The use of antimony and its implication for the

luminescence properties of ancient mosaic tesserae

Anna Galli
*
, Marco Martini, Cinzia Montanari, Emanuela Sibilia
INFM and Dipartimento di Scienza dei Materiali, Universit aa degli Studi di Milano Bicocca, via R. Cozzi 53, 20125 Milan, Italy
Abstract
The potential of using luminescence techniques to characterise and eventually to date ancient glass mosaic tesserae
has been investigated. A number of ancient mosaic samples coming from the Mediterranean basin have been studied
examining the features of their thermally stimulated luminescence (TSL) emission. We have mainly investigated the role
played by antimony oxide (III and V oxidation states) in the optical properties of the vitreous tesserae, both ancient and
modern prepared ad hoc. The presence of antimony is always associated with relatively higher TSL sensitivities. In the
ancient samples, the presence of antimony led to the formation of calcium antimoniate crystals while the addition of
antimony oxide to a modern frit did not determine the formation of such crystals. Analysing the characteristics of the
dierent wavelength-resolved TSL spectra, a tentative interpretation of this phenomenon has been put forth.
2003 Elsevier B.V. All rights reserved.
PACS: 78.55.Qr; 78.60.Ku
1. Introduction
Thermally stimulated luminesce (TSL) can be
sketched as follows: the absorption of energy from
ionising radiation by an insulator produces the
excitation of electrons in the lattice and the sub-
sequent trapping of some of these electrons at
defects within the material itself. When the sample
is heated, the thermal energy detraps the electrons,
that are then free to recombine with charge carri-
ers of the opposite sign. If the recombination is
radiative, luminescence (TSL) is emitted [1]. The
simplied scheme sketched here for electrons holds
for holes as well. The emitted light, registered as a
function of temperature, is the so-called glow
curve. Apart from the specic experimental con-
ditions (like for instance the light detector and the
heating rate) the shape of the glow curve and the
spectral composition of the emitted light is related
to the presence of defects in the material. The
study of the TSL of crystals gives important in-
formation on defects and impurities and on their
kinetics. Moreover, the TSL properties of many
archaeological and geological materials are the
base of the current well established dating tech-
nique [2]. TSL is usually observed in ordered
crystals, but the phenomenon also occurs in dis-
ordered materials such as glasses.
*
Corresponding author. Tel.: +39-026 448 5165; fax: +39-
026 448 5400.
E-mail address: anna.galli@mater.unimib.it (A. Galli).
0022-3093/03/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-3093(03)00292-8
Journal of Non-Crystalline Solids 323 (2003) 7277
www.elsevier.com/locate/jnoncrysol
In this work we focused our attention on the
particular characteristics that determine the lumi-
nescent properties of ancient mosaic tesserae, in
order to investigate whether TSL can contribute
to the understanding of some of the many ques-
tions still open about glass production in antiq-
uity: the making of the glass base, the addition of
colouring materials and opaciers, the evolution in
the production techniques and the commercial
trades. To study the luminescence properties we
used TSL, rather than photoluminescence, because
one of our main goals is to achieve a dating
technique and we have recently observed that the
TSL signal of mosaic glasses is more intense than
in other glasses, making TSL a promising tool for
dating [3].
The rst regular production of glass in a con-
trolled way occured in Mesopotamia and Egypt in
the middle of the second millenium BC. The
main type of glass produced for many centuries,
was silica-soda-lime glass; it was still produced
in Roman imperial time [4]. Also in later times,
when mixed-alkali and woodash glasses were more
common, soda-lime glasses are still found,
maybe due to re-melting of materials produced
elsewhere [5].
The main colouration was caused by transition
metal ions, either present in the original sand,
(iron and manganese), or intentionally added
during melting, like typically copper and cobalt
[6,7]. On the nal colouration, duration of heating,
temperature and furnace atmosphere were funda-
mental agents.
Opaciers were also added to modify the chro-
matic eect, as frequently observed in mosaic
glasses. In antiquity, the opacity of glass could be
obtained with dierent techniques [8]. For in-
stance, the addition of specic elements in the
fused glass, leading to the separation of white
microcrystals (de-vitrication or secondary crys-
tallisation) was a common practice. In pre-Roman
and Roman periods calcium antimoniate was the
main opacier employed and it was still in use in
the late rst millennium. The tin oxide was instead
more diused in later times [8].
In a recent work [7], during the study of dif-
ferent sets of ancient mosaic tesserae, the material
of the entire series could be dened as soda-lime
silica glass. The colouring elements found in the
samples were chiey four: iron, manganese, copper
and cobalt. They were analysed by electron spin
resonance technique. As regards the optical prop-
erties, we have observed a correlation between the
antimony content of a sample and its TSL sensi-
tivity [10].
The aim of the present work was a better un-
derstanding of the role played by antimony in the
TSL properties of glasses. In particular, we tried to
determine whether the enhancement of the lumi-
nescence intensity, related to the presence of anti-
mony, was due to calcium antimoniate crystals,
detected in some ancient mosaic tesserae, or to
other antimony compounds. To this aim, we pre-
pared a modern glass matrix having a composition
as close as possible to the ancient glass one, then
added controlled amounts of antimony salt. Once
we measured the XRD spectrum of both ancient
and modern glasses, we investigated their wave-
length resolved TSL emissions and compared them
with the one produced by pure crystals of calcium
antimoniate.
2. Experimental procedures
We considered a set of samples of dierent or-
igins, all coming from the Mediterranean basin,
their chronology spanning from V to XIII Century
AD, detailed described elsewhere [7]. The samples
were prepared according to Sanderson et al. [11];
the dating protocol prescribe storage and manip-
ulation under safe laboratory illumination, but in
our case this precaution was not necessary because
we were not interested in dating, but in under-
standing why some samples had a good TSL signal
and some not.
Tesserae were cut into dierent slices to a
thickness between 500 and 800 lm, with a dia-
mond saw (Bueheler, Isomet type 11/1180 Low-
speed Saw, Diamod Wafering Blade). On the basis
of the composition of the ancient glass tesserae, a
modern colourless glass frit, chemically very sim-
ilar to the mosaic studied but free of the impurities
which inevitably occur in the raw materials used
in antiquity, was prepared [7]. To this base,
controlled quantities of Sb
2
O
3
were added.
A. Galli et al. / Journal of Non-Crystalline Solids 323 (2003) 7277 73
A CaSb
2
O
6
standard was also prepared, starting
from pure antimony(V)oxide (99.995%) and cal-
cium oxide (99%).
For conventional TSL measurements we used a
home-made system, consisting of an oven for
controlled heating, where the glow-curves were
measured in ultrapure N
2
atmosphere (heating rate
10 C/s), using a photon counting technique with
an EMI9635QB photomultiplier tube coupled to
Corning BG12 blue lters.
Articial irradiations were performed using a
1400 MBq
90
Sr
90
Y beta source (dose rate 1.4 Gy/
min) and an X-ray tube (operating conditions:
20 kV, 10 mA. Dose rate: 16.6 Gy/min).
To study the wavelengths of TSL emission,
a high-sensitivity home-made apparatus was used,
with a detector consisting of a two-stage micro-
channel plate (MCP) with a 512-photodiode array.
The whole system, cooled by a Peltier control
unit, reached a signal-to-noise ratio and a sensi-
tivity comparable with that of a photomultiplier.
The spectra, recorded at 2 C/s, were corrected
for the wavelenght response of the detection sys-
tem, about which details are reported elsewhere
[12].
3. Results and discussion
After performing dierent typical procedures to
fully investigate the TSL behaviour of our samples
[3], we found that their TSL emissions were char-
acterised by good reproducibility, strong bleaching
induced by light exposure and by a sensitivity
relatively higher than previously observed in other
ancient glasses [11]. This was ascribed to a higher
density of crystals in the amorphous matrix.
Muller et al. [13] showed that changes in the lu-
minescent properties of glass appeared when
passing from vitreous to crystalline state. In par-
ticular, they noted that the thermoluminescent
sensitivity (TSL/Gy, signal intensity per unit of
absorbed dose) increased with the crystallinity
level of the sample. It should be underlined that
the signal intensity, as just dened, is strongly
dependent on the lters and the detector (generally
a photomultiplier tube, PMT) that are used. To
partially correct for this drawback we have also
analysed the emission wavelength as described
below.
From the analysis of the intensity of the TSL
signal of the mosaic tesserae we could evidence
that the addition of colouring and opacifying ions
aects the TSL sensitivity. This is summarised in
Fig. 1 where the TSL sensitivity is reported as a
function of the absorbed dose in the glass base and
in samples prepared adding to the same base dif-
ferent concentrations of metal ions (Fe, Mn, Pb
and Sb). While the addition of colouring ions de-
termined a lowering of TSL sensitivity, an increase
was evident in the antimony-enriched sample. This
result agrees with the fact that high TSL sensitivity
were systematically observed in the samples with
high Sb concentration. As already mentioned, the
emission wavelength of the mosaic tesserae con-
taining dierent ions was measured [3]; the data
reported in Fig. 1 are generally conrmed by the
measurements of the wavelength resolved emis-
sions. The sample having the lower intensities
(containing Mn and Pb) can hardly be measured
with a wavelength dispersive system, but the low
level of the TSL signal is conrmed. This can ei-
ther be due to a lower concentration of traps or to
a lower uorescence eciency. At this stage of our
work preliminary results of radioluminescence
measurements (light emitted under X-ray excita-
tion at room temperature) indicate that the low
TSL intensity is due to a lower uorescence e-
ciency.
1000
10
4
10
5
10
6
10
7
10
8
0 10 20 30 40 50
Sb oxide 1.5%
Base
Fe oxide 1%
Pb oxide 2%
Mn oxide 1%
T
L

