turquoise blue glaze. deep greenish
- Colonies of blue glaze.
It should be taken into consideration that generally the ashes needle-like crystals - Colonies of
also contain residual carbon. The residual carbon in both ashes and observed. needle-like
charcoal may produce a reduction atmosphere during the firing - Runs and drip crystals
process, particularly in mass production. On the other hand, in the marks observed. observed.
- Runs and
GPR experiment, a successful cementation glazing was conducted
drip marks
without any use of charcoal. Thus, the question arises whether observed
charcoal was indeed one of the raw materials used in cementation extensively.
glazing. As observed in the GP4 and GP5 experiments, there is only BR - Smooth shiny - Shiny whitish - Very uneven
one advantage in using charcoal, i.e. a slightly more porous sintered turquoise blue glaze, pale blue and holey
glaze. only in patches. with shiny
glazing powder. It seems that this advantage cannot be
- Needle-like - Underside of deep greenish
a convincing argument for the use of charcoal in cementation crystals observed objects is almost blue glaze.
glazing. This issue will be discussed further in part 2 of this study. in the SEM image. unglazed or - No considerable
- Runs and drip roughly vitrified. difference
marks observed. between the
4.4. Potassium nitrates
- Underside of glaze coatings
objects more or on the upper
In the GP8 experiment, the potassium carbonate was replaced less glazed, but side and
by potassium nitrate, and, once again, a successful cementation with rough underside of
patches. objects. Both
glazing was observed, which practically demonstrates the potential
are glazed.
B1 - Uneven but shiny - Uneven whitish - The same as
turquoise blue glaze. glaze, pale blue above.
only in patches.
B2 - Uneven but shiny - The same as above. - The same as
turquoise blue glaze. above.
- Only thinner
objects were
translucent.
- Needle-like
crystals observed
in the SEM image.
B3 - Shiny turquoise - Shiny whitish - The same as
blue glaze. glaze, pale blue above.
- Runs and drip marks only in patches.
observed.
Fig. 6. Faience object surrounded by its capsule.
 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776 769

Table 7
EDS analyses of needle-like crystals (normalised to 100%).

Raw no. Crystal appearance Fig. no. Glazing Sample Crystal Crystal composition Glazing
mixture type position mechanisma
SiO2 Al2O3 CaO MgO Na2O K2O CuO Cl
1 Needle-like grey crystals 11g GPR Faience BR Buffer 87.6 1.1 0.9 0.1 1.5 6.3 1.3 1.2 Combined
2 Needle-like grey crystals 9b GPR Faience B2 Body 83.0 1.5 5.1 0.2 1.8 4.6 2.9 0.9 mechanism
3 Needle-like grey crystals 10a GP2 Quartz Glaze 89.9 0.6 1.0 bd 0.6 0.9 6.2 0.8
4 Needle-like white crystals 10b GP2 Quartz Glaze 80.9 0.6 1.5 0.1 2.8 2.5 9.9 1.7 CGMb

bd: below detection limits.

a
Discussed in Sections 4e8.
b
Chloride Glazing Mechanism.

