Appl. Phys.
A 92, 109–116 (2008)
DOI: 10.1007/s00339-008-4456-8
s. lahlil1,u Rediscovering ancient glass technologies
i. biron1
l. galoisy2 through the examination of opacifier crystals
g. morin2 1 C2RMF Centre de Recherche et de Restauration des Musées de France, 14 quai François Mitterrand,
Palais du Louvre, Porte des Lions, 75001 Paris, France
2 IMPMC, Institut de Minéralogie et de Physique des Milieux Condensés, Universités Paris 6 et 7,
IPGP, 140 rue Lourmel, 75015 Paris, France
Received: 10 October 2007/Accepted: 15 January 2008
Published online: 4 April 2008 • © Springer-Verlag 2008
ABSTRACT The aim of the study is to understand how anti-
monate opacifying crystals were obtained throughout history.
Two archaeological glass productions opacified with calcium
and lead antimonates are studied in this paper, in order to
rediscover ancient opaque glass technologies: Roman mosaic
tesserae (1st cent. B.C.–4th cent. A.D.) and Nevers lampwork-
ing glass (18th cent. A.D.). The fine examination of crystalline
phases and of the vitreous matrix is undertaken using vari-
ous and complementary techniques. Results are compared with
a modern reference production, for which the technological
process is well known. We demonstrate that Ca-antimonate
opacifiers in Roman mosaic tesserae, as well as in Nevers
lampworking glass, were obtained by in situ crystallization.
Nevertheless, Roman and Nevers glass would have undergone
different firing processes. We propose that the addition of pre-
viously synthesized crystals or the use of “anime” could be the
process used to obtain Pb-antimonate opacified glass, for both
productions studied. We demonstrate that CaO, PbO and Sb2 O3
concentrations in the bulk compositions and in the matrices, and
their evolution with the crystallinity ratio, offer robust criteria
for the distinction of the opacification process used. Also, the
different crystalline structures help to provide information on
the experimental conditions.
PACS 81.05.Kf; 81.10.Fq; 61.50.Lt; 61.05.cp; 82.80.Ej
1 Introduction
Glass is usually opacified by small crystalline par-
ticles, called opacifiers, dispersed in the vitreous matrix.
Different types of opacifier have been used throughout his-
tory. Antimonates are especially interesting because they have
been used for a long time, from Ancient Egypt to the present
time, with periods of interruption. Two types of antimonate
can be distinguished: Ca-antimonate (white colored) and Pb-
antimonate (yellow colored). The crystal color may or may
not induce a modification of the glass coloration. For example,
the combination of a translucent turquoise matrix with Ca-
antimonate crystals results in a lightened turquoise opaque
glass, whereas the combination of a translucent turquoise ma-
trix with Pb-antimonate crystals results in a green opaque
glass.
u Fax: +33-140202422, E-mail: sophia.lahlil@culture.gouv.fr
Applied Physics A
Materials Science & Processing
In this paper, we aim to understand how two groups of
ancient opaque glass products were obtained by comparing
their physical and chemical characteristics with the contem-
porary opaque glass production (“corpo” technology). Ne-
vers lampworking glass figures, dating from the 18th cent.
A.D. – coming mainly from the French “Musée des Arts
Décoratifs” – are studied through seven white glasses opaci-
fied with Ca-antimonates, and three green glasses opaci-
fied with Pb-antimonates. Eight pink, blue and turquoise co-
lored Ca-antimonate opacified Roman mosaic tesserae and
three Pb-antimonate opacified glasses (two yellow and green
tesserae, and one yellow decorated bead), dating from the 1st
cent. BC–4th cent. AD, are studied.
An approach based on the fine examination of the crys-
talline phases and of the vitreous matrices, using comple-
mentary analytical techniques, is proposed. Furthermore, we
attempt to use the glass microstructure and the elements sub-
stituted in the antimonate crystals as indicators of the fabrica-
tion conditions and of the raw materials used.
Toproduce these crystals, three opacification processes are
proposed: the addition to a translucent glass of natural crystals
or crystals synthesized separately, the addition to a translucent
glass of an opacifier-rich glass called “corpo”, and the in situ
crystallization (separation from the melt of the crystals). The
“corpo” technique is studied through the reference production
of contemporary mosaic tesserae made by the Orsoni Com-
pany in Venice. It consists of a three step process.
– A soda-lime-silica glass containing lead is prepared in
a furnace at a temperature of 900 – 1000 ◦ C (antimony is in-
troduced as oxidized stibnite). This glass, called “corpo”,
is white due to the high amounts of Ca-antimonate crystals
formed in situ.
– Independently, a translucent soda-lime-silica Pb-rich
glass, colored or not, is prepared.
– To opacify this translucent glass, the “corpo” is then in-
troduced in several steps at a temperature around 900 ◦ C,
and its concentration is adjusted according to the tint de-
sired. In the case of uncolored glass, a white opaque glass
is obtained; in the case of colored glass, the addition of the
“corpo” allows one to make different hues (the crystals act
as clarifiers).
In contrast, in the in situ crystallization process stricto sensus,
Ca- or Pb-antimonate crystals are formed by the diffusion and
the combination of the elements present in the raw material
mixture or in the melt. The quantity and the nature of crys-
110 Applied Physics A – Materials Science & Processing