(
a
.
u
.
)
Dose (Gy)
Fig. 1. TSL growth vs. articial beta dose of modern glass
samples free of oxides (base) and enriched with dierent oxides.
74 A. Galli et al. / Journal of Non-Crystalline Solids 323 (2003) 7277
X-ray diraction analysis performed on some of
those samples showed the presence of crystals
surely identiable as calcium antimoniate [9]
(CaSb
2
O
6
), as shown in Fig. 2.
In Fig. 3 the emission spectrum of an ancient
tessera and that of a CaSb
2
O
6
pure sample are
compared, both recorded after 100 Gy of X-rays
irradiation. The light intensity is plotted as a
function of both temperature and emission wave-
length. The relative contour plots are also shown.
Fig. 3(a) reports the spectrum of an ancient sample
containing 0.24% of antimony oxide. A main
emission is evident at about 430 nm (temperature
range 100180 C). A second recombination cen-
tre, emitting at approximately 600 nm and asso-
ciated to the glow peaks at 150 and 300 C, was
also observed. The same main emission at 430 nm
is present in the spectrum of the CaSb
2
O
6
standard
(Fig. 3(b)).
It could therefore be deduced that CaSb
2
O
6
crystals play an important role in the radiative
recombination processes, being probably respon-
sible for most of the emitted TSL.
To better understand the behaviour of anti-
mony in the vitreous matrix, we analysed some
modern glass standards prepared ad hoc. X-ray
diraction analysis showed that CaSb
2
O
6
crystals
were not present in the matrix, even though both
calcium and antimony oxide were originally pre-
sent. The presence of CaSb
2
O
6
crystals in the an-
cient samples could then be due to a deliberate or
unconscious addition of calcium antimoniate
crystals to the fused glass by ancient glassmakers.
Alternatively, the absence of calcium antimoniate
in modern samples could be due to the fact that
Sb
2
O
3
was not reduced to Sb
2
O
5
preventing the
crystal formation.
The TSL spectrum of the modern glass to which
antimony oxide was added, reported in Fig. 4,
shows that the main emission is now centred at
370 nm, dierently from the CaSb
2
O
6
standard
and from the ancient glass samples of Fig. 3(a) and
(b). As previously mentioned, we have however
observed that the addition of Sb to the modern
glass always increased the TSL sensitivity. Not
only the calcium antimoniate crystals are therefore
responsible for a TSL enhancement but also the
antimony oxide plays a similar role.
We propose two possible explanations of this
phenomenon. It is known that the Sb
3
ions can
act as sensitizer [14], emitting in the blue wave-
length region under ultraviolet irradiation. If, for
instance, Sb
3
ions were spatially close to ions like
Mn
2
, that are not excited by ultraviolet radiation,
such excitation energy could be transferred
from Sb
3
to Mn
2
. On the contrary, if there are
not Mn
2
ions in the vicinity, Sb
3
exhibited its
own blue emission. A similar phenomenon could
be present in our samples, giving an energy
transfer from Sb
3
ions to other ions unidentied
so far.
A second interpretation for the TSL enhance-
ment caused by antimony oxide can be put forth:
Sb
3
ions could substitute for Si
4
ions in the lat-
tice, causing oxygen vacancies which are known to
act as emitting centres in silica. Against this second
hypothesis we could observe that the atomic radii
of Sb
3
and Si
4
are 0.90 and 0.42