replication experiments. For example, in the GPR experiment, all
samples exhibited glaze runs and drips (particularly on vertical
sides of the objects). Indeed, it was difficult to find even one sample
with fairly uniform glaze. These observations dispute the argument
identifying uniform glaze thickness as a characteristic of cemen-
tation glazing.
4.6. Microstructural criteria
As pointed out in Section 1, a thin interaction or buffer layer and
the absence of interparticle glass are widely accepted as criteria for
cementation glazing. However, in the GPR experiment, using
coarser sand in the body mixture (B2), an entirely translucent
object approximately 6.5 mm in thickness was obtained, which is
shown in Fig. 7 (in the authors’ previous unpublished replication
experiments, such translucent samples were observed in objects
that were fired with a glazing mixture containing 10 wt% alkali
oxide, at 920 " C). It is apparent that this observation reveals more
interparticle glass in the body of the B2 object. SEM images of the
aforementioned sample show a glaze layer (GLZ) with variable
thickness, between 150 and 300 mm, and the absence of a buffer
layer (Fig. 9a), but the presence of a continuous glass matrix (light
grey) between quartz particles (darker grey) in the body (BDY,
Fig. 9b). Furthermore, needle-like crystals were observed in the
glass matrix, which will be discussed further in Section 4.7. This
experiment indicates once again that, as previously mentioned by
Vandiver (1998), such microstructural criteria should be used with
more caution.
4.7. Alkali chlorides: the essential glazing powder ingredient
In the GP1 experiment, chloride elimination from the glazing
powder composition resulted in an unglazed and white quartz
piece and an entirely white glaze coating with small blue patches
on the faience objects (Fig. 5a). These observations reflect the fact
that in cementation glazing the main and essential factor in
furnishing the glaze with copper blue colour is the presence of
alkali chlorides. More than forty years ago, Wulff et al. (1968: 106)
pointed out the relation between copper vaporisation and alkali
chlorides. They stated that “We suspect that the 1% copper oxide in
the glazing powder reacts with the salt (NaCl) in the plant ash to
form cupric chloride (CuCl2) which decomposes to cuprous chlo-
ride (CuCl) and chlorine at 993 " C. We also assume that there is
a significant concentration of copper in the vapour phase at the
firing temperature in the kiln (1000 " C) to react with the newly
formed glaze on the bead surface, turning the glaze colour into
a deep turquoise blue. Only at spots where there is direct contact
with larger copper oxide particles is a direct colouring effected in
the form of the darker specks mentioned above.” However, in the
authors’ previous replication experiments (not published), the
vaporisation of copper at a lower temperature (920 " C) was
observed. In other words, if the GPR composition were fired at
920 " C, the quartz piece would be covered by a blue glaze coating.
In the presence of alkaline chlorides, the excessive deposited
copper, with contributions from alkalis, may crystallise as needle-
like crystals, as mentioned for the first time by Wulff et al.
(1968). The presence of needle-like crystals in the continuous
interparticle glass matrix in the B2 sample (glazed by GPR mixture)
was pointed out in the previous section (Fig. 9b). Further micro-
structural investigations on the objects produced by GPR and GP2
demonstrated the presence of these crystals in the glass matrixes.
For instance, the needle-like crystals (darker grey) in the glaze layer
(GLZ) on the quartz object glazed by GP2 are shown in Fig. 10a. In
addition, at higher magnifications on the same image, the small
(about1e3 mm) white needle-like crystals were detected in the
glaze (Fig. 10b). The analytical data obtained by SEM-EDS on typical
crystal samples (both white and grey crystals) are shown in Table 7.
It should be noted that in the GP6 experiment, by using more
alkali carbonates in the glazing powder composition, a pale blue
glaze coating was achieved both on the quartz piece and the faience

Table 8
EDS analyses of the glass phases of objects glazed by GP1, GP2 and GPR glazing mixtures (normalised to 100%).

Experiment Sample type Glass phase Raw no. Glass phase composition Glazing
code position mechanism
SiO2 Al2O3 CaO MgO Na2O K2O CuO Cl
GP1 Faience BR Glaze 1 61.8 1.7 0.6 bd 6.2 27.6 2.1 bd IGMa
Buffer 2 70.8 6.8 0.3 bd 3.8 17.6 0.7 bd
Body 3 50.9 18.9 0.1 0.2 4.6 24.8 0.5 bd
GP2 Faience BR Glaze 4 69.4 9.8 0.7 0.4 2.3 1.7 14.3 1.4 CGMb
Buffer 5 80.3 9.5 1.4 0.2 2.1 1.9 3.4 1.2
Body 6 85.1 7.8 0.5 0.2 1.2 2.0 2.8 0.4
Rock quartz Glaze 7 80.8 0.4 0.1 0.4 4.8 0.6 10.9 2.0
GPR Faience BR Glaze 8 67.2 2.0 0.6 bd 5.1 15.6 8.4 1.1 Combined
Buffer 9 72.0 7.3 2.4 0.3 0.7 15.7 0.9 0.7 mechanism
Body 10 75.7 8.7 1.6 bd 0.6 12.7 0.4 0.3
Faience B2 Glaze 11 68.6 0.7 4.2 0.1 4.9 13.6 6.5 1.4
Body 12 67.3 2.0 11.4 0.8 2.9 13.0 1.6 1.0

bd: below detection limits.

