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Investigation of medieval bulgarian glass bracelets from Drastar-castle (XI-

XIII AD)

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 Доклади на Българската академия на науките
Comptes rendus de l’Académie bulgare des Sciences

Tome 63, No 1, 2010

CHIMIE
Chimie inorganique

INVESTIGATION OF MEDIEVAL BULGARIAN GLASS

BRACELETS FROM DRASTAR–CASTLE (XI–XIII AD)

Ralitsa Georgieva, Albena Detcheva, Yanko Dimitriev∗,

Bisserka Samuneva

(Submitted by Academician D. Klissurski on October 6, 2009)

Abstract

Since ancient times glass was used for manufacturing of glass jewelry. Ob-
ject of our study were medieval glass bracelets from XI–XIII AD excavated in
Drastar–castle (Silistra, Bulgaria). Weight chemical analysis was applied for sil-
ica assessment. The other oxides were determined by flame photometry (sodium
and potassium) or flame atomic absorption spectrometry (aluminum, calcium,
iron and magnesium) after dissolution using a mixture of acids. The results ob-
tained were compared with literature data. According to their composition all
fragments are soda-lime-magnesium-glasses made by following the Near East
recipe norm.
Key words: medieval glass, chemical composition, recipe norm

Introduction. Archaeological excavations in villages and necropolises have

proved that glass has been used in Bulgarian territories since the end of VI BC [1 ].
During the Middle Ages intense development of material culture, in particular,
of production and trade of glassware in Bulgaria was observed. Glass was used
not only for decoration of churches, monasteries, palaces and household, but also
for manufacturing of glass jewelry. Together with the import of glass, Bulgarian

The authors acknowledge the financial support by the National Science Fund of Bulgaria
(National Centre for New Materials UNION, Contract No DO-02-82/2008).

71
glass workshops have been discovered in Gabrovo (IV–VII AD) [2 ], Pliska (IX–X
AD) [3 ], Preslav (IX–X AD) [4 ], Stara Zagora (X–XI AD) [5 ], Hissar (X–XI AD)
[6 ] and Veliko Tarnovo (XIV AD) [7 ]. Numerous glass fragments of beads and
bracelets dated from XI to XII AD were found by archaeological explorations
in medieval villages and necropolises [8 ]. Among them the glass bracelets from
Drastar–castle (situated near to the city of Silistra, Bulgaria) were of great inter-
est. Most of the artifacts dated from XI to XIII AD were used in funeral rituals
and as adornments. In the present study the chemical composition of four bracelet
fragments excavated in Drastar–castle was established in order to get information
concerning the type of glass, glassmaking technology and recipe norm.
Experimental. The investigated glasses were homogeneous, without gas
bubbles and crystalline inclusions. Four glass samples from four different series
(see Fig. 1) were taken as follows: 1.1. (deep blue twisted fragment); 2.1. (deep
brown smooth fragment); 3.3. (violet furrowed fragment) and 4.1. (light blue
smooth fragment).
In order to determine the chemical composition small parts were taken from
each archaeological fragment. After washing with distilled water and drying at
120 ◦ C, the samples were ground to fine powder in an agate mortar. 0.5 g sam-
ple powder was melted with Na2 CO3 than dissolved according to classical wet-
digestion procedure [9 ] and weight chemical analysis was applied for silica assess-
ment. Sodium and potassium content was determined by flame photometry after

Fig. 1. Medieval glass fragments of bracelets excavated in Drastar–castle, Silistra

