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Journal of Cultural Heritage 9 (2008) e129ee133

Original article

Float glass colouring by ion exchange

Abel Puche-Roig*, Vicent Primo Martn, Sonia Murcia-Mascaros, Rafael Iba~
nez Puchades
Instituto de Ciencia de los Materiales de la Universidad de Valencia (ICMUV), P.O. Box 22085, 46071 Valencia, Spain
Received 30 March 2008; accepted 5 August 2008

Abstract

Back in the Middle Ages, glass artists used to produce yellowish colorations in soda-lime glasses using mixtures that contained silver salts,
clay composites and natural oils. The resulting colour was a characteristic pale yellow known as silver-stain. This coloration is mainly caused by
the extinction e absorption and, to a lesser extent, scattering e of light occasioned by silver nanoparticles formed inside the glass. This colouring
technique comprises a heat treatment divided in two stages: in the first one, an ion exchange between the silver ions in the mixture and the alkali
ions in the glass takes place. This process is called nucleation of silver nanoparticles. The second stage consists of a reduction process that causes
the growth of these nanoparticles and the development of colour. This is known as growth and aggregation of nanoparticles. In our work,
systematic working procedures have been developed with the aim of reproducing silver-stain in modern soda-lime glasses formed by flotation.
2008 Elsevier Masson SAS. All rights reserved.

Keywords: Silver nanoparticles; Surface plasmon resonance; Silver-stain; Ion exchange; Kaolinite; Sepiolite; Sodium bentonite; Light extinction; Light absorption;
Light scattering; Float glass; Soda-lime glass; Mie theory

1. Introduction establishing that the process or ion exchange speed is influ-

Yellow coloration by silver is a technique that started to be
used early in 14th century to obtain yellow tonalities in glasses
[1]. The production of this colour consisted of diverse stages.
First of all, silver mixtures were elaborated from water-based
suspensions containing four basic ingredients: water, silver
salts, clay mineral composites and natural oils [2e4]. These
mixtures were spread over the surface of the sample glasses,
which were then submitted to a heat treatment whose aim was
to generate a ion exchange process of silver ions from the
contact surface to the glass interior: the alkali ions in the glass
were exchanged by the silver ions contained in the mixture
covering the glass surface. The ion exchange process produces
a silver ion concentration gradient inside the sample glass. The
whole process was ruled by Ficks law of diffusion, whose first
approach considers the only diffusion of the silver ion species,
* Corresponding author.
E-mail addresses: abel.puche@uv.es (A. Puche-Roig), sonia.mascaros@
uv.es (S. Murcia-Mascaros), rafael.ibanez@uv.es (R.I. Puchades).
enced by diverse factors, such as temperature at which it takes
place, and concentration of surface silver ions. Several silver
salts, (nitrates, sulphates or sulphides), can be used to produce
the coloration. Solubility in water simplifies the mixtures
production but is not necessary since colloidal suspensions can
also colour the glass. The maximum treatment temperature is
frequently higher than melting and decomposition temperature
for the majority of silver salts used in the mixtures (silver
nitrate melts at 212  C and decomposes at 440  C in example).
Melted silver salts over the glass surface improves the ion
exchange process due to the higher ion mobility, actually
melted salt bath has been used more recently extensively to
produce silver ion gradient in glass [5]. Thermal silver salt
decomposition (combustion) produces local oxidizing or
reducing conditions (depending on the anion), but the total
amount of salt is low and in consequence do not perturbs ion
exchange or metal cluster formation. The process was fav-
oured by the similarity in ionic charge and radius of the ions
involved, and its general scheme can be described with the
following equation [6]:

1296-2074/$ - see front matter 2008 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.culher.2008.08.006
e130 A. Puche-Roig et al. / Journal of Cultural Heritage 9 (2008) e129ee133
^SieO eM RAg %^SieO eAg
RM R^NO 2 2
3 ; SO4 ; SO ; M^Na ; K
After the first treatment, glass pieces underwent a reducing
heat treatment, which was achieved by combustion of vege-
table organic matter inside the furnace. This treatment acti-
vated diverse redox processes, causing the reduction of silver
ions and the oxidation of other species present in the glass.
Metallic silver atoms acted as metallic silver nuclei for crys-
tallization, which, after the heat treatment, incorporated the
silver ions located around them. The final result was the
growth of the aggregate ions until they became silver nano-
particles with a size larger than tens of nanometers [7e9].
M e /M0
M0 M /M 2
M
2 M0 /M3
/ used in original mixtures; of other species e such as antimony
M
n1 M0 /Mn
 0
Mn e /Mn
The species involved in the redox processes of silver could
be metals such as Sb3 and As3, which were frequently
added to glass composition in ancient times. However,
nowadays it is widely known that silver ion reduction can
occur due to chemical interaction with non-linking oxygens
present in the glass network, so the presence of traditional
reducing agents in the glass is no longer required to accom-
plish these processes [4,10].
When electromagnetic radiation penetrates a glass con-
taining metal nanoparticles, various light extinction
phenomena occur, giving it the characteristic yellow colora-
tion. Light extinction is mainly due to the absorption induced
by the presence of silver nanoparticles: a collective oscillation
of their electrons in the conduction band, called surface
plasmon resonance (SPR), can take place under the action of
the electromagnetic radiation field, provided it has the proper
frequency (energy). The chemical composition and geometric
parameters of nanoparticles as well as the environment that
surrounds them, determine their spectroscopic behaviour e
resonance position and width at half absorption e and thus the
final colour of the glass [7]. To a lesser extent, the light
scattering caused by larger nanoparticles contributes to the
final colour of the glass by producing certain chromatic
nuances that absorption alone cannot achieve. By mastering
this technique, glass artists achieved a chromatic diversity that
ranged from pale yellow to reddish hues.
The components that glass artists used to employ in their
mixtures had a very specific function, but we ignore to what
extent that function was known in ancient times. Mixtures
used to be water-based, and they were mixed with organic
components based on vegetable extracts and oils, and with
clay mineral materials that were often extracted from mineral
deposits located near the glass workshops. This seems to
indicate that colour could be obtained from a wide range of
raw materials, whose function was to provide good rheology
for the deposition and coating of the glass surfaces which were
to be coloured. Nowadays, the excellent ion exchange capacity
of phyllosilicates is widely known. Their crystalline structure
e which can be laminar, as in montmorillonite, or present
three-dimensional channels, as in sepiolite e enables them to
retain the alkali ions extracted from glass during the ion
exchange process, facilitating it. The combustion of organic
matter created slightly reducing conditions inside the furnace
which facilitated the reduction of the silver ions that had been
exchanged in the glass. The water base of the mixture allowed
the dissolution of the silver salts e which were likely to
contain ionic compounds of other metals due to the absence or
inefficiency of the purification procedures employed e that
were used in the colouring process.
The glass we chose to carry out our work is a common
soda-lime float glass. The presence e inherent to the float
forming process e of tin species on one of the glass sides
introduced a new source of variation in the colour, and was
used as a substitute for the reducing power of the essential oils
or arsenic e found in the raw materials employed in the
elaboration of glass, or of the atmosphere used in original
treatments [4,11].
The aim of our work is the systematization and simplifi-
cation of yellow coloration by silver in modern glasses. First
of all, we developed our own silver mixtures based on modern
and commercial components e whose number was kept to
a minimum to eliminate variability sources in the final colour.
In order to simplificate the mixture formulations and reduce
the subproducts of their combustion during the treatment, no
essential oils were used in these mixtures. The silver source
we used was silver nitrate, a common and available salt.
Finally, we chose three minerals with different structural
features as ion exchangers: kaolinite, sodium bentonite and
sepiolite. They all belong to the group of phyllosilicates, and
are capable of exchanging the ions fixed on the outer surface
of their crystals, or in the interlaminar spaces (kaolinite and
bentonite), or inside the three-dimensional channels (sepiolite)
of their structures for other ions present in the surrounding
water-based solutions. We tested different glass coloration
procedures, studying, first of all, the influence of diverse
parameters e the amount of silver and the mineral employed
e related to the mixtures we used. Subsequently, we studied
the influence that heat treatment characteristics have on the
final colour of the glass, evaluating this influence at the highest
temperature reached.
2. Experimental procedure
The silver mixtures we used were formed by the commercial
variety of the ion exchanger (sepiolite, bentonite or kaolinite)
employed in each case. The variety of sepiolite we used came from
Spanish mineral deposits, and was provided by the firm Sepiolsa
S.A. under the commercial denomination Sepiolita <100. The