a
Interface Glazing Mechanism.
b
Chloride Glazing Mechanism.
770 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776
Fig. 8. (a): Rock quartz glazed by GPR mixture. (b): Macrophotograph exposing the
details of a crystal colony on the quartz glaze. The framed area in Fig. 8a shows the
magnified section.
object, reflecting a decrease in copper vaporisation. On the other
hand, in the absence of alkali carbonates in the GP2 experiment,
a greenish navy blue was exhibited both by the faience objects and
the quartz piece (Fig. 5b). Typically, these deep greenish blue tones
are associated with a high concentration of copper in the low alkalis
glass phases, as it can inferred from the analytical data presented in
Table 8, rows 4e7. On the whole, these observations reveal
a converse linear relation between the copper vaporisation rate and
the alkali carbonates content. In other words, more alkali carbon-
ates in the glazing powder result in less vaporised copper. This
parameter is one of the main factors that explain why the firing
temperature must be about 1000 " C in cementation glazing; at
lower temperatures, an increased amount of alkali carbonates is
required for glaze formation (e.g., at 920 " C, a concentration of
about 10 wt% alkali oxides may be needed), and therefore less
vaporisation of copper and consequently pale blue products. In
summary, the observations derived from the GPR, GP1, GP2 and
GP6 experiments demonstrate that in cementation glazing, by
increasing the concentrations of alkali chlorides and carbonates in
the glazing powder composition, the vaporised copper content will
increase and decrease, respectively.
As mentioned in Section 1 and based on the recent investiga-
tions conducted by Rehren (2008) and Tanimoto and Rehren
(2008), partial contributions of alkali chlorides to faience glazes is
expected. In the GP1 and GP2 experiments, both the glazed quartz
pieces and glazed faience objects exhibited contributions of alkali
Fig. 9. Microstructure of translucent sample B2, glazed by GPR mixture. (a): SEM-BSE
image of a cross-section through the glaze (GLZ) and body (BDY). (b): SEM-BSE image
showing extensive interparticle glass in the body. BDY: body; GLZ: glaze.
chlorides in the faience glazing process. This issue will be discussed
further in the Section 4.8.
4.8. The glazing mechanism in the cementation method
To provide a clearer background for the present discussion, SEM
images of cross-sections of BR faience samples glazed by the GP1,
GP2 and GPR mixtures are shown in Fig. 11. In addition, EDS
analytical data on glass phases present in the aforementioned
samples are provided in Table 8.
Macroscopic, microstructural and compositional evidence
reveal that in the cementation method, the glazing of faience
objects is carried out by two different mechanisms, namely the
Interface Glazing Mechanism (IGM) and the Chloride Glazing
Mechanism (CGM).
4.8.1. Interface Glazing Mechanism (IGM)
This mechanism has for the most part been known and dis-
cussed extensively by researchers. It involves the diffusion and
migration of alkalis from the glazing powder to the siliceous faience
body, and subsequent interactions between them to produce glass
phases which cover the object surfaces as glaze coating, and then
penetrate into the body to produce the buffer layer and interpar-
ticle glass between the fine grains of quartz. It is obvious that the
 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776
Fig. 10. SEM-BSE image of a cross-section through a quartz object glazed by GP2
mixture. (a): The needle-like crystals (darker grey) in the glaze matrix (GLZ, light grey).
(b): The grey and white needle-like crystals at higher magnification. BDY: body; GLZ:
glaze.
occurrence of this mechanism depends on the direct contact
between the glazing powder and the surfaces of siliceous objects,
and it operates exclusively in the interfaces, as its name indicates.
The objects produced by the GP1 glazing mixtures e in the absence
of chlorides e were glazed by this mechanism (Table 5). The major
characteristics of this mechanism can be categorised under three
headings, namely ‘object appearance’, ‘microstructure’ and ‘glass
phase composition’.
4.8.1.1. Object appearance. Glaze coatings on the objects glazed by
this mechanism are typically white or whitish blue; however, pale
blue/blue patches may also be observed (Fig. 5a). The coating is
normally shiny, without any evidence of glaze runs or drip marks,
but may also be even and smooth or holey and uneven, depending on
body paste recipes (Table 3). The underside of objects, where they
were rested, generally exposes a semi-vitrified coating and appears
poorly glazed or unglazed (particularly in the central parts). The rock
quartz which is placed above the glazing mixture (without any direct
contact with the glazing mixture) exhibits an entirely unglazed
surface, which reflects the absence of any alkalis vaporisation.
4.8.1.2. Microstructure. The microstructure of the BR sample glazed
by the IGM mechanism is shown in Fig. 11a and b. The thickness of
the glaze (GLZ, light grey) is moderately even but thin, and varies
771
between 50 and 100 mm (Fig. 11a). The buffer layer (BFR) has well
defined boundaries and is about the same thickness as the glaze
layer. The quartz particles (darker grey) are more or less uniformly
distributed in the body (pores appear as black). Fig. 11b shows the
microstructure of the body at higher magnification, in which the
presence of interparticle glass (IPG, light grey) between quartz
particles (Q, darker grey) is visible.
4.8.1.3. Glass phase composition. The glass phase compositions of
the glazes made by this mechanism are essentially ‘high alkalis-low
copper’. The typical glaze composition is provided in Table 8, row 1.
A comparison between the glaze, buffer layer and interparticle
glasses reveals a decrease in copper content from the glaze layer to
the body. This aspect supports the previous observations of
Vandiver (1998). The significant amount of potash in glass phases
confirms the strong preference of the siliceous body and glass
network for Kþ (rather than Naþ), as has been pointed out by Tite
and Shortland (2008: 51e53) and Paynter (2001).
It seems that needle-like crystals in the glass matrixes are not
present in the objects produced by this mechanism, or at least they
have not been observed in this investigation.
4.8.2. Chlorides glazing mechanism (CGM)
This mechanism is fundamentally a type of vapour glazing,
based on the vaporisation of alkali chlorides. It involves deposition
of glaze on the objects by vaporised copper and alkalis. The prod-
ucts of the GP2 glazing mixture (Table 5) were glazed by this
mechanism. This mechanism plays a leading role in furnishing the
faience objects with copper green-blue hues. The main character-
istics of this mechanism are as follows:
4.8.2.1. Object appearance. Extensively holey glaze coating
(regardless of the body recipe) presenting deep greenish navy blue
hues (Fig. 5b) is the characteristic appearance of faience objects made
by this mechanism. Furthermore, there is no considerable difference
between glaze coatings on the upper side of the object and its
underside (where they were rested on the capsule). Indeed, it is
generally difficult to identify the upper side and underside of faience
objects glazed by this mechanism. In addition, runs and drip marks
are not discernible because of the holey glaze coating. On the cross-
section, a thick buffer layer and a very pale green-blue colour can be
observed with the naked eye throughout the unvitrified texture of
the body. As compared to objects glazed by the IGM mechanism, the
mechanical strength of faience objects glazed by CGM is typically
considerably lower, and, as a result, they break easily.
The rock quartz (standing above the glazing mixture during the
firing process) exhibits a rich shiny smooth glaze with the same
colour and extensive runs and drip marks, reflecting strong
vaporisation of alkalis and copper.
4.8.2.2. Microstructure. A widespread and thick buffer layer,
generally thicker than 1000 mm and up to 2000 mm, is a typical
characteristic of the microstructure of faience objects glazed by this
mechanism, as shown in Fig. 11c. However, neither the buffer nor
the glaze layers display a continuous uniformity in their thickness.
The microstructure of the body (Fig. 11d) shows minimal inter-
particle glass. In addition, the distribution of quartz particles and
glass phase is markedly uneven and there appears to be no
uniformity in the body texture overall.
In contrast to faience objects, there is no obvious buffer layer in
the microstructure of rock quartz, but an extensive glaze layer is
present, as shown in Fig. 10a.
4.8.2.3. Glass phase composition. In contrast to the objects glazed
by the IGM mechanism, the glass phases present in the glazes
772 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776