tals formed depend on the chemical composition of the glass,
on the oxidation state of antimony and on the experimental
conditions used (temperature, duration, cooling rate, furnace
atmosphere and nature of the crucible).
2 Analytical methods
2.1 Microstructure and chemical analyses
Millimeter-sized fragments of glass were removed
from all the samples studied. These fragments were embed-
ded in a polyvinyl resin block and polished using diamond
pastes down to 0.25 µm, vacuum coated with carbon and ex-
amined in a scanning electron microscope at 20 kV accelera-
ting potential (SEM; JEOL 840, Oxford Instruments). Ele-
mental compositions of vitreous matrices and crystals were
determined using an energy-dispersive X-ray spectrometer
FIGURE 1 SEM-BSE images of Ca-antimonate crystals in a white contemporary Orsoni glass, in a white Nevers lampworking glass and in a blue Roman
mosaic tesserae
coupled with the SEM (EDX), and electron microprobe ana-
lyses (EPMA). The results in weight oxides were normalized
at 100%. Samples presenting very small crystals (< 1 µm)
were also observed with a field electron gun (FEG; Gemini
15-25, Carl Zeiss instruments) at 5 kV (SE images) or 20 kV
(BSE images) accelerating potential.
2.2 Crystallographic measurements
X-ray diffraction analyses (XRD) were performed
directly on Orsoni and Roman mosaic tesserae using a X-Pert
Pro diffractometer (Panalytical device) with vertical go-
niometer under Bragg–Brentano geometry, with Cu K α Ni-
filtered radiation. Measurements were performed in a 5–120◦
range, with a time step of 0.017 s. Suitable databases were
used for peak assignments using X-Pert Panalytical software.
Rietveld refinement was performed with FullProf software.
LAHLIL et al. Rediscovering ancient glass technologies through the examination of opacifier crystals
Microdiffraction (µDRX) measurements were performed in
the C2RMF, (Cu K α , 5–50◦ range) on Nevers lampworking
glass samples as they all measure less than 3 mm length.
3 Results and discussion
3.1 Calcium antimonate opacified glass
3.1.1 The microstructure as an indicator of the technological
conditions. In the Orsoni, Nevers and Roman glasses studied,
the microstructure is characterized by a rather homogeneous
distribution of small geometrical crystals of Ca-antimonates,
with sometimes small aggregates of various shapes and sizes
(Fig. 1). The amount of crystals varies from one sample to an-
other. Considering Orsoni glass, we notice that the addition
of a “corpo” to a translucent glass modifies neither the crystal
distributions nor their morphologies.
Some differences can be noticed: large aggregates are
present in Nevers and Roman glasses, but not in the Orsoni
glasses (Fig. 2). The individual crystal size is generally lower
in Nevers (mean size ∼ 3 µm) and Roman glasses (mean size
∼ 2 µm), compared to Orsoni glass (mean size ∼ 4 µm). The
large aggregates can have very peculiar morphologies and
relatively high sizes (from 7 to 70 µm) (Fig. 2). These ob-
servations are in good agreement with previous studies made
on white and blue Roman glasses [1–3]. In turquoise Roman
tesserae, aggregates are especially different: they are very fre-
quent, have generally high sizes (from 20 to 200 µm), and
are constituted by small crystals compacted together (Fig. 2).
These noticeable differences could indicate variable techno-
logical conditions and/or the possible influence of copper –
used as a glass colorant in these tesserae – on the precipitation
of Ca-antimonate crystals.
FIGURE 2 SEM-BSE images of Ca-antimonates aggregates in a white Nevers glass and in blue and turquoise Roman mosaic tesserae
111
If the density, the morphology and the chemical homo-
geneity of the crystals are all dependent upon their formation
history, the observation of the microstructure is not always
sufficient to define the technological process used. Develop-
ment of an imaging treatment is in progress, in order to find
evidence of new features in the glass microstructure, charac-
teristic of each production.
3.1.2 Using CaO and Sb2 O3 concentrations to identify the
opacification process. In order to evaluate the crystal quan-
tity in each opaque glass, we define the crystallinity ratio
as the surface of crystals/surface of the amorphous phase in
a sample. It is determined by the area ratio according to BSE
images and by theoretical calculations. We assume that CaO
and Sb2 O3 concentrations in the bulk compositions (vitreous
matrix + crystals) and in the vitreous matrices and their evo-
lution with the crystallinity ratio could be good criteria for the
distinction of different opacifying processes.
In the reference samples of Orsoni contemporary glass
(soda-lime-silica glass containing lead, Table 1), the amounts
of CaO and Sb2 O3 in the bulk compositions, as well as in the
vitreous matrices, are positively correlated (Fig. 3) and their
values increase with the crystallinity ratio. This is due to the
fact that they are opacified using the “corpo” process: during
the opacification, part of the “corpo” (matrix and crystals) can
dissolve within the translucent glass to re-establish the ther-
modynamic equilibrium. Consequently, the more “corpo” is
added, the higher the amounts of CaO and Sb2 O3 in the bulk
compositions and in the vitreous matrices.
In Roman mosaic tesserae (soda-lime-silica glass, Table 1)
and Nevers lampworking glass (mixed alkali-lime-silica glass
with low lead contents, Table 1) the evolutions of the amounts
of CaO and Sb2 O3 in the bulk compositions are very different
112 Applied Physics A – Materials Science & Processing

