Research article

Received: 7 November 2010 Revised: 6 June 2011 Accepted: 24 June 2011 Published online in Wiley Online Library: 23 September 2011

(wileyonlinelibrary.com) DOI 10.1002/sia.3810

Cobalt absorption bands for the differentiation

of historical Na and Ca/K rich glass
A. Ceglia,a* W. Meulebroeck,a K. Baert,b H. Wouters,c K. Nys,c
H. Thienponta and H. Terrynb
The main purpose of this publication is to define sensing parameters by means of optical spectroscopy to study and
characterize ancient glass. Because during different times different flux agents were used, a chemical individuation of these
elements provides a first dating classification. Normally, X-ray-based chemical methods are applied to this kind of
investigation. On the basis of the Ligand-field theory, the absorption band positions of a transition metal ion undergo a
change when the ion is placed in different chemical environments. A total of 25 cobalt coloured Roman, post-medieval and
industrial glasses were analyzed by means of SEM–energy dispersive X-ray spectroscopy to group them according to their
chemical composition. Optical spectroscopy was applied to build a method to study glass with this low-cost and non-
destructive technique. It is proved that the cobalt absorption band situated around 535.5 nm for sodium-rich glasses (Roman
and industrial material) is shifted towards 526.5 nm for calcium–potassium-rich glasses (post-medieval window glass). This
feature was employed as a marker in the case study of the Renaissance window of the Church Wardens from the Church of
Our Lady in Bruges, Belgium to distinguish the post-medieval material from the 19th and 20th century restoration material.
Copyright © 2011 John Wiley & Sons, Ltd.

Keywords: ancient glass; optical spectroscopy; cobalt; ligand-field theory

Introduction The principal network modifiers are alkali elements such as

Glass is a widespread material in archaeological and historical
contexts. Consequently, the interest of archaeologists and art
historians in applying techniques from natural sciences as a way
to help characterize these materials has grown during the last
decades.[1–6] The issues that are interesting to investigate
concerning historical glasses are multiple. Examples are: to
obtain knowledge about the place of production, the period of
fabrication, the technological processes, the type and prove-
nance of raw materials and its functionality. However, the
questions to be answered are different according to the context
in which the glass is conserved. Archaeological glass collections
are studied from a different point of view with respect to
museological and in situ preserved stained glass windows.
During their life-time, medieval and post-medieval stained glass
windows kept in situ undergo many different restoration
campaigns. In the current conservation treatment, the dating,
origin, and authenticity of glass pieces are of paramount
importance in deontological discussions. To acquire scientific
information about many of these topics, the knowledge about
the chemical composition is of major importance.
A glass consists of the melting of three main constituents: a
network former and two types of network modifiers.[7]
In ancient glass the network former is almost exclusively
silicon oxide (SiO2), which is able to create a three-dimensional
tetrahedral network with a silicon atom at the centre and an
oxygen atom at each corner. Each oxygen atom is shared by two
silicon atoms with a covalent bond. Because pure silica is
strongly bonded, the melting temperature is too high to be
reached in ancient ovens. Therefore, network modifiers (the
sodium and potassium. On the other hand, they lose the
structure so much that the resulting glass is porous and has
poor durability. To avoid this drawback, another kind of
network modifier has to be added: the stabilizers. Earth
alkaline metals carry out this task very well, as they strengthen
the durability of the network, linking two oxygen atoms.
Transition metal ions such as Fe2+, Co2+, Mn3+, and Cu2+ are
added as colouring agents.
In Fig. 1 a simplified chronological representation of the
different window glass compositions in North-West Europe is
given.[8] During the Roman period, glass was made using natron,
a natural mixture of sodium salts,[2] in the entire Roman empire.
Around 800/900AD potash-rich ash obtained by burning forest
wood was used to lower the melting temperature during the
glass fabrication process in North-West Europe. This resulted in a
new type of glass composition, characterized by the presence of
high quantities of calcium and potassium and by the presence of
magnesium and phosphor.[7] For the production of window glass
* Correspondence to: Andrea Ceglia, Faculty of Engineering, Brussels Photonics
team B-PHOT, TONA-FirW, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussels,
Belgium. E-mail: and.ceglia@gmail.com
a Faculty of Engineering, Brussels Photonics team B-PHOT, TONA-FirW, Vrije
Universiteit Brussel, Pleinlaan 21050 Brussels, Belgium
b Faculty of Engineering, Research Group Electrochemical and Surface
Engineering, Department of Materials and Chemistry, SURF-FirW, Vrije
Universiteit Brussel, Pleinlaan 2B-1050 Brussels, Belgium
c Department of Art Sciences and Archaeology, Vrije Universiteit Brussel,
219