Fig. 11. SEM-BSE images of cross-sections through replicated BR samples. (a, b): Glazed by GP1 glazing mixture (IGM mechanism). (c, d): Glazed by GP2 glazing mixture (CGM
mechanism). (e, f, g): Glazed by GPR glazing mixture (combined mechanisms). BDY: body; BFR: buffer layer; GLZ: glaze; Q: quartz.
 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776 773

produced by the CGM mechanism are of the ‘low alkalis-high
copper’ type, as it can be inferred from the analytical data
provided in Table 8, rows 4 and 7.
The glaze coating on the rock quartz objects extensively exhibits
needle-like crystals, as discussed above in Section 4.7 (Fig. 10a and
b; Table 7, rows 3 and 4).
4.8.3. Combined glazing mechanisms
It is obvious that in actual practice, the faience objects are nor-
mally glazed by neither of the aforementioned mechanisms, but by
a combination of both. Accordingly, the features presented by these
mechanisms may differ from the cases mentioned above. Hence, it
appears useful to regard this case as an independent mechanism,
which is consequently referred to as ‘combined glazing mechanism’
in this paper.
Considering the GPR glazing powder ingredients (Table 5), the
main characteristics of the relevant products glazed by ‘combined
glazing mechanisms’ are classified as follows:
very important to note that in the objects glazed by this mecha-
nism, the microstructure and the amount of interparticle glass
heavily depends on the firing schedule and particle size of the raw
material (silica), as noted for instance on the B2 sample glazed by
GPR (Fig. 9).
4.8.3.3. Glass phase composition. The composition of glaze coatings
produced by combined mechanisms can be classified as belonging
to the ‘high alkalis-high copper’ type. The typical composition of
such glazes is provided in Table 8, rows 8 and 11. Generally, the
glass matrixes made by this mechanism may contain needle-like
crystals, for instance in the interparticle glass (see Fig. 9b), buffer
glass (see Fig. 11g), or glaze (see Fig. 10a and b).
For purposes of clarity, a comparison between the main char-
acteristics of the different glazing mechanisms is provided in
Table 9.
4.9. Firing shrinkage of faience objects