Production Orsoni glass 21st cent. A.D. Nevers glass 18th cent. A.D. Roman glass 1st cent. B.C.–4th cent. A.D.
Opacifier Ca-antimonate Ca-antimonate Pb-antimonate Ca-antimonate Pb-antimonate
Color Corpo White Blue Turquoise White Green Pink Blue Turquoise Green Yellow
Nb samples 1 3 3 1 7 3 1 5 2 1 2

Na2 O 15.5 ± 0.7 13.1 ± 2.8 16.8 ± 1.8 14.5 ± 0.6 6.5 ± 1.6 9.1 ± 4.6 16.8 ± 0.7 15.3 ± 0.5 17.8 ± 0.5 18.3 ± 0.5 10.8 ± 4.3
MgO nd nd 0.3 nd 2.3 ± 0.5 1.7 ± 0.9 1.4 ± 0.1 0.5 ± 0.1 0.5 ± 0.1 0.5 ± 0.1 0.5 ± 0.2
Al2 O3 nd nd 0.4 nd 0.5 ± 0.4 0.3 ± 0.2 1.7 ± 0.2 2.2 ± 0.2 1.7 ± 0.7 1.7 ± 0.4 0.9 ± 0.6
SiO2 47.3 ± 2.2 54.2 ± 4.1 51.9 ± 1.0 49.8 ± 0.6 58.1 ± 3.0 59.8 ± 4.0 67.3 ± 1.2 67.9 ± 0.6 64.8 ± 1.8 65.4 ± 1.3 55.6 ± 16.8
SO3 0.5 nd 0.6 nd 0.5 ± 0.1 0.4 ± 0.3 0.4 ± 0.1 0.4 ± 0.1 0.2 ± 0.4 nd 0.9 ± 0.2
K2 O 0.2 ± 0.1 0.1 ± 0.1 0.7 ± 0.9 0.6 ± 0.1 10.8 ± 1.3 9.3 ± 1.5 0.6 ± 0.1 0.6 ± 0.2 0.5 ± 0.1 0.7 ± 0.1 0.3 ± 0.5
CaO 5.5 ± 0.3 3.2 ± 1.8 1.6 ± 0.4 2.3 ± 0.1 8.6 ± 1.7 5.6 ± 1.4 6.2 ± 0.3 8.2 ± 0.1 4.5 ± 0.5 6.3 ± 0.3 5.3 ± 1.1
Fe2 O3 nd nd nd nd 1.0 ± 1.0 0.3 ± 0.2 0.8 ± 0.1 0.9 ± 0.2 0.8 ± 0.1 0.8 ± 0.3 2.5 ± 1.5
CoO nd nd nd nd nd 0.1 ± 0.1 nd 0.1 ± 0.1 nd nd nd
CuO nd nd 1.3 ± 1.1 1.9 ± 0.1 nd 3.8 ± 2.0 nd 0.2 ± 0.1 3.7 ± 0.2 2.7 ± 0.4 0.1 ± 0.1
SnO2 nd nd nd nd nd nd nd nd nd 0.3 ± 0.3 nd
Sb2 O3 10.6 ± 1.0 6.2 ± 3.4 3.0 ± 0.5 3.4 ± 0.2 6.4 ± 1.0 0.6 ± 0.2 3.8 ± 1.2 2.9 ± 0.7 4.1 ± 0.7 1.0 ± 0.8 3.5 ± 2.5
PbO 20.3 ± 1.6 22.8 ± 1.5 24.0 ± 1.0 25.4 ± 1.4 4.3 ± 2.5 8.7 ± 5.8 nd nd nd 2.5 ± 0.6 18.7 ± 17.4

