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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-


enced by diverse factors, such as temperature at which it takes
Yellow coloration by silver is a technique that started to be place, and concentration of surface silver ions. Several silver
used early in 14th century to obtain yellow tonalities in glasses salts, (nitrates, sulphates or sulphides), can be used to produce
[1]. The production of this colour consisted of diverse stages. the coloration. Solubility in water simplifies the mixtures
First of all, silver mixtures were elaborated from water-based production but is not necessary since colloidal suspensions can
suspensions containing four basic ingredients: water, silver also colour the glass. The maximum treatment temperature is
salts, clay mineral composites and natural oils [2e4]. These frequently higher than melting and decomposition temperature
mixtures were spread over the surface of the sample glasses, for the majority of silver salts used in the mixtures (silver
which were then submitted to a heat treatment whose aim was nitrate melts at 212  C and decomposes at 440  C in example).
to generate a ion exchange process of silver ions from the Melted silver salts over the glass surface improves the ion
contact surface to the glass interior: the alkali ions in the glass exchange process due to the higher ion mobility, actually
were exchanged by the silver ions contained in the mixture melted salt bath has been used more recently extensively to
covering the glass surface. The ion exchange process produces produce silver ion gradient in glass [5]. Thermal silver salt
a silver ion concentration gradient inside the sample glass. The decomposition (combustion) produces local oxidizing or
whole process was ruled by Ficks law of diffusion, whose first reducing conditions (depending on the anion), but the total
approach considers the only diffusion of the silver ion species, amount of salt is low and in consequence do not perturbs ion
exchange or metal cluster formation. The process was fav-
* Corresponding author.
oured by the similarity in ionic charge and radius of the ions
E-mail addresses: abel.puche@uv.es (A. Puche-Roig), sonia.mascaros@ involved, and its general scheme can be described with the
uv.es (S. Murcia-Mascaros), rafael.ibanez@uv.es (R.I. Puchades). 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 of phyllosilicates is widely known. Their crystalline structure
e which can be laminar, as in montmorillonite, or present
RM R^NO 2 2
3 ; SO4 ; SO ; M^Na ; K

three-dimensional channels, as in sepiolite e enables them to
After the first treatment, glass pieces underwent a reducing retain the alkali ions extracted from glass during the ion
heat treatment, which was achieved by combustion of vege- exchange process, facilitating it. The combustion of organic
table organic matter inside the furnace. This treatment acti- matter created slightly reducing conditions inside the furnace
vated diverse redox processes, causing the reduction of silver which facilitated the reduction of the silver ions that had been
ions and the oxidation of other species present in the glass. exchanged in the glass. The water base of the mixture allowed
Metallic silver atoms acted as metallic silver nuclei for crys- the dissolution of the silver salts e which were likely to
tallization, which, after the heat treatment, incorporated the contain ionic compounds of other metals due to the absence or
silver ions located around them. The final result was the inefficiency of the purification procedures employed e that
growth of the aggregate ions until they became silver nano- were used in the colouring process.
particles with a size larger than tens of nanometers [7e9]. The glass we chose to carry out our work is a common
soda-lime float glass. The presence e inherent to the float
M e /M0 forming process e of tin species on one of the glass sides
M0 M /M 2 introduced a new source of variation in the colour, and was
M
2 M0 /M3

used as a substitute for the reducing power of the essential oils
/ used in original mixtures; of other species e such as antimony
M
n1 M0 /Mn