fluxes) are added to the batch to lower the melting temperature. Pleinlaan 21050 Brussels, Belgium

Surf. Interface Anal. 2012, 44, 219–226 Copyright © 2011 John Wiley & Sons, Ltd.

Figure 1. Window glass types produced in North-West Europe during time.
this kind of composition was applied until the introduction of
industrial soda (mid-19th century), but after the 17th century it
coexisted with salt marsh plant ash glass. The ash of these plants
was characterized by high tenor of sodium and the presence of
little quantities of potassium, magnesium, and phosphorous
oxides.[8]Material manufactured after 1865 was made using
industrial soda invented and produced by Solvay. As a
consequence glass of this period is again characterized by the
presence of high quantities of sodium and low impurities.[7] In
conclusion, we can state that depending on the period of
production, a different type of fluxing agent was applied. If we
are able to identify the type of flux, it is easier to distinguish
between post-medieval and industrial glass.
In practice the type of flux is identified by measuring the
chemical composition of the artefact making use of techniques
such as SEM coupled with energy dispersive X-ray spectroscopy
(SEM-EDX),[8–10] laser ablation inductively coupled plasma mass
spectrometry (LA-ICP-MS)[11–13] and X-ray fluorescence spectros-
copy (XRF).[14–16] Although these techniques have high perfor-
mances, some disadvantages exist. They require the use of
complex instrumentation and skilled people and – except for
XRF – these techniques can only be applied ex situ. Recently,
non-destructive ion beam analysis techniques, such as PIXE
(particle induced X-rays emission) and PIGE (proton induced
gamma ray emission), have been extensively employed
allowing the chemical characterization of glasses.[17–20] On
the other hand these techniques need a particle accelerator,
which is not always available. All this strengthens the demand
from the cultural heritage sector to have a straightforward,
portable and non-destructive technique.
The application of ultraviolet–visible–near–infrared (UV–VIS–
NIR) spectroscopy could accomplish all these requests. This
technique is fast, non-destructive and low-cost compared with
the expensive equipment for standard chemical analysis.
These features make optical spectroscopy appropriate for a
first-line analysis of a large, unexplored glass collection.
Moreover, this technique is non-destructive as it requires only
a restricted cleaning of the glass. Another strong point is the
availability on the market of portable spectrum analyzers,
which would allow in situ measurements.
Although optical spectroscopy is a suitable technique, it is
not widely employed in the study of ancient glass. Previous
applications are limited to the late Roman Palestine glass from
the archaeological sites of Galilea[1] and Jalame,[2] to the 1st
and 2nd century Roman glass from Coppergate, York,[21] to
the Roman glass from Colchester,22] to the 7th century glass
fragments of the Crypta Balbi in Rome,[23,24] to the Islamic
glass from Al-Andalus,[6] to the Neoreinassance/Neobaroque
stained glass windows from Madrid,[5] to pre-Roman glass
beads from Numantia,[25] to silver painted medieval glass[26]
and to the stained windows by Nicolò di Pietro Gerini in
Florence.[27]
In all of these publications the technique was mainly applied
to identify the specific absorption bands of the colouring agents.
220
In some of them spectroscopic data were used to gain
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A. Ceglia et al.
information about the redox conditions in the furnace during
the fabrication process.[1,2,21,23,24] Sometimes, the calculation of
the colour coordinates of the samples was carried out either to
draw conclusions about the production facilities and the
colouring agents used[2,23,24] or to make previsions about the
polymerization index of glass.[26] In [28] Bacci and Picollo analyzed
two glass pieces from two different 15th century churches, one
in Pisa and the other in Bologna, and they found a correlation
between the chemical composition of the samples and the
spectral position of their cobalt absorption bands.
In previous publications, our group has showed that some
parameters extracted from optical spectra can be helpful in
characterizing ancient glass.[29–31] The identification of the
colouring agents gives useful information about the raw
materials, and in some cases it can help the dating, such as for
the case of chromium coloured glasses.[29] The colour coordi-
nates can be related to the redox conditions of the furnace
employed for glass production, while the UV absorption edge is