nd = not detected
TABLE 1 Elemental compositions obtained by EDX measurements of three opaque glass productions expressed in weight percent oxide

from the contemporary glasses (Fig. 3). Both glass produc-
tions would have been made using an opacifying process
different from the “corpo” one. It seems that the proportions
of CaO and Sb2 O3 were adjusted according to the opacity de-
sired, and consequently, that Ca-antimonates had crystallized
in situ.
The in situ crystallization of Ca-antimonates in Roman
glass has been suggested by some authors according to mi-
crostructural observations and chemical analyses [1–7]. They
propose that antimony was added as stibnite in the raw
form (Sb2 S3 gray mineral) [8], or as roasted stibnite (Sb2 O3 ,
Sb2 O5 ) [1, 2], to the raw materials or to a translucent glass.
Foster and Jackson [7] obtained Ca-antimonate opacified
soda-lime-silica glass by in situ crystallization using two
manufacturing methods:
– a one stage process where Sb2 O3 (6 wt. %) was introduced
in the raw materials;
– a two stage process, where Sb2 O3 (6 wt. %) or Sb2 S3
(6.99 wt. %) was added to a typical Roman soda-lime-
silica glass and the batches were re-melted.
The chemical analyses and the crystalline structure of Ca-
antimonates have not been investigated.
courages us to think that Roman mosaic tesserae were made
at higher temperature than Nevers and contemporary glasses
(T > 900 – 1000 ◦ C). Therefore, assuming that the same opaci-
fication process – in situ crystallization – was used, diffe-
rences observed in Roman and Nevers glass productions
could be due to different experimental conditions and/or to
different glass compositions (Fig. 3). In order to test this hy-
pothesis and to evaluate the phase transition temperature of
the Ca2 Sb2 O7 –CaSb2 O6 system in vitreous matrices, synthe-
ses of Ca-antimonate opacified soda-lime-silica glasses are in
progress in the laboratory.
The presence of elements such as Na or Pb, in the vitreous
matrix, could also play a role in the crystallization of Ca-
antimonates. Indeed, significant amounts of Na are detected
in large aggregates of Ca2 Sb2 O7 crystals, in turquoise Roman
tesserae (Table 2). These glasses have the same levels of Na2 O
and lower levels of CaO than the other Ca-antimonate opaci-
fied Roman glasses but contain copper as a colorant (Table 1).