or arsenic e found in the raw materials employed in the
 0
Mn e /Mn elaboration of glass, or of the atmosphere used in original
The species involved in the redox processes of silver could treatments [4,11].
be metals such as Sb3 and As3, which were frequently The aim of our work is the systematization and simplifi-
added to glass composition in ancient times. However, cation of yellow coloration by silver in modern glasses. First
nowadays it is widely known that silver ion reduction can of all, we developed our own silver mixtures based on modern
occur due to chemical interaction with non-linking oxygens and commercial components e whose number was kept to
present in the glass network, so the presence of traditional a minimum to eliminate variability sources in the final colour.
reducing agents in the glass is no longer required to accom- In order to simplificate the mixture formulations and reduce
plish these processes [4,10]. the subproducts of their combustion during the treatment, no
When electromagnetic radiation penetrates a glass con- essential oils were used in these mixtures. The silver source
taining metal nanoparticles, various light extinction we used was silver nitrate, a common and available salt.
phenomena occur, giving it the characteristic yellow colora- Finally, we chose three minerals with different structural
tion. Light extinction is mainly due to the absorption induced features as ion exchangers: kaolinite, sodium bentonite and
by the presence of silver nanoparticles: a collective oscillation sepiolite. They all belong to the group of phyllosilicates, and
of their electrons in the conduction band, called surface are capable of exchanging the ions fixed on the outer surface
plasmon resonance (SPR), can take place under the action of of their crystals, or in the interlaminar spaces (kaolinite and
the electromagnetic radiation field, provided it has the proper bentonite), or inside the three-dimensional channels (sepiolite)
frequency (energy). The chemical composition and geometric of their structures for other ions present in the surrounding
parameters of nanoparticles as well as the environment that water-based solutions. We tested different glass coloration
surrounds them, determine their spectroscopic behaviour e procedures, studying, first of all, the influence of diverse
resonance position and width at half absorption e and thus the parameters e the amount of silver and the mineral employed
final colour of the glass [7]. To a lesser extent, the light e related to the mixtures we used. Subsequently, we studied
scattering caused by larger nanoparticles contributes to the the influence that heat treatment characteristics have on the
final colour of the glass by producing certain chromatic final colour of the glass, evaluating this influence at the highest
nuances that absorption alone cannot achieve. By mastering temperature reached.
this technique, glass artists achieved a chromatic diversity that
ranged from pale yellow to reddish hues. 2. Experimental procedure
The components that glass artists used to employ in their
mixtures had a very specific function, but we ignore to what The silver mixtures we used were formed by the commercial
extent that function was known in ancient times. Mixtures variety of the ion exchanger (sepiolite, bentonite or kaolinite)
used to be water-based, and they were mixed with organic employed in each case. The variety of sepiolite we used came from
components based on vegetable extracts and oils, and with Spanish mineral deposits, and was provided by the firm Sepiolsa
clay mineral materials that were often extracted from mineral S.A. under the commercial denomination Sepiolita <100. The
deposits located near the glass workshops. This seems to sodium bentonite also came from Spain and its supplier was Mario
indicate that colour could be obtained from a wide range of Pilato Blat S.A. The kaolinite came from an Australian mineral
raw materials, whose function was to provide good rheology deposit located in Queensland. The optimal water/mineral
for the deposition and coating of the glass surfaces which were proportions for each exchanger were determined to achieve the best
to be coloured. Nowadays, the excellent ion exchange capacity rheology. For kaolinite and sepiolite, these proportions were 6.7 g
A. Puche-Roig et al. / Journal of Cultural Heritage 9 (2008) e129ee133 e131