linearly correlated to the presence of impurities such as iron.[30]
The objective of this paper is to extend the knowledge about
the relations between the glass chemistry and the spectral
position of the absorption bands of cobalt. Indeed, according to
the ligand field theory, when a transition metal ion experiences a
different electrostatic environment, its absorption bands change
in position.[32–34] The effect of the flux type on the position of
cobalt bands has already been noticed by Bacci and Picollo[28]
and by Green and Hart.[22] However, here, a systematic study of
this effect is proposed, and in addition, a real case-study will
illustrate how this phenomenon can contribute to the dating of
the different glass pieces present in a stained glass window.
Because of the spectral position of the cobalt absorption bands it
is possible to distinguish post-medieval from 19th and 20th
century restoration material in the case study of a Renaissance
stained glass window from the Church of Our Lady in Bruges,
Belgium. It is proved that optical spectroscopy is a powerful
technique in the study of ancient glass windows, especially
taking into account its non-destructive feature.
Research framework / hypothesis formulation
The selected material for this research contains only blue-
coloured glass. This article aims at building a reliable method
for distinguish glasses with deviant glass matrices using the
position of the absorption bands of cobalt. The blue colour is
developed when cobalt is tetrahedral coordinated by four
oxygen ions.[35] For this configuration three transitions are
allowed, but only two are detectable with normal spectro-
photometers: A2!T1(F) and A2!T1(P), which appear in the
near-infrared and in the visible region respectively.[33] Actually,
because of the Jahn–Teller effect, both bands are character-
ized by three sub-peaks located around 530 nm, 590 nm, and
650 nm for the visible peak and 1275 nm 1500 nm, and 1740
nm for the infrared region.[28] However, according to the
ligand field theory, the position of the absorption peaks of
transition metals is influenced by the ligand field strength.
Therefore, a change in chemical composition results in a shift
of the absorption bands.[32–34]
We suppose that by studying the position of the spectral
bands of this transition metal ion, it is possible to recognize the
main flux agents employed during the production of glass.
Surf. Interface Anal. 2012, 44, 219–226
Cobalt absorption bands for the differentiation of historical glass
Methodology
In general, our research consisted in building a reliable
method to study ancient glass material and consequently to
apply it to a case study to verify its effectiveness. The chemical
composition of 25 cobalt-coloured samples was measured
with SEM–EDX. This collection contains glasses from the
Roman period of the Renaissance window of the Church
Wardens from the Church of Our Lady in Bruges, Belgium, and
present-day industrial glasses. The chemical data were used to
classify the glasses according to their composition. Starting
from this point of view, optical spectra were recorded for all
the samples and compared. The spectra were studied in the
region between 190 and 1700 nm. However, the study will
mainly focus on the visible region (380–780 nm) because of the
common presence of iron in glass. In its reduced form (Fe2+)
it absorbs with a broad band centred at about 1050 nm,
which is very often strong enough to hide the absorption
peaks in the IR of cobalt.[35,36] Subsequently, a case-study was
worked out. We applied the parameter extrapolated from the
first investigation to the material of a renaissance stained
glass window of the Church of Our Lady in Bruges, Belgium.
The aim was to identify the post-medieval material and 19th
and 20th century restoration pieces, which might be an
important issue for deontological discussions.
Materials
One group consisted of 13 glass pieces coming from different
archaeological sites of the Roman period (five samples from Trou
de Han, Belgium; one from Olbia, France; two from Grobben-
donk, Belgium; two from Treignes, Belgium; and three from
Figure 2. On the left side, a picture of the window from the Church of Our Lady, Bruges, Belgium. On the right side, a schematic drawing of the six
upper panels where the glass was sampled. Sodium-rich glass and calco-potassic glass are represented in different stripe patterns. Samples were taken
from the edge of the panels hidden by the lead cames.
Surf. Interface Anal. 2012, 44, 219–226 Copyright © 2011 John Wiley & Sons, Ltd.
Avenches, Switzerland). A second group contained three con-
temporary mouth-blown window glass pieces from Glashütte