sodium bentonite also came from Spain and its supplier was Mario
Pilato Blat S.A. The kaolinite came from an Australian mineral
deposit located in Queensland. The optimal water/mineral
proportions for each exchanger were determined to achieve the best
rheology. For kaolinite and sepiolite, these proportions were 6.7 g
 A. Puche-Roig et al. / Journal of Cultural Heritage 9 (2008) e129ee133
of water per gram of mineral, whereas bentonite required a relation
of 3.5 g of water per gram of mineral. The amount of mixture
deposited on the surface of each glass sample was 0.5 g. The
proportions of AgNO3 are given in percentage in relation to the
mass of mineral in the mixture. The water we employed came from
a MiliQ purifier, and the silver source was silver nitrate supplied by
Metalor S.A. Soda-lime float glass is a 2-mm-thick common
commercial glass used for framing prints. We cut it in sample
pieces of 3.5 cm long and 2.5 cm wide that were washed for 15 min
in an ultrasound bath using commercial soap. They were subse-
quently cleaned with acetone and laboratory paper, and dried in
a drying oven at 120  C for 1 h. The glass pieces were placed under
a 294 nm UV lamp to distinguish unequivocally the tin side from
the non-tin side.
3. Results and discussion
Distinguishing the tin side from the non-tin side is easy
after observing the glass samples under UV light (294 nm UV
lamp). The float conformation process causes the Sn(II) to
diffuse into the glass [11].
The fact that during the Middle Ages, many different
workshops throughout Europe accomplished yellow coloration
by silver based on recipes that contained clay composites from
diverse origins, allows us to formulate the hypothesis that the
function of this ingredient is to accept and retain the alkali ions
extracted from the glass. To test this hypothesis, we used diverse
silver mixtures, each of them containing an exchanger with
different composition and crystalline structure. The amount of
silver introduced in the mixture remained unchanged, and the
samples were submitted to a heat treatment at 600  C for 6 h.
The spectrum of the coloured glass samples is shown in Fig. 1.
As can be observed, a characteristic spectrum of glass
samples coloured by silver nanoparticles was obtained for the
three exchangers employed. The resonance frequency of
the silver plasmon was about 3.0 eV, which is equivalent to
approximately 425 nm. These results are compatible with
5
Na-Bentonite
Sepiolite
Kaolinite
4 5%
3
OD
2
1
0 0
2.0 2.5 3.0 3.5
E (eV)
Fig. 1. UVeVis spectra of glass samples coloured with mixtures containing
different ion exchangers.
e131
those obtained in previously published works [11e14]. Of the
three mixtures employed, the kaolinite mixture shows the
minimum absorption intensity. The mixture using sodium
bentonite as an exchanger is the one that presents a higher
absorption, even saturating the detector response. The sepiolite
mixture holds an intermediate position between the former
two. After observing the glass samples coloured with the
sodium bentonite mixture, we appreciated that the colour
intensity was similar to the one achieved using sepiolite, but
the surface that had been in contact with sodium bentonite was
very affected mechanically: it was more translucent, and the
traces of sodium bentonite had not been completely removed
from some areas of the sample. A possible explanation for this
deterioration is the high sodium content in sodium bentonite,
and the role this element plays as a flux. The contact with
sodium oxide at high temperatures produces a lowering of the
glass transition temperature that is more noticeable than the
one produced in the samples which are in contact with sepi-
olite or kaolinite. We decided to use sepiolite in our work
because of its sensible lack of effects on the glass surface, its
better performance on the final colour, and the good rheologic
properties it gives to the suspension.
In ancient times, very low concentrations of silver were
used to obtain coloured glass. We tested different amounts of
silver in the mixtures (1% is equivalent to 0.001 g and 10% is
equivalent to 0.010 g AgNO3 contained in the 0.5 g of
mixture) to know the variation of spectroscopic properties
according to the silver content. The UVevis spectrum of these
glass samples (submitted to a heat treatment at 600  C for 6 h)
is shown in Fig. 2.
The maximum absorption intensity e and the coloration
intensity e depends on the silver content of the mixture, since
it increases according to the amount of silver employed. The
area under the curve in the UVevis spectrum is linked to the
total volume of absorbing species in the environment (silver
nanoparticles in this case). Fig. 3 e where the area under the
curve from the previous figure is represented against the
4
1%
2%
10%
3
OD
2
1
2.0 2.5 3.0 3.5
E (eV)
Fig. 2. UVeVis spectra of glass samples that have been coloured using
mixtures with variable amounts of AgNO3.
e132 A. Puche-Roig et al. / Journal of Cultural Heritage 9 (2008) e129ee133
300
250
200
Area (a.u.)
150
100
50
0 In order to evaluate the influence of the heat treatment
0 2 4 6 8 10
Nominal AgNO3wt.%
Fig. 3. Representation of the area under the curve from the previous figure
against the nominal amount of AgNO3 present in the mixtures used in the
coloration process.
nominal content of silver used in the mixtures e shows that
this delineating relation can be supposed.
In many cases the amount of doping ions entering the
glass is proportional to the surface concentration of the
species to be diffused. By increasing the nominal amount of
silver nitrate in the mixture employed in the coloration, we
increased the total amount of doping ions entering the glass
e and therefore, the concentration of Ag ions, since all the
processes occurred during the same time interval. A higher
number of Ag ions inside the glass can cause two different
situations: 1) an increase in the average size of the metal