of water per gram of mineral, whereas bentonite required a relation those obtained in previously published works [11e14]. Of the
of 3.5 g of water per gram of mineral. The amount of mixture three mixtures employed, the kaolinite mixture shows the
deposited on the surface of each glass sample was 0.5 g. The minimum absorption intensity. The mixture using sodium
proportions of AgNO3 are given in percentage in relation to the bentonite as an exchanger is the one that presents a higher
mass of mineral in the mixture. The water we employed came from absorption, even saturating the detector response. The sepiolite
a MiliQ purifier, and the silver source was silver nitrate supplied by mixture holds an intermediate position between the former
Metalor S.A. Soda-lime float glass is a 2-mm-thick common two. After observing the glass samples coloured with the
commercial glass used for framing prints. We cut it in sample sodium bentonite mixture, we appreciated that the colour
pieces of 3.5 cm long and 2.5 cm wide that were washed for 15 min intensity was similar to the one achieved using sepiolite, but
in an ultrasound bath using commercial soap. They were subse- the surface that had been in contact with sodium bentonite was
quently cleaned with acetone and laboratory paper, and dried in very affected mechanically: it was more translucent, and the
a drying oven at 120  C for 1 h. The glass pieces were placed under traces of sodium bentonite had not been completely removed
a 294 nm UV lamp to distinguish unequivocally the tin side from from some areas of the sample. A possible explanation for this
the non-tin side. deterioration is the high sodium content in sodium bentonite,
and the role this element plays as a flux. The contact with
3. Results and discussion sodium oxide at high temperatures produces a lowering of the
glass transition temperature that is more noticeable than the
Distinguishing the tin side from the non-tin side is easy one produced in the samples which are in contact with sepi-
after observing the glass samples under UV light (294 nm UV olite or kaolinite. We decided to use sepiolite in our work
lamp). The float conformation process causes the Sn(II) to because of its sensible lack of effects on the glass surface, its
diffuse into the glass [11]. better performance on the final colour, and the good rheologic
The fact that during the Middle Ages, many different properties it gives to the suspension.
workshops throughout Europe accomplished yellow coloration In ancient times, very low concentrations of silver were
by silver based on recipes that contained clay composites from used to obtain coloured glass. We tested different amounts of
diverse origins, allows us to formulate the hypothesis that the silver in the mixtures (1% is equivalent to 0.001 g and 10% is
function of this ingredient is to accept and retain the alkali ions equivalent to 0.010 g AgNO3 contained in the 0.5 g of
extracted from the glass. To test this hypothesis, we used diverse mixture) to know the variation of spectroscopic properties
silver mixtures, each of them containing an exchanger with according to the silver content. The UVevis spectrum of these
different composition and crystalline structure. The amount of glass samples (submitted to a heat treatment at 600  C for 6 h)
silver introduced in the mixture remained unchanged, and the is shown in Fig. 2.
samples were submitted to a heat treatment at 600  C for 6 h. The maximum absorption intensity e and the coloration
The spectrum of the coloured glass samples is shown in Fig. 1. intensity e depends on the silver content of the mixture, since
As can be observed, a characteristic spectrum of glass it increases according to the amount of silver employed. The
samples coloured by silver nanoparticles was obtained for the area under the curve in the UVevis spectrum is linked to the
three exchangers employed. The resonance frequency of total volume of absorbing species in the environment (silver
the silver plasmon was about 3.0 eV, which is equivalent to nanoparticles in this case). Fig. 3 e where the area under the
approximately 425 nm. These results are compatible with curve from the previous figure is represented against the

5
Na-Bentonite 4
Sepiolite 1%
Kaolinite 2%
4 5%
10%
3

3
OD

OD

2
2

1
1

0 0
2.0 2.5 3.0 3.5 2.0 2.5 3.0 3.5
E (eV) E (eV)

Fig. 1. UVeVis spectra of glass samples coloured with mixtures containing Fig. 2. UVeVis spectra of glass samples that have been coloured using
different ion exchangers. mixtures with variable amounts of AgNO3.
e132 A. Puche-Roig et al. / Journal of Cultural Heritage 9 (2008) e129ee133

300 increase in silver content generates an increase in the


concentration of metal nanoparticles formed inside the glass,
250 but does not modify significantly their average radius.
Therefore, the average distribution radius of metal nano-
200 particles is a parameter which is not directly related to the
silver content of the mixture. Nevertheless, further studies are
Area (a.u.)