AA respectively,
and that the ion substitution in a crystal is possible
only if the dierence between the atomic radii is
less than 0.15

AA. The situation could however be
dierent in glassy materials.
To understand which interpretation is correct,
the study of the TSL emission of modern glasses
rich in antimony oxide submitted to high temper-
ature annealing (about 700 C) is planned. This
treatment should in fact modify the concentration
of the oxygen vacancies in the sample.
Fig. 2. X-ray powder diractogram of a sample from Faragola,
showing the presence of calcium antimoniate crystals.
A. Galli et al. / Journal of Non-Crystalline Solids 323 (2003) 7277 75
4. Conclusions
Summarising what has been presented above,
we rstly observe that the presence of antimony
enhanced the TSL signal of the vitreous matrix.
This opacier possibly forms new TSL centres or,
alternatively, activates the existing ones. Even if
our investigations are at a preliminary step, all
the experimental results obtained until now con-
rmed this interpretation. Further analyses on
other standard glasses are on-going, in order to
denitely determine if the crystals of calcium an-
timoniate are responsible for the observed en-
hancement of the TSL signal in glass and if the
Fig. 3. Emission spectrum and contour plot of an ancient mosaic tessera from Faragola (a) and of a CaSb
2
O
6
standard (b) Heating
rate 2 C/s, absorbed dose 100 Gy.
76 A. Galli et al. / Journal of Non-Crystalline Solids 323 (2003) 7277
signal enhancement of the modern glass enriched
in Sb
2
O
3
is due to a phenomen of energy transfer
or to new defect creation.
Acknowledgements
This work has been partially supported by
CNR, Roma, Progetto Finalizzato per i Beni
Culturali. We are grateful to Dr Norberto Chio-
dini for the preparation of the antimony stan-
dards.
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Fig. 4. Emission spectrum and contour plot of a modern glass
sample with 1.5% Sb
2
O
3
. Heating rate 2 C/s, absorbed dose
100 Gy.
A. Galli et al. / Journal of Non-Crystalline Solids 323 (2003) 7277 77