4.8.3.1. Object appearance. Shiny glaze coating with turquoise blue
shades is the typical appearance of these objects (Fig. 5c). The glaze
coating on the faience objects may be smooth and even or holey
according to the body paste recipes (see Tables 3 and 4). The
underside of objects is broadly covered by glaze coating; however,
it may also be rough, especially in central parts. Runs and drip
marks are generally observed, particularly on the vertical sides of
the objects.
In samples produced by this mechanism, the rock quartz is
always glazed and exhibits the same colour as the faience objects,
as well as extensive runs and drip marks. Colonies of crystals may
be observed on the thicker part of the glaze coating (Fig. 8).
4.8.3.2. Microstructure. The microstructure of faience objects made
by BR paste and glazed by combined glazing mechanisms is shown
in Fig. 11eeg. Well defined glaze and buffer layers, both about
200e450 mm in thickness, are displayed in Fig. 11e. Generally, there
is extensive interparticle glass (light grey) between quartz particles
(darker grey), mostly distributed uniformly (Fig. 11f). However, it is
In comparison with most ceramic objects, faience objects
produced by the cementation method show unusual firing
shrinkage behaviour. The main unusual aspects of their shrinkage
process are as follows:
1) There is no limitation to the rate of shrinkage; the amount of
shrinkage for a determined glazing mixture and firing
temperature depends largely on the duration of the firing
process, particularly the ‘soaking time’ (the term used in the
firing schedule to denote the maintenance of the maximum
temperature for a period of time). As the firing time rises, the
shrinkage increases more and more, and no evidence of object
melting has yet been identified.
2) Considering the firing time and the object’s size, the rate of
shrinkage may be remarkable. In exceptional cases, the
shrinkage process may continue to such an extent that the object
depletes entirely and the remainder is only an empty capsule.
3) The endless shrinkage process may occur at any temperatures
between approximately 920 " C and 980 " C, and it should be

Table 9
The main characteristics of glazing mechanisms.

Specification Object Interface Glazing Mechanism (IGM) Chlorides Glazing Mechanism (CGM) Combined glazing mechanisms
Appearance Faience (BR) - Shiny, smooth, white or - Holey glaze coating with deep - Shiny, smooth turquoise blue glaze coating.
whitish blue glaze coating. greenish navy blue hues. - Runs and drip marks observed, particularly
- No evidence of runs or drips. - The recognition of runs and drips on the vertical sides.
- The underside of objects is is not possible due to extensive - The underside of objects is covered by
poorly glazed or unglazed. holey surface. glaze coating; however, it may be rough,
- Quite similar glaze coatings on particularly in central parts.
the upper side and underside of objects.
- A thick buffer layer on the cross-section,
visible with the naked eye.
- Low mechanical strength.
Rock quartz - Entirely unglazed. - Smooth, shiny, deep greenish navy - Smooth, shiny, turquoise blue glaze
blue glaze coating. coating.
- Extensive runs and drip marks. - Extensive runs and drip marks.
Glaze Faience (BR) - The glass phase of the glaze - The glass phase of glaze layer is - The glass phase of glaze layer is of the
composition layer is of the ‘high of the ‘low alkalis-high copper’ type. ‘high alkalis-high copper’ type.
alkalis-low copper’ type.
Microstructure Faience (BR) - Generally, thin glaze and - A thick but very uneven glaze and - Well defined glaze and buffer layers,
buffer layers with buffer layers, generally thicker with extensive needle-like crystals
obvious and than 1000 mm. on the latter.
defined boundaries. - Needle-like crystals in the buffer layer. - Extensive interparticle glass between
- Limited interparticle glass - Minimal interparticle glass, unevenly uniformly distributed quartz particles.
between uniformly distributed between irregular
distributed quartz textures of body.
particles.
Rock quartz - Entirely unglazed. - No obvious buffer layer, but a thick - No obvious buffer layer, but a thick
glaze layer containing needle-like crystals. glaze layer containing needle-like crystals.
774 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776