being performed in order to show results that may corrobo-


150
rate this conclusion. Considering the amount of AgNO3
contained in the mixture (1% wt. or 0.001 g) and the glass
100
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
50 AgNO3/cm2 is enough to obtain an appreciable glass colour
in glass.
0 In order to evaluate the influence of the heat treatment
0 2 4 6 8 10
maximum temperature on coloration, we treated four glass
Nominal AgNO3wt.%
samples with the same mixture (2 wt.% AgNO3 in relation to
Fig. 3. Representation of the area under the curve from the previous figure the mass of sepiolite), but at different maximum temperatures.
against the nominal amount of AgNO3 present in the mixtures used in the The results are depicted in Fig. 4.
coloration process. 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
nominal content of silver used in the mixtures e shows that exists a minimum temperature between 300  C and 400  C at
this delineating relation can be supposed. which metal nanoparticles begin to absorb light. Under that
In many cases the amount of doping ions entering the temperature, the ionic interdiffusion process does not reach
glass is proportional to the surface concentration of the proper extension, and the redox reactions involved in the
species to be diffused. By increasing the nominal amount of formation of metal nanoparticles do not occur. The result is the
silver nitrate in the mixture employed in the coloration, we absence of absorption in the UVevis area of the spectrum due
increased the total amount of doping ions entering the glass to an unnoticeable concentration of the optically active
e and therefore, the concentration of Ag ions, since all the species. By analyzing the position of the absorption maximum
processes occurred during the same time interval. A higher according to temperature, we can establish that there exists an
number of Ag ions inside the glass can cause two different inverse relation between these parameters, since the energy of
situations: 1) an increase in the average size of the metal the absorption maximum decreases as the treatment tempera-
nanoparticles formed inside the glass, their concentration ture increases (3.07 eV for the glass sample treated at 500  C
being kept constant; 2) an increase in the concentration of and 2.97 eV when the temperature reached 600  C). Accord-
those metal nanoparticles inside the glass whose average ing to Mie theory, a shift towards lower values of absorption
radius does not vary significantly depending on the amount of energy is related, all other factors being equal, to an increase
Ag present in their environment. According to Mie theory in the average distribution radius of metal nanoparticles: an
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 3
300C
response. According to diverse interpretations, a shift in the 400C
absorption maximum towards lower resonance energies could 500C
be produced by an increase in the average silver nanoparticle 600C

radius [12]. Observing the position of the absorption 2


maximum in the UVevis spectra according to the nominal
amount of silver nitrate, we can affirm that its energy value
OD

does not change significantly in relation to the amount of


silver employed. Furthermore, according to the Lamberte 1
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
0
in the graph is an increase in the maximum intensity
2.0 2.5 3.0 3.5
according to the concentration of silver employed in the
mixture. This suggests that an increase in the concentration of E (eV)
silver in the mixture causes an increase in the amount of Ag Fig. 4. UVeVis spectra of sample glasses treated at different maximum
inside the glass. Accordingly to this results we suggest that an temperatures for 6 h using a mixture with 2 wt.% AgNO3.
A. Puche-Roig et al. / Journal of Cultural Heritage 9 (2008) e129ee133 e133