3.1.3 Using crystal structure to approach experimental con-

ditions (temperature, duration, cooling rate, ...). Generally,
Ca-antimonates are present in opaque glass as Ca2 Sb2 O7
(orthorhombic structure) and CaSb2 O6 (hexagonal struc-
ture) [1, 2, 8–10]. We suggest that the ratio of the contents
of Ca-antimonate phases CaSb2 O6 /Ca2 Sb2 O7 , could provide
information on the range of temperature used to produce
opaque glass. In fact, the synthesis of pure crystals of Ca-
antimonates shows that CaSb2 O6 is formed at higher tem-
perature than Ca2 Sb2 O7 . CaSb2 O6 crystallizes from 927 ◦ C at
the expense of Ca2 Sb2 O7 and becomes the major phase from
1094 ◦ C [11].
In contemporary and Nevers glasses, Ca-antimonate com-
pounds are mainly present as Ca2 Sb2 O7 with an orthorhom-
bic structure, whereas in Roman glasses, the two crystalline FIGURE 3 CaO vs. Sb2 O3 concentrations in the bulk compositions (vit-
phases are always detected: CaSb2 O6 hexagonal is the major reous matrix + crystals) of Orsoni glass (full squares), Nevers glass (full
phase and Ca2 Sb2 O7 orthorhombic is the minor phase. It en- triangles) and in Roman tesserae (hollow triangles) (EDX analyses)
LAHLIL et al. Rediscovering ancient glass technologies through the examination of opacifier crystals 113

FIGURE 4 SEM-BSE images of crystals distri-

bution in an opaque green Nevers lampworking
glass and in an opaque green Roman mosaic
tesserae

FIGURE 5 SEM-BSE images of yellow aggre-

gates of Pb-antimonate crystals in an opaque
green Nevers glass and in an opaque green Ro-
man mosaic tesserae

wt.% Orsoni glass 21st cent. AD Nevers glass 18th cent. AD Roman glass 1st cent. BC–4th cent. AD
Color White-blue-turquoise White Turquoise
Nb analyses ∼ 70 ∼ 40 ∼ 20

Na2 O nd nd 5.5–11.5
CaO 20.6–22.3 69.6–73.1 6.5–9.0
Sb2 O3 65.8–67.9 23.8–25.4 71.5–83.4
PbO 8–10 1–3 nd

nd = not detected
TABLE 2 Elemental compositions obtained by EDX measurements of Ca-antimonate crystals in the three opaque glass productions expressed in weight
percent oxide