highlighted that in actual practice there is no evidence of object
melting (such as body vitrification, melting deformations,
observation of melted glasses, or adhesion of sintered objects
to the glazing powder).
4) The objects shrink extensively only in their thickness (or
height), but not in their length or width (see Fig. 12). The
faience object shown in Fig. 12 has been made with BR body
paste as a small brick-like shape (40 # 21 # 7.5 mm) and glazed
by a GPR glazing mixture. It was fired according to the schedule
shown in Fig. 4, but with an additional 20 min soaking time.
hand to the formation of a capsule around the object (the latter is
discussed in Section 4.10). It is obvious that the presence of ‘inter-
faces’ between the siliceous body and the glazing powder is
a prerequisite for diffusion. Therefore, in the initial stages of the
shrinkage process, silica migration occurs in all interfaces (Fig. 13a
and b), whereas by proceeding with the process, the silica migra-
tion takes place only through the underside of the object (Fig. 13c
and d). Thus, after the initial stage of the shrinkage process, the
objects shrink only in their heights or thicknesses.

According to the mechanisms and main causes involved, the

firing shrinkage of faience objects can be categorised as follows:

4.9.1. Firing shrinkage caused by glass phases produced by the IGM

mechanism
The glass phase produced by the IGM mechanism has been
discussed in Section 4.8.1. This shrinkage mechanism has been
previously discussed by researchers. For instance, Kingery and
Vandiver (1986: 277) state that: “the sodium carbonate diffuses
to the quartz paste body, where it reacts, releasing carbon dioxide
and forming an alkali silicate.as the first liquid is formed, it
penetrates into the quartz powder [body] so that the bead shrinks
away from the surrounding powder to allow room for the shiny
coating to be formed.” As it was discussed in Section 4.8.1, it is clear
that direct contact between the glazing powder and the surfaces of
the faience object is a prerequisite for the production of glass phase
by this mechanism. However, it should be noted that after the
initial stages of the shrinkage process, there would not be any
contact between the glazing powder and surfaces of the faience
object (except for the base of the object, where it stands on the
glazing powder). Therefore, this mechanism is effective only during
the early stages of the shrinkage process.

4.9.2. Firing shrinkage caused by glass phases produced by the CGM

mechanism
In comparison with glasses produced by the ICM mechanism,
those produced by the CGM mechanism (Section 4.8.2) provide
small contributions to firing shrinkage, mainly due to the minimal
amount of interparticle glass (see Fig. 11c and d). Furthermore, the
resulting glass is of the low alkalis type (Table 8, rows 4e7), and,
thus, it is less effective as a flux of silica.

4.9.3. Firing shrinkage caused by depletion of the siliceous body

from the faience object
In the cementation method, diffusion and migration of silica
from the siliceous body of the faience object to the glazing powder
occurs during the firing process. This phenomenon leads on the one
hand to the endless shrinkage of faience objects, and on the other

Fig. 12. Broken capsule showing the approximate amount of a faience object’s
shrinkage.
Fig. 13. Schematic diagrams illustrating the depletion of a siliceous faience object,
caused by silica migration to and reaction with the glazing mixture. (a): Interactions
which cause the shrinkage of objects during firing. (b): The initial stage of the
shrinkage process, simultaneous with the formation of the capsule. (c): Silica migra-
tion through the object’s underside causes a decrease in the height of the object. (d):
By continuing the silica migration, the object shrinks more and more.
 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776 775