increase in temperature causes an increase in the average References


radius of the metal nanoparticles formed inside the glass
[11,12]. The reason for the increase in the average size of [1] F. DellAcqua, Lux et Vitrium: the evolution of stained glass from the late
nanoparticles lies fundamentally in their thermodynamic roman empire to the gothic age chapter from the book, in: When Glass
Matters: Studies in the History of Science and Art from Graeco-Roman
stabilization (reduction of free energy), which takes place Antiquity to Early Modern Era (2006), ISBN 88-222-53183 Firenze.
when temperature rises above a specific value [7]. To sum up, [2] J.M. Fernandez Navarro, El Vidrio, CSIC Ed., 2003, ISBN 84-00-08158-7,
treatment temperature has two combined effects on the Madrid.
formation of metal nanoparticles: first, it increases the [3] A. Miotello, G. De Marchi, G. Mattei, P. Mazzoldi, A. Quaranta, Clus-
concentration of silver inside the glass due to an increase in tering of silver atoms in hydrogenated silveresodium exchanged glasses,
Appl. Phys. A-Mater. Sci. Process. 70 (2000) 415e419.
the speed of the ionic diffusion process. As we have previously [4] J.M. Fernandez Navarro, A. La Iglesia, Estudio de la coloracion roja y
observed, this causes an increase in the concentration of metal amarilla de vidrios de la catedral de Toledo, Bol. Soc. Esp. Ceramica y
nanoparticles. And second, with the increase in temperature, Vidrio 33 (1994) 333e336.
the thermodynamic stability of larger metal nanoparticles [5] C. Maurizio, F. DAcapito, C. Sada, E. Cattaruzza, F. Gonella, G. Battaglin,
increases too, resulting in a growing maximum absorption Site of transition metal ions in ion-exchanged metal-doped glasses, Mater.
Sci. Eng. B-Solid State Mater. Adv. Technol. 149 (2008) 171e176.
intensity and a shift in the absorption position towards lower [6] A. Quaranta, E. Cattaruzza, F. Gonella, Modelling the ion exchange
energy values as the treatment temperature increases. process in glass: phenomenological approaches and perspectives, Mater.
Sci. Eng. B-Solid State Mater. Adv. Technol. 149 (2008) 133e139.
4. Conclusions [7] R. Espiau de Lamaestre, Synthe`se assistee par faisceau dions dagregats
dans les verres, p. 21, PhD memory, Universite de Paris Sud e UFR
In our work, the basic ingredients described in different Scientifique dOrsay, 2005. Available from: <http://hal.archives-
ouvertes.fr/docs/00/06/81/57/PDF/these.pdf>.
mediaeval recipes for obtaining silver-stain glasses have been
[8] D. Jembrih-Simburger, C. Neelmeijer, O. Schalm, P. Frederickx,
employed in the preparation of modern mixtures to achieve the M. Schreiner, K. De Vis, M. Mader, D. Schryvers, J. Caen, The colour of
aforementioned colour. It has been determined that the use of silver stained glass e analytical investigations carried out with XRF,
clay minerals in the mixtures is not restricted to a specific kind SEM/EDX, TEM and IBA, J. Anal. At. Spectrom. 17 (2002) 321e328.
[9] J. Perez-Arantegui, J. Molera, A.  Larrea, T. Pradell, M. Vendrell-Saz,
of them, since we have verified that silver-stain glasses can be
I. Borgia, B.G. Brunetti, F. Cariati, P. Fermo, M. Mellini, A. Sgamellotti,
obtained using three crystalline structures that present signif-
C. Vitti, Luster pottery from the thirteenth century to the sixteenth
icant differences. Finally, we have established the influence century: a nanostructured thin metallic film, J. Am. Ceram. Soc. 84
that the treatment temperature and the amount of AgNO3 (2001) 442e446.
contained in the mixture have on the characteristics of the [10] R. J. Araujo, Essentially colorless silver-containing glasses through ion
silver nanoparticles distribution inside the glass e which exchange, US Patent 5007948, 1991.
[11] S. Takeda, K. Yamamoto, K. Matsumoto, Coloration due to colloidal Ag
ultimately account for the spectroscopic properties of the
particles formed in float glass, J. Non-Cryst. Solids 265 (2000) 133e142.
glass. [12] D.D. Evanoff, G. Chumanov, Synthesis and optical properties of silver
nanoparticles and arrays, Chemphyschem 6 (2005) 1221e1231.
Acknowledgements [13] T. Jensen, L. Kelly, A. Lazarides, G.C. Schatz, Electrodynamics of noble
metal nanoparticles and nanoparticle clusters, J. Clust. Sci. 10 (1999)
Our acknowledgements go to the Spanish Ministerio de 295e317.
Educacion y Ciencia (Project ref. MAT2006-04072) and [14] A.Y. Zhang, T. Suetsugu, K. Kadono, Incorporation of silver into soda-lime
silicate glass by a classical staining process, J. Non-Cryst. Solids 353
Generalitat Valenciana (grant ref. CTBPRB/2003/137) for
(2007) 44e50.
economical support. S.M.M. is funded by the program Ramon [15] E. Cottancin, G. Celep, J. Lerme, M. Pellarin, J.R. Huntzinger, J.L. Vialle,
y Cajal. A.P.R. is funded by the program F.P.I. Authors are M. Broyer, Optical properties of noble metal clusters as a function of the
very grateful to the reviewers for their useful comments and size: comparison between experiments and a semi-quantal theory, Phys.
suggestions. Rev. B. 70 (2004) 165409.