In the same way, Ca is partially substituted by Pb – coming
from the vitreous matrices – in Ca2 Sb2 O7 crystals in all con-
temporary and Nevers glasses (Tables 1 and 2). These latter
crystals undoubtedly contain Pb because:
1. the EDX and EMPA analyses are mainly undertaken on
large size crystals (∼ 10 µm > EDX and EPMA beam ra-
diation areas),
2. the average concentration of lead in the crystals is very
stable for a large number of analyses (Table 2),
3. the Rietveld refinement of XRD patterns is in good agree-
ment with the incorporation of Pb in the structure of Ca-
antimonate crystals.
This feature has not yet been reported in the literature. The
presence of lead in the glass could possibly aid the precipi-
114 Applied Physics A – Materials Science & Processing
FIGURE 6 Fe2 O3 vs. Sb2 O3 and PbO concentrations in the bulk compositions of Pb-antimonate opacified Roman glass (EDX analyses)
tation of Ca-antimonate crystals as suggested by Foster and
Jackson [7].
3.2 Lead antimonate opacified glass
Orsoni glass could not serve as a modern reference
in the study of Nevers and Roman Pb-antimonates opacified
glasses because yellow and green contemporary tesserae are
now opacified with cadmium sulfide.
Roman glass is soda-lime-silica glass whereas Nevers
lampworking glass is mixed alkali-lime-silica glass. They
both contain variable amounts of lead (Roman glass: PbO =
2–32 wt. %, Nevers glass: PbO = 5–16 wt. %, EDX ana-
lyses) (Table 1). Yellow glasses are colored by yellow Pb-
antimonate crystals, whereas green glasses are colored by the
same opacifiers and copper oxide dissolved in the vitreous
matrix.
3.2.1 The microstructure as an indicator of the technological
conditions. The microstructure of Roman and of Nevers
glasses is characterized by a rather homogeneous distribution
of geometrical crystals in the vitreous matrix (Fig. 4). In both
productions, several aggregates formed by crystals closely
packed together are observed (Fig. 5). The morphology of
these aggregates differs notably in the two groups of glass
studied. In Roman glass, aggregates are often constituted by
very small acicular or granular crystals (∼ 0.5 µm), whereas
in Nevers glass, aggregates are larger, more frequent, and con-
stituted by regular geometrical crystals (mean size = 2 – 3 µm)
(Fig. 5). These noticeable differences could indicate variable
technological conditions.
In both productions, opacifiers contain mainly Pb and Sb
and correspond to a crystalline phase close to Pb2 Sb2 O7 with
a cubic pyrochlore structure. SEM-EDX and EPMA measure-
ments show that tin oxide is sometimes present in aggregates
of Nevers and Roman glasses. Heterogeneous aggregates are
illustrated by BSE images (Fig. 5): white areas correspond to
a mixture of Pb, Sb and Sn oxides, whereas gray areas cor-
respond mainly to tin oxide (SnO2 = 90 wt. %). While tin is
present only in aggregates in Roman glasses, it is also de-
tected in isolated crystals in Nevers lampworking glass and
no stoichiometric formula has been established (PbO = 44–
56 wt. %; Sb2 O3 = 18–35 wt. %; SnO2 = 9–20 wt. %). Fur-
thermore, isolated crystals of SnO2 are sometimes observed in
Nevers glass. Note that the presence of tin in Pb-antimonate
crystals of Roman mosaic tesserae has not been reported yet.
For both productions, it is possible that tin was brought
with raw materials, or was added deliberately, because only
traces of SnO2 are detected in the vitreous matrices of Ne-
vers and Roman glasses, and aggregates with a tin-rich center
are present. The low concentrations of Sn in glass matrices
could also reflect the fact that tin is less soluble than Sb in
glass. It would nucleate first and serve as a nucleus for the
antimonate crystals. Tin playing a role in Pb-antimonate crys-
tallization would explain why it is present in crystals of glass
productions from periods more than 1400 years apart. For, Ro-
man glass, tin seems to occur mainly in the opacifiers of the
green glasses and its concentration is higher in the green than
in the yellow glasses. This may be a result of the addition of
tin with copper in the form of bronze scale, a well known co-
lorant in ancient glasses. The Sn : Cu ratios are right for a 10%
Sn bronze (Table 1).
Tin is commonly found with a mixture of Pb and Sb, in
other productions of opaque glass or in yellow glass-based
pigments, dating from the 16th –late 19th cent. A.D. [12–18].
Moreover, recipe books of Murano glassmakers, contempo-
rary with Nevers glass, dating from the 18th –19th cent. A.D.,
describe the preparation of a yellow pigment called “anime”,
from raw materials containing Pb, Sb, tin and sand [18–21].
Recipes report that in a first step, metallic lead and tin were
calcinated together, in order to obtain an oxide of lead-tin yel-
low. This product was then mixed with Sb sulphide, minium
and sand, to obtain a glassy yellow pigment, called “anime”,
which was used as an opacifying product [18, 19]. In this pro-
cess, tin is introduced with lead, as lead-tin yellow (type I
Pb2 SnO4 or type II PbSnO3 ), or as residual cassiterite SnO2 -
by-product of the tin calcination [19].
Differently from Nevers glass, the presence of iron in
the crystals of Roman glass is detected (Fe2 O3 = 3.85 wt. %;
mean value EDX analyses). It indicates that Pb2 Sb2 O7 opaci-
fiers, in the two productions, would not have been elabo-
rated from the same raw materials. The correlations between
LAHLIL et al. Rediscovering ancient glass technologies through the examination of opacifier crystals
the amounts of Fe2 O3 , PbO and Sb2 O3 in the bulk com-