Lamberts, used for restoration purposes. A third group consisted
of nine blue glass samples taken from a stained glass window of
the Church Wardens designed for the Church of Our Lady (Bruges,
Belgium) and presumably dated around the 16th century. These
samples will be used as a case study to test the capabilities of our
method. In Fig. 2 a picture of the window under examination is
presented along with a schematic representation of the six upper
panels from where the blue samples were taken.
Instrumentation
Chemical analysis
The technique used to determine the major chemical composi-
tion of the artefacts was SEM–EDX. A JEOL JSM-6400 (JEOL LTD,
Tokyo, Japan) system was employed. All the spectra were
collected under the same experimental conditions. The current
in the tungsten filament was 1 nA and the voltage was set at 20
kV to excite all the elements present in the glass samples. Emitted
X-rays were recorded for 300 s of live time. To analyze properly
the bulk composition, the glass samples were inserted in the
epoxy resin, polished, and carbon coated; hence, all the
measurements were carried out on the freshly made cross-
section area. Peak identification was performed by filtering
without standards and the quantification was made by using the
PROZA correction method.[37] PROZA calibration factors were
recalculated for oxygen, sodium, potassium, manganese, iron,
calcium, magnesium, and aluminium using four Corning
standards (A, B, C, and D), the SRM 1830 (National Institute of
Standards and Technology), and the SRM 620 (National Bureau of
221
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Standards) standards. It can be stated that for major elements with
concentrations higher than 10 wt.% accuracy is less than 3%; for
minor elements, between 1 wt.% and 10 wt.%, it is normally lower
than 10%. Even though very good results in accordance with the
certified values were obtained for Fe, Mn, and Cu, EDX should be
considered semiquantitative for trace elements (less than 1 wt.%) as
errors are comparable with the total amount of an element.[38]
Optical analysis
Optical transmission spectra were recorded with a high-performance
optical spectrum analyzer (SA320, Instrument System, München,
Germany) between 300 and 1600 nm with a spectral resolution of 1.5
nm. The time required for the collection of a single spectrum is about
70 s. Two lamps were used as light source: a 30-W deuterium lamp for
the UV region (emitting between 190 nm and 400 nm) and a 20-W
halogen lamp for the VIS–NIR (emitting between 350 and 1700
nm) region. The light was guided from the sources towards the
sample by means of an optical fibre bundle transmitting light in
the spectral range between 300–2200 nm. A microscope objective
M-60 was used to focus the beam onto the sample with a spot size
of about 1.5 mm. The transmitted light was received in an optical
fibre (acceptance angle of 43 ), which guides the light towards
the entrance slit of the optical spectrum analyzer. The
transmission spectra presented below are smoothed using the
7-point adjacent average function of ORIGINPRO 7.5 software
(Originlab Corporation, Northampton, MA, USA) and the peak
positions were determined identifying the local minima of the
obtained spectra. The optical resolution of the instrument is given
as uncertainty on the spectral position. However, other aspects, such
as the stability of the source, play an important role in the quality of
the data. Hence, two series of repeatability measurements were
carried out using modern cobalt-coloured glass: first, a series of 11
measurements in the same session day; second, 11 measurements
were performed in different days. The standard deviations for the
cobalt peaks in the visible region were lower than 1.4 nm.[38]
In our set-up the technique has a spot size of 1.5 mm, therefore
for the analysis is required a minimum sample size of 22 mm,
which is comparable to the sample amount needed for a portable
XRF analysis.[39] Nevertheless, when a bigger volume needs to be
probed, it is possible to change the focusing lens of the optical
system to produce a larger spot size.
Results
Table 1 shows the chemical composition of all the samples
obtained by means of SEM–EDX. Roman glass is characterized by
high tenor of sodium oxide (between 13.8 wt.% and 18.8 wt.%)
and low quantities of potassium oxide (less than 1.2 wt.%). As
expected the industrial glass shows an important amount of
sodium oxide at about 15 wt.%. Concerning the samples from
the post-medieval stained glass window, seven out of nine
samples have a calco-potassic composition (K2O=4–9 wt.% and
CaO>16 wt.%), while two of them show high quantities of