The data obtained by wet chemistry analytical methods,
provided in Table 10, support the observations and schematic
diagram (Figs. 12 and 13) and demonstrate the silica migration to
and reaction with the glazing powder. The compositions of the
glazing mixtures (after firing) are provided in rows 1 and 3 and
their associated capsules in rows 2 and 4, respectively. As shown in
Table 10, the silica contents in capsules are significantly higher than
those in the glazing mixtures.
4.10. The mechanism of capsule formation
In the cementation method, a further aspect that needs to be
considered is capsule formation. During the firing process, the
capsule prevents adhesion of glazing powder to the surface of the
melting glaze coating. Thus, the capsule formation process plays
a crucial role in a successful cementation glazing.
Calcium oxide is a refractory material with a melting point of
approximately 2570 " C. In silicates however, it may act as a flux,
depending on its content in the mixture. In the replication exper-
iments mentioned above, the ratio of CaO/SiO2 has been more than
2, as shown in the calculated composition data in Table 5 or the
analytical data in Table 10, rows 1 and 3. Generally, the melting
points of cementation glazing mixtures with such ratios are too
high for producing dense sintered mixtures at about 1000 " C. Thus,
in these cases, a friable glazing mixture will be achieved after firing
that enables an easy removal of objects. However, by decreasing the
CaO/SiO2 ratio to a value lower than 1, a dense sintered mixture will
be obtained in actual practice. In other words, increasing the SiO2
content in the glazing mixture leads to a significant reduction in the
melting point of the glazing mixture and hence in the formation of
a dense sintered material.
The aforementioned phenomenon is the main cause of capsule
formation. By diffusion of silica into the glazing mixture (and the
resulting reduction of the CaO/SiO2 ratio), a layer of dense sintered
mixture forms around the object, which is known as a ‘capsule’.
After the initial stage of the shrinkage process and the simulta-
neous formation of the capsule, silica migration continues only
through the object’s underside, at the bottom of the capsule. Thus,
the bottom or the base of the capsule is generally thicker than its
walls, as shown in the schematic diagram (Fig. 13c and d).
As mentioned above, silica migration is the major cause of
capsule formation. However, as Table 10 shows, the capsule
composition is generally richer in alkalis, which leads to more
reduction in the melting point of the mixture, and consequently
facilitates the process of capsule formation.
4.11. Body mixture
The glaze coating on samples B1 and B2, as compared with BR
and B3, was not even and smooth. The glaze on B2 was more holey
and uneven, which reflects the fact that by using finer sand in the
body, the faience glaze will be more even and smooth.
The BR and B3 samples exhibited a smooth and even glaze
coating. As shown in Table 3, they respectively contain feldspar and
clay. According to the mineral compositions of feldspar and clay, it
can be concluded that in cementation glazing the presence of
alumina in faience body compositions in minor proportions (see
Table 4) improves the glaze appearance. Indeed, in the actual
production of faience objects by cementation glazing, using too
pure sand leads to uneven and wavy glazes, as noted on the B1 and
B2 samples in the GPR experiment.
The analytical data provided in Table 8 demonstrate the
contribution of aluminium ions in the glass networks (glaze, buffer
layer, and interparticle glass) associated with the BR sample
(Table 8, rows 8e10), whereas there is little alumina in glass phases
associated with the B2 sample (rows 11 and 12). Aluminium ions in
glass networks significantly increase their surface tension and
viscosity. On the other hand, the glasses which contain too low
a concentration of Al3þ are very fluid. As a general rule, very fluid
glazes usually cannot produce even glaze coatings on the porous
bodies, because they penetrate very easily and quickly into the
pores.
Overall, it appears that in cementation glazing, there are addi-
tional decisive factors contributing to glaze smoothness. For
instance, in the GP2/BR experiment, despite the aluminium
contribution in the glass network (Table 8, rows 4e6) and conse-
quently a more viscous glaze, the glaze coating was uneven and
holey, as mentioned in Section 3 and Table 6. By drawing
a comparison between the microstructures of the different samples
shown in Figs. 9 and 11, in conjunction with analytical data on glass
phases (Table 8), it becomes apparent that in cementation glazing,
the smoothness of the glaze coating is determined by complex
interactions between different decisive factors, such as the amount
of glass phases present in the body, buffer and glaze layers, the
nature and composition of the glass phases e which is in turn
determined by body contaminations and particularly glazing
mechanisms e, distribution and size of body particles, etc.
As it is known in ceramic technology, the suspensions and
pastes of non-plastic materials such as quartz or sand are dilatant.
When mechanically disturbed, the dilatant paste appears to stiffen,
but if the disturbing force is removed, it becomes mobile again.
Dilatancy is a destructive factor in faience pastes, causing a reduc-
tion in their plasticity and ‘workability’ and limitations in the
forming process. By using aqueous solutions of plasticisers such as
Serish, gum Arabic and gum tragacanth, the plasticity (or more
precisely termed ‘workability’) of paste will improve slightly.
However, by mixing dry Serish powder with sand and then adding
the required water, the workability of the resulting paste improves
considerably, so that it may be wedged and kneaded (just like the
clay-based pastes). Furthermore, these pastes can be easily formed
in moulds, and the mould patterns are reflected on the bodies in
more detail. It should be considered that, unlike the clay-based
pastes, the ‘aging’ of such pastes has a destructive effect on their
workability, and thus it must be avoided in replication experi-
ments; the rheological properties of the aqueous solutions (or

Table 10
Chemical composition of capsules and sintered glazing mixtures resulting from GPR and GP2 experiments, obtained by wet chemistry analytical method.