positions (to confirm with more analyses) let us think that
iron would come from Sb and/or Pb sources or would have
been added on purpose during crystal elaboration (Fig. 6a
and b). Crystal stoichiometry in aggregates would be close to
Pb2 (Fe y Snx Sb2−y−x )O7−y−x/2 with x = 0–1 and y = 0–1. The
presence of iron in yellow opacifiers of Roman glasses has not
been reported yet in the literature.
It is known that the substitution of Sb in Pb-antimonate
opacifiers can modify the crystal coloration: tin would slightly
brighten the yellow color, whereas iron produces a yellow-
orange color [17–19, 22].
3.2.2 Using PbO, Sb2 O3 concentrations to identify the opaci-
fication processes. Considering Roman tesserae, the evolu-
tion of PbO and Sb2 O3 concentrations in the bulk analyses
show that they are positively correlated (Fig. 7). These preli-
minary results show a general trend already observed in yel-
low and green Roman glasses [2]. If the same evolution with
the crystallinity ratio is verified through further analyses, the
hypothesis that yellow and green Roman glasses were opaci-
fied by the addition to the melt of natural or previously synthe-
sized crystals or by using a “corpo” process will be confirmed.
The interpretation of different studies based on microstruc-
tural and chemical analyses tends to confirm this hypothe-
sis. Mass et al. [2] suggest that natural Pb-antimonates were
present in litharge sources resulting from the cupellation pro-
cess, and that once added at a relatively low temperature to
the melt, a further crystallization occurred during the cooling.
Brun et al. [3] propose the addition of powdered Pb-Sb com-
pounds, which would decompose due to the temperature at
which it is added to the glass. At this stage of the study, we
cannot discard any of these hypotheses.
Considering Nevers lampworking glass, the evolution of
PbO and Sb2 O3 concentrations in the bulk analyses are still
not sufficient to determine the opacification process. How-
ever, clues are provided by the study of ancient glassmaking
recipes and techniques contemporary to Nevers production
(Muranese recipe books of the 18th –19th cent. A.D.). The
FIGURE 7 Sb2 O3 vs. PbO amounts in the bulk compositions of Pb-
antimonate opacified Roman glass (EDX analyses)
115
“anime” was powdered and added to a translucent glass melt,
at a relatively low temperature, in order to prevent the yel-
low pigment from dissolving within the glass [18–21]. Thus,
such an opacification process consists in the addition of syn-
thesized crystals directly to the melt. Nevertheless, more ana-
lyses on new samples and XRD measurements, as well as
syntheses of opaque glass in laboratory are in progress in
order to help us discovering how these glasses were made.
4 Conclusions
The detailed study of the vitreous matrices and
crystals of opaque glasses is a very profitable approach for the
determination of the technological processes used to produce
ancient opaque glass. Our results show that the in situ crys-
tallization process was used to produce Roman tesserae and
Nevers lampworking Ca-antimonate opacified glasses. Ne-
vertheless, Roman and Nevers glass would have undergone
different firing processes. In green Nevers lampworking glass,
yellow lead-tin-antimonate opacifiers could have been pro-
duced using the contemporary “anime” recipes (addition to
the glass of opacifiers synthesized separately). In the case of
Roman glass opacified with Pb-antimonates, preliminary re-
sults demonstrate that a similar process, but still different from
Nevers glass, would have been used. Nevertheless, for both
productions, more experiments and measurements should be
done to confirm these hypotheses.
Useful criteria to distinguish different opacification pro-
cesses are proposed: assuming a homogeneous production,
the correlation between the concentrations of CaO (or PbO)
and Sb2 O3 in the bulk compositions and in vitreous matri-
ces and their evolution with the crystallinity ratio can help
to differentiate a “corpo” technique, or an addition of crys-
tals, from an in situ crystallization. Furthermore, in the case
of Ca-antimonates opacified glass, the presence of the two
crystalline phases CaSb2 O6 and Ca2 Sb2 O7 and their relative
proportions could provide information about the range of tem-
perature used to produce opaque glass. Besides, elements sub-
stituted in the antimonate crystals could give clues about the
experimental conditions and/or the raw materials used and
can modify the crystals coloration.
To test the different hypotheses proposed and to under-
stand both the influence of the initial mixture composition
and the firing process on the crystallization, syntheses of
Ca- and Pb-antimonate opacified glass are in progress in the
laboratory.
ACKNOWLEDGEMENTS For allowing us the access to the
glass samples studied, we are very grateful to the following glassmakers,
scientists and curators: The Angelo Orsoni Company (Venice), C. Moretti,
J.-L. Olivié (Musée de Arts Décoratifs, Paris), P. Santopadre (Istituto Cen-
trale del Restauro, Rome), M. Verità (Stazione Sperimentale del Vetro,
Venice). Experiments were successfully performed only with the fruitful co-
operation of other scientists: P. Walter (C2RMF), M. Fialin and F. Couffignal
(Service Camparis, Université Paris 6), S. Poissonnet (CEA). Special thanks
to Y. Adda for his everyday support and advices. M. Menu, M. Verità, I. Free-
stone, P. Lehuédé and R. Pillay are gratefully acknowledged for their help.
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