sodium oxide (about 14 wt.%) together with the presence of
approximately 6 wt.% of lead oxide.
Considering the chemical data of all the samples, it is possible
to cluster the glasses in two new groups based on the flux agent
used for the production. Figure 3 presents a ternary plot of
sodium, calcium, and potassium oxides, which shows the
presence of the two groups: Ca/K-based and Na-based material.
Following our proposed methodology (see Section 3), after the
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chemical measures, the samples were analyzed by means of
wileyonlinelibrary.com/journal/sia Copyright © 2011 John Wiley & Sons, Ltd.
A. Ceglia et al.
optical spectroscopy. The results are presented taking into
consideration separately the two chemical groups, Na-based and
Ca/K-based material.
Figure 4(a) shows the transmission spectrum of sample
72GRO349C, belonging to the Na-group. Although by means of
SEM–EDX cobalt was not detected, UV–VIS–NIR spectra are
characterized by the presence of its absorption bands. In the
visible region the triplet (535, 595.5 and 640 nm) is attributed to
the Jahn–Teller split transition A2!T1(P) of tetrahedral geom-
etry of Co2+. In the infrared part of the spectrum, two of the three
sub-peaks (1260 and 1466 nm) because of the A2!T1(F)
transition are detectable.[33] The third one is located at about
1740nm and therefore it lies outside the range of the recorded
spectrum. Besides determining the presence of cobalt, spectro-
photometry allows the identification of iron in both redox states
Fe2+ and Fe3+. The ferric ion is detected because of the presence
of three weak absorption peaks at about 380, 420, and 440 nm,
whereas the ferrous ion is characterized by a broad absorption
band centred at about 1050 nm.[35,36]
Figure 4(b) presents the transmission spectrum of sample
C6s5, belonging to the group of calco-potassic glasses. Cobalt
absorption bands are recognizable both in the visible and in the
IR regions. Also, the bands attributed to iron are shown by the
spectrum, even though less evidently. Nevertheless, in this case
the positions of the cobalt bands are slightly different: 525.5, 594,
and 640nm in the visible region; 1205 and 1470nm in the IR.
In Figs 4(c) and (d) the transmission spectra of the Ca/K-based
sample (C6s5) and the Na-based one (72GRO349C) are compared
in the visible and IR regions. In both graphs a different position is
noticeable for the first sub-peak of the two cobalt absorption
bands. In the visible region the first peak is positioned at 526.5
nm for calco-potassic glass and at 535.5nm for the sodic glass. In
the IR region the lower wavelength absorption peak is placed at
1205nm and at 1260 nm for the Ca/K glass and the Na glass,
respectively. In both regions the first sub-peak is located at
shorter wavelengths in calco-potassic glass with respect to sodic
glass, suggesting a stronger ligand field in the first glass type.
Although for the short component of the triplet in the IR region
the shift is bigger than in the visible region, often this peak
cannot be detected, unless the glass is deeply coloured, as it is
hidden by the broad absorption of Fe2+ centred at about 1050
nm (Fig. 5). Indeed, looking at Table 1, it is clear that iron is
almost always present as an impurity in ancient glass.
Nevertheless, in the visible region the presence of iron, in any
of its oxidation states, does not affect the identification of cobalt
bands; hence, this feature can be used in the study of glass.
In Table 2 the positions of the triplet band in the visible region
for cobalt are listed for all the samples. It is easy to observe that in
all the samples of the Na-based group the position of the first
component of the triplet is placed between 532 and 536nm.
Regarding the Ca/K-based group, the first peak is located at 526.5
nm in all the samples. Similar results were found in 1987 by Green
and Hart, who studied a group of Roman and a group of 15th
century blue glasses. They discovered that Na-rich Roman glass
had a peak position of cobalt at about 535nm, while for the 15th
century calco-potassic material, the peak appeared at about 520
nm, both values with a range of about 5nm.[22]
To test the method, we applied it to a case study: the blue
glasses of the window of the Church of Our Lady. This window is
dated between the 15th and the 16th century and, accordingly
to Fig. 1, should be made of calco-potassic glasses. During the
following restoration – especially after the industrial revolution –
Surf. Interface Anal. 2012, 44, 219–226
 Table 1. SEM–EDX analysis of Roman, post-medieval, and industrial samples
Location Sample Na2O MgO Al2O3 SiO2 P 2O 5 SO3 Cl K 2O CaO TiO2 MnO Fe2O3 Pb2O CuO