Experiment code Raw no. Sample Chemical composition (wt%) Glazing mechanism

SiO2 Al2O3 CaO MgO K2O Na2O CuO Cl Totala

GPR 1 Glazing mixture 26.2 0.6 60.7 1.1 1.6 3.1 3.4 1.9 98.6 Combined mechanism
2 Capsule 44.3 0.9 42.5 1.0 1.0 7.7 1.2 0.6 99.2
GP2 3 Glazing mixture 25.4 0.5 58.4 1.1 0.3 4.6 1.7 6.8 98.8 CGMb
4 Capsule 53.2 0.7 34.7 0.8 0.2 5.5 2.1 1.3 98.5
a
Fe2O3, TiO2, MnO: not analysed.
b
Chloride Glazing Mechanism.
776 M. Matin, M. Matin / Journal of Archaeological Science 39 (2012) 763e776
suspensions) of Serish change significantly in time. For instance, if
such a solution is allowed to stand for 2 or 3 h, its viscosity
decreases significantly, and the dilatancy tendency increases. More
dilatancy means less plasticity and, consequently, lower
workability.
Regarding the B3 paste, it should be mentioned that the pres-
ence of 5 wt% kaolin in its recipe did not have any considerable
effect on the paste workability.
5. Conclusions
1) A concentration of only about 5 wt% of alkali oxides (supplied
by carbonates) in the glazing powder composition is sufficient
for a successful cementation glazing at 980 " C. In actual prac-
tice, the requirement of only such a low amount of alkalis in the
glazing mixture means that in ancient faience production,
there could have been more sources for alkali fluxes having
lower amounts of alkalis in their composition, and not only
soda rich plant ashes and natron, which both have significant
amounts of alkalis in their composition. In other words, a wider
range of options for selecting the sources of alkaline fluxes can
be considered, and this aspect opens a new window into
studying potential alkali flux sources. This issue will be inves-
tigated further in part 2 of the present study.
2) Calcium carbonate is not a suitable source for supplying CaO. It
has a destructive effect on the glazing process. Calcium
hydroxide is a proper alternative.
3) There is no convincing reason for confirming the use of char-
coal as a raw material in the glazing powder.
4) It appears that potassium nitrate, like the fully reactive alkali
carbonates, contributes to the cementation glazing process.
5) Our observations did not confirm the macroscopic criteria
employed for identifying cementation glazing. In contrast,
glaze runs and drip marks were extensively observed on the
replicated cementation glazes.
6) Translucent faience objects with 6.5 mm thickness at temper-
atures in the range 920e980 " C have been made by cementa-
tion glazing which, in this case, did not confirm the
microstructural criteria employed for the identification of
cementation glazing. Such observations again emphasise that
microstructural criteria must be used with more caution.
7) Alkali chlorides are essential raw materials for the cementation
glazing process. They contribute to the formation of glass
phases (interparticle glass, buffer and glaze). In addition, they
play a prominent role in furnishing the glaze coating with
copper blue hues, because the vaporisation of copper basically
depends on the presence of chlorides in the glazing powder.
8) The alkali carbonates limit copper vaporisation. Increasing the
concentration of alkali carbonates in the glazing mixture leads
to a reduction in copper vaporisation.
9) Deposition of alkalis and copper vapours on the surfaces of
faience objects is the major cause of runs and drip marks. Also,
the aforementioned vapours play a leading role in glazing the
object’s underside (where it stands on during firing).
10) By adding about 5 wt% Serish powder to the body mixture, and
then adding water, a more plastic paste was obtained that was
easily formed and moulded. The mould patterns could be
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reflected on this paste in more detail. The propensity of such
a paste for forming by a potter’s wheel, at least in the case small
objects, should be studied in future research.
11) In the body mixture, alumina bearing contaminations, such as
feldspar and clay minerals, improve the glaze appearance. It
seems that in cementation glazing, using too pure silica in the
body mixture leads to a low quality glaze coating.
Acknowledgements
This project was financed by Shex Porcelain Co. The authors
wish to thank Mehdi Shokr-e-Khodaie for drawing our attention to
the production of faience in early decades of the last century in
Shushtar, providing video data, and establishing a personal
communication with his grandmother, who was involved in
producing faience. We would also like to thank Yazdan Ghassemi-
nia for preparing raw materials and Mahmoud Nader for photo-
graphs and illustrating the figures. We are also grateful to Prof.
Thilo Rehren and two anonymous referees for their helpful
comments, which have greatly improved the original manuscript.
Special thanks go to Raul Carstocea for his invaluable help with the
final editing.
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