nanoparticles formed inside the glass, their concentration
being kept constant; 2) an increase in the concentration of
those metal nanoparticles inside the glass whose average
radius does not vary significantly depending on the amount of
Ag present in their environment. According to Mie theory
for light extinction caused by metal colloids randomly
distributed in a dielectric medium, the average distribution
radius of colloids is a fundamental parameter in their optical
response. According to diverse interpretations, a shift in the
absorption maximum towards lower resonance energies could
be produced by an increase in the average silver nanoparticle
radius [12]. Observing the position of the absorption
maximum in the UVevis spectra according to the nominal
amount of silver nitrate, we can affirm that its energy value
does not change significantly in relation to the amount of
silver employed. Furthermore, according to the Lamberte
Beer law for the absorption of radiation, absorption intensity
is proportional to the absorption coefficient that is related to
the absorption cross-section of silver nanoparticles and their
density in the glass environment [15]. What can be observed
in the graph is an increase in the maximum intensity
according to the concentration of silver employed in the
mixture. This suggests that an increase in the concentration of
silver in the mixture causes an increase in the amount of Ag
inside the glass. Accordingly to this results we suggest that an
increase in silver content generates an increase in the
concentration of metal nanoparticles formed inside the glass,
but does not modify significantly their average radius.
Therefore, the average distribution radius of metal nano-
particles is a parameter which is not directly related to the
silver content of the mixture. Nevertheless, further studies are
being performed in order to show results that may corrobo-
rate this conclusion. Considering the amount of AgNO3
contained in the mixture (1% wt. or 0.001 g) and the glass
surface coloured (2.5  3.5 cm 8.5 cm2), we observed that
a silver nitrate surface density as low as 1.14$104 g of
AgNO3/cm2 is enough to obtain an appreciable glass colour
in glass.
maximum temperature on coloration, we treated four glass
samples with the same mixture (2 wt.% AgNO3 in relation to
the mass of sepiolite), but at different maximum temperatures.
The results are depicted in Fig. 4.
As can be observed, the maximum temperature of the
treatment has a dramatic effect on the UVevis spectrum of the
sample glasses. With regard to the absorption intensity, there
exists a minimum temperature between 300  C and 400  C at
which metal nanoparticles begin to absorb light. Under that
temperature, the ionic interdiffusion process does not reach
proper extension, and the redox reactions involved in the
formation of metal nanoparticles do not occur. The result is the
absence of absorption in the UVevis area of the spectrum due
to an unnoticeable concentration of the optically active
species. By analyzing the position of the absorption maximum
according to temperature, we can establish that there exists an
inverse relation between these parameters, since the energy of
the absorption maximum decreases as the treatment tempera-
ture increases (3.07 eV for the glass sample treated at 500  C
and 2.97 eV when the temperature reached 600  C). Accord-
ing to Mie theory, a shift towards lower values of absorption
energy is related, all other factors being equal, to an increase
in the average distribution radius of metal nanoparticles: an
3
300C
400C
500C
600C
2
OD
1
0
2.0 2.5 3.0 3.5
E (eV)
Fig. 4. UVeVis spectra of sample glasses treated at different maximum
temperatures for 6 h using a mixture with 2 wt.% AgNO3.
 A. Puche-Roig et al. / Journal of Cultural Heritage 9 (2008) e129ee133
increase in temperature causes an increase in the average
radius of the metal nanoparticles formed inside the glass
[11,12]. The reason for the increase in the average size of
nanoparticles lies fundamentally in their thermodynamic
stabilization (reduction of free energy), which takes place
when temperature rises above a specific value [7]. To sum up,
treatment temperature has two combined effects on the
formation of metal nanoparticles: first, it increases the
concentration of silver inside the glass due to an increase in
the speed of the ionic diffusion process. As we have previously
observed, this causes an increase in the concentration of metal
nanoparticles. And second, with the increase in temperature,
the thermodynamic stability of larger metal nanoparticles
increases too, resulting in a growing maximum absorption
intensity and a shift in the absorption position towards lower
energy values as the treatment temperature increases.
4. Conclusions
In our work, the basic ingredients described in different
mediaeval recipes for obtaining silver-stain glasses have been
employed in the preparation of modern mixtures to achieve the
aforementioned colour. It has been determined that the use of
clay minerals in the mixtures is not restricted to a specific kind
of them, since we have verified that silver-stain glasses can be
obtained using three crystalline structures that present signif-
icant differences. Finally, we have established the influence
that the treatment temperature and the amount of AgNO3
contained in the mixture have on the characteristics of the
silver nanoparticles distribution inside the glass e which
ultimately account for the spectroscopic properties of the
glass.
Acknowledgements
Our acknowledgements go to the Spanish Ministerio de
Educacion y Ciencia (Project ref. MAT2006-04072) and
Generalitat Valenciana (grant ref. CTBPRB/2003/137) for
economical support. S.M.M. is funded by the program Ramon
y Cajal. A.P.R. is funded by the program F.P.I. Authors are
very grateful to the reviewers for their useful comments and
suggestions.
e133
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