ROMAN GLASS
3*Avenchesa Av(no.13) 16.4 0.4 1.8 72.4 nd 0.1 0.9 0.5 6.1 0.1 0.2 0.8 nd 0.2
Av(no.15) 16.4 0.5 2.1 68.7 nd 0.2 0.9 0.6 7.8 nd 0.6 1.8 nd 0.3
Av(no.18) 17.3 0.5 2.1 68.1 nd 0.2 0.9 0.7 7.9 0.1 0.4 1.6 nd 0.2
5*Trou de Han (SIB) 16.9 0.2 2.5 70.9 nd nd 1.3 0.5 6.3 nd 0.5 0.9 nd nd
(SIA) 13.8 0.6 2.4 71.7 nd nd 1.0 0.8 7.8 nd 1.1 0.9 nd nd

Surf. Interface Anal. 2012, 44, 219–226

A78-11 18.8 0.6 2.5 65.7 nd 0.6 1.0 0.6 8 nd 1.2 0.9 nd nd
A70-185 17.7 0.7 2.3 70 nd 0.4 1.0 0.6 6.5 nd 0.2 0.7 nd nd
C78-102 17 0.3 1.9 71.1 nd nd 1.1 0.4 6.1 nd 1 1.1 nd nd
2*Treignes TreignesA 15.3 0.5 2.6 70.9 nd nd 1.1 0.5 6.7 nd 1.7 0.9 nd nd
(X-Z/26-28) 17.6 0.5 2.6 68.7 nd nd 1.1 0.8 7 nd 0.6 1.1 nd nd
1*Olbiaa 061-3 18.8 1 2.4 64.6 nd 0.1 0.6 1.2 6.4 0.1 2.1 2.4 nd 0.3
2*Grobbendonk 72GRO349C 16.1 0.3 1.9 72.1 0.2 0.2 1.3 0.4 5.9 nd 0.7 1.0 nd nd
73GRO54 15.4 0.4 2.6 70.9 0.2 0.2 1.1 0.5 7.1 0.2 0.4 1.2 nd nd
POST-MEDIEAVAL
9*Church of Our Lady (Bruges) A6s11 2.5 4.3 2.4 57.9 3.5 0.3 0.6 6.8 19.7 0.6 0.9 0.7 nd nd
A6s49 14.7 nd 5 62.8 0.4 nd 0.7 2.3 7 nd nd 1.2 6.1 nd
Cobalt absorption bands for the differentiation of historical glass

B5s23 2.8 5.2 2.5 58.6 3.3 0.3 0.5 8.5 16.7 0.1 0.7 0.7 nd nd
B6s16 2.6 5.3 2.4 58.1 3.4 0.2 0.5 8.5 17.2 0.3 0.8 0.7 nd nd
B6s28 2.7 5.2 2.2 57.9 3.3 0.3 0.5 8.7 17.4 0.3 1 0.7 nd nd
C2s9 2.8 3.9 3.5 60.9 3 0.2 0.8 4.1 19 0.2 0.9 0.7 nd nd
C6s5 2.8 3.8 3.3 60.8 3 nd 0.7 4.2 19.7 0.3 0.6 0.8 nd nd
C6s42 2.7 5 2.1 57.9 3.2 0.3 0.5 9.0 17.5 0.2 0.8 1.0 nd nd

Copyright © 2011 John Wiley & Sons, Ltd.