72 R. Georgieva, A. Detcheva, Y. Dimitriev et al.

dissolution of 0.2 g sample powder with H2 SO4 and HF acids. The elements Al,
Ca, Fe and Mg were determined by flame atomic absorption spectrometry after
dissolution of 0.2 g sample powder with HF, HNO3 and HClO4 acids.
Results and discussion. Archaeological objects are very precious and the
sample amount is usually not sufficient for several parallel determinations. In the
present study the glass fragments were of about 1 g weight and were subjected to a
single analytical procedure each. According to [9 ] the accuracy of weight chemical
analysis is about 1%. The results from the chemical analysis of the investigated
glasses are presented in Table 1. In all cases the sum of the oxides is around
100% which is a proof for the absence of outliers and systematic errors and is an
excellent accuracy for the purposes of our study.
It is obvious that main components are SiO2 , Na2 O and CaO (more than
8%) and additional components are Fe2 O3 , MgO, Al2 O3 and K2 O (in the range
of 1–5%). According to their chemical composition all glasses could be related
to the soda-lime-magnesium-silica group [10 ], which is typical for glass produc-
tion in Middle-East, Mediterranean and Rhine area [11 ], for Byzantium [12 ] and
Bulgarian glasses from in XI AD [13, 14 ]. In all samples the concentration of MgO
is relatively high (about 4%). This is probably due to the fact that magnesium-
containing carbonates (as dolomite) were used as raw material by the glassmaking.
The concentration of Al2 O3 is in the range of 1.6% and 2.5% which also proves
the use of clay-kaolin sands. In all samples the concentration of K2 O is more than
1% which indicates that plant ash is added to the batch as a source of alkaline
components by the technology of glassmaking [10 ]. Thus we confirm the use of
plant ash in the technology of glassmaking during the Middle Ages. The approach
of Shtapova uses the ratio alkali oxides to alkaline earth oxides to propose the
so-called “recipe norm”. In general, three recipes for glassmaking were simulta-
neously used in the past independently of the place of production [10 ]. Figure 2
presents a comparison of the investigated glasses with other glasses of different ori-
gin – from Pliska, Preslav and Oescus (Bulgaria) [14 ]; from Poitieres (France) [15 ],

Table 1
Chemical composition of medieval Bulgarian glass bracelets from
Drastar–castle (XI – XIII AD)

Sample Oxides [wt %]

No SiO2 Na2 O CaO MgO Fe2 O3 Al2 O3 K2 O
1.1 65.2 14.21 9.59 3.44 3.79 2.54 1.35
2.1 64.6 15.32 8.09 3.97 4.20 2.08 1.65
3.3 64.9 16.47 8.73 4.33 1.31 1.63 1.77
4.1 68.2 15.75 8.43 3.96 1.70 1.64 1.96

Compt. rend. Acad. bulg. Sci., 63, No 1, 2010 73

from Patras [16 ] and Phillippi [17 ] (Greece), from Venetzia and Aquileia (Italy) [18 ]
and from the Near East [19 ]. The glasses from Preslav, Venetzia and Patras were
produced according to the so-called Near East recipe norm (ratio around 1.5)
while for the glasses made in Aquileia, Philippi, Patras and Poitieres the Roman-
province recipe norm (ratio around 2.0–2.5) was used. The Roman-capital recipe
norm (ratio around 3) was used only for the production of glasses from Pliska
and Oescus. Applying this approach it was proved that all glasses in the present
study were made according to Near East recipe norm (ratio values around 1.5).
This indicates the strong influence of the Near East tradition on the glass making
technology in our country.

Fig. 2. The ratio [M2 O]: [MO] vs. MO in archeological glasses of different origin where:
[M2 O] = [Na2 O+K2 O] and [MO] = [CaO+MgO]. Origin of the glass samples: Silistra,
Bulgaria, XI – XIII AD [present study]; Pliska, Bulgaria, IX – X AD [13 ]; Preslav, Bul-
garia, IX – X AD [13 ]; Oescus, Bulgaria , II – IV [13 ]; Poitieres, France, VIII – XII AD
[14 ]; Patras, Greece, IX – X AD [15 ]; Philippi, Greece, VI AD [16 ]; Venetzia, Italy, VIII
– XIV AD [17 ]; Aquileia, Italy, I AD [17 ]; Near East, XII AD [18 ]

74 R. Georgieva, A. Detcheva, Y. Dimitriev et al.

 Conclusions. The present paper deals with four glass fragments of bracelets
excavated in Drastar–castle (Silistra, Bulgaria) dated from the period XI – XIII
AD. According to their chemical composition, all glasses were related to the soda-
lime-magnesium-silica group, which was typical for Middle-East- and Mediter-
ranean countries, the Rhine area, Byzantium and Bulgaria in the Middle Ages.
Glasses were prepared using Ca- and Mg-containing carbonates (e.g. dolomite),
clay-kaolin-sands and plant ashes as raw materials. All artifacts subjected to
chemical analysis in the present study were made corresponding to Near East
recipe norm. This indicates the strong influence of the Near East tradition on the
glassmaking technology in our country during the Middle Ages.
Acknowledgements. Thanks are due to Prof. DSc. L. Doncheva-Petkova
and to the National Institute of Archaeology with Museum, BAS for supplying
the glass fragments.

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Institute of General
and Inorganic Chemistry ∗
University of Chemical Technology
Bulgarian Academy of Sciences and Metallurgy
Acad. G. Bonchev Str., Bl. 11 8, Kliment Ohridski Blvd
1113 Sofia, Bulgaria 1756 Sofia, Bulgaria

76 R. Georgieva, A. Detcheva, Y. Dimitriev et al.

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