C6s43 13.6 nd 5.3 62.7 0.9 nd 0.9 2.2 7 nd 0.2 1.3 5.9 nd
INDUSTRIAL
3*Lambert Glashütten (Germany) 1201xx 14.4 0.1 0.9 71.7 0.2 0.3 nd 2.0 8.3 nd 1.3 0.8 nd nd
1254F 15 1.1 1.2 70.1 nd 0.2 nd 1.7 7.8 nd nd 1.5 nd nd
3219xx 15.6 1.6 1.1 70.3 nd 0.3 nd 1.4 7.9 0.1 nd 1.1 nd nd
STANDARDS
Corning A (certified) 14.3 2.7 1.0 66.6 0.1 0.1 0.1 2.9 5 0.8 1.1 1 — 1.2
Corning A (measured) 14.3(0.1) 2.7(0.1) 1.0(0.1) 68.5(0.2) 0.2(0.1) 0.2(0.1) 0.1(0.1) 2.9(0.1) 5.2(0.1) 1.4(0.1) 1.1(0.1) 1.1(0.1) 1.3(0.2)
Corning D (certified) 1.2 3.9 5.3 55.2 3.9 0.3 0.4 11.3 14.8 0.4 0.6 0.5 — 0.4
Corning D (measured) 1.4(0.1) 4.1(0.1) 5.3(0.1) 55.8(0.2) 4.2(0.1) 0.2(0.1) 0.2(0.1) 11.5(0.1) 15.3(0.1) 0.7(0.1) 0.6(0.1) 0.5(0.1) 0.4(0.1)

Values are given in wt.%. Uncertainties are specified in the text; however, for a quantification of the accuracy, Corning standard A and Corning standard D values are reported. In brackets are given
the standard deviations calculated on 11 measurements.
nd=not detected.
a
Data kindly provided by Peter Cosyns.

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223

Figure 3. Plot of sodium, calcium, and potassium oxides normalized to
1. The circles highlight two separated groups.
the restoration material would have been soda glass. It is
possible to use the position of cobalt bands as marker of the flux
employed to distinguish original from restoration material.
Figure 6 shows a magnified view of the first cobalt band in the
visible region for four samples of the window. Samples A6s49
and C6s43 of the window have the first absorption band of
cobalt placed at 535.5 and 534.0nm, whereas the other seven
glasses taken from the window show the absorption band at
Figure 4. (a) Transmission spectrum of the sodic glass sample 72GRO349C. (b) Transmission spectrum of the calco-potassic sample C6s5. (c) Visible
224
and (d) infrared transmission spectra of the calco-potassic glass and the sodic glass. Shifts towards higher energies are noticeable for the Ca/K glass.
wileyonlinelibrary.com/journal/sia Copyright © 2011 John Wiley & Sons, Ltd.
A. Ceglia et al.
526.5nm (in the figure only two are reported to make the graph
easier to read). These values are compatible with a soda and a
calco-potassic glass matrix, respectively.
Indeed, considering the chemical data reported in Table 1,
samples A6s49 and C6s43 have about 14wt.% of sodium oxide
content, while the other samples are characterized by 4–9wt.%
of potassium oxide and an amount of calcium oxide higher than
16wt.%. In the schematic representation of the panels of Fig. 2,
post-medieval glass is reported in horizontal lines, while more
recent restoration material is filled with vertical lines.
Using optical spectroscopy, it was possible to recognize the post-
medieval blue glasses of the window without using destructive and
expensive techniques such as SEM–EDX. This optical parameter can
be used in deontological discussions during conservation campaigns
to distinguish post-medieval from 19th and 20th century pieces.
Conclusions and Future work
In archaeometric research, glass materials are usually studied by
means of X-ray elemental analysis, such as XRF or SEM–EDX. We
showed that optical spectroscopy can be used in a straightfor-
ward way to identify the band positions of the colouring agents.
This paper shows that cobalt is an efficient marker to identify the
fluxes used for glass production; therefore, it can help to
distinguish medieval and post-medieval material from pieces
added during more recent restoration campaigns. Starting from
the chemical analyses of Roman, post-medieval, and industrial
glasses, two compositional groups were identified: a calco-potassic
Surf. Interface Anal. 2012, 44, 219–226
Cobalt absorption bands for the differentiation of historical glass

Figure 5. Transmission spectrum of a Roman sodic glass. The absorption

bands of cobalt in the IR are hidden by the presence of ferrous iron.
and a sodic one. Optical spectroscopy was employed to compare
the spectra of the two compositional groups. Considering the
spectral position of the short wavelength band of the samples, it
was demonstrated that in calco-potassic glasses cobalt showed a
shift towards shorter wavelengths with respect to the cobalt
absorption bands in soda glass.
Afterwards this parameter was applied to the case study of the
blue samples of the Renaissance stained glass window of the
Church of Our Lady in Bruges, Belgium. Two groups of glasses
Figure 6. Transmission spectra of two sodium-rich (A6s49 and C6s43)
and two calco-potassic glasses (B6s28 and B5s23) from the window of the
Church of Our Lady. The range of wavelength was chosen to underline
the shift of the first cobalt absorption band in the visible region.
were classified as sodic restoration glasses in agreement with the
chemical analysis. The rest of the samples were calco-potassic
glasses, in accordance with the periods of fabrication. This
method may be applied to other cases of blue glasses from the
similar period of production, helping to distinguish the post-
medieval from the industrially produced material.

Table 2. Spectral position of the peaks of cobalt for Na-rich and K-rich glasses
Glass type Location Sample Peak 1 (nm) Peak 2 (nm) Peak 3 (nm)

Roman
3*Avenches Av(no.13) 535.51.5 5941.5 643.51.5
Av(no.15) 5341.5 595.51.5 646.51.5
Av(no.18) 535.51.5 595.51.5 646.51.5
5*Trou de Hana (SIB) 5362 5922 6442
(SIA) 5342 5962 6422
A78-11 5342 5962 6422
b b
A70-185 5342
b b
C78-102 5362
a
2*Treignes TreignesA 5322 5942 6422
(X-Z/26-28) 5362 5962 6462
Na-rich 1*Olbia 061-3 535.51.5 594.01.5 645.01.5
2*Grobbendonka 72GRO349C 5362 5942 6402
b
73GRO54 5342 5942
Post-medieval
2*Church of Our Lady (Bruges) A6s49 535.51.5 595.51.5 6481.5
C6s43 5341.5 595.51.5 646.51.5
Industrial
3*Lambert Glashütten (Germany) 1201xx 5341.5 5941.5 6421.5
1254F 535.51.5 598.51.5 6481.5
3219xx 5341.5 5971.5 6451.5
Ca/K-rich Post-medieval
7*Church of Our Lady (Bruges) A6s11 526.51.5 595.51.5 646.51.5
A6s28 526.51.5 595.51.5 649.51.5
B5s23 526.51.5 595.51.5 649.51.5
B6s16 526.51.5 595.51.5 6511.5
B6s28 526.51.5 595.51.5 649.51.5
C6s5 526.51.5 5941.5 642.0b
C6s42 526.51.5 5971.5 6511.5
a
Data collected with a spectral resolution of 2nm.
b
Peak completely or partially saturated because of the high intensity of the absorption.
225

Surf. Interface Anal. 2012, 44, 219–226 Copyright © 2011 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/sia

In the future, research should be conducted to study the
correlations between different glass types and the absorption
bands of other transition metals normally used as colourants in
glassmaking. Also, a subdivision of the large group of post-
medieval calco-potassic window glass will enable us to differentiate
the material used from the 16th until the mid-19th century. This will
permit us to refine the dating of archaeological and in situ preserved
collections.
Acknowledgements
The authors would like to express their gratitude to the Vrije
Universiteit Brussel for the funding of this research in the framework
of different projects (HOA15 - IOF-POC1). The authors are also very
grateful to all persons who granted us the kind permission to study
their material and in particular A. de Pyre-Gysel (Avenches samples);
M. Gansbeke, K. Van Dorpe and church wardens (Bruges samples); R.
Annaert and S. Vanhoutte (Grobbendonk samples); Souen Fontaine
of the University of Aix-Marseille, LAMM and Michel Bats of the
CNRS-Lattes (Olbia sample) and E. Warmenbol (Treignes and Trou-
de-Han samples). The authors are also grateful to three anonymous
reviewers for their precious remarks and advices.
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