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Luster decoration of ceramics: Mechanisms of metallic luster formation

Article  in  Applied Physics A · May 2006

DOI: 10.1007/s00339-006-3508-1

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Appl. Phys. A 83, 203–208 (2006)
DOI: 10.1007/s00339-006-3508-1
t. pradell1,u Luster decoration of ceramics:
j. molera2
c. bayés2 mechanisms of metallic luster formation
p. roura2 1 Dept. Fı́sica i Enginyeria Nuclear, UPC, Campus Baix Llobregat. ESAB. Av. Canal Olı́mpic s/n,
08860 Castelldefels, Barcelona, Spain
2 GRMT, Dept. Fı́sica, UdG, campus Montilivı́, 17071 Girona, Spain
Received: 5 December 2005/Accepted: 12 December 2005
Published online: 15 February 2006 • © Springer-Verlag 2006
ABSTRACT Luster is a metallic decoration produced since early
Islamic times (9th century AD in Iraq). Different studies have
shown that medieval lusters are a metal-glass nanocompos-
ite (metal nanoparticles embodied in a silica glassy matrix)
obtained from the reaction of a copper and/or silver contain-
ing paint with a glaze. The mechanisms of formation of these
metallic-like layers are investigated by laboratory reproductions
of Medieval luster. Copper and silver lusters are obtained based
on different thermal paths and atmospheres, and by using differ-
ent glaze compositions. The ionic exchange between Cu+ and
Ag+ ions from the luster paint with Na+ and K+ of the glaze, is
demonstrated in either oxidizing or inert atmospheres and at fir-
ing temperatures between 500 ◦ C and 600 ◦ C. The reduction of
copper and silver to their metallic state is obtained by introduc-
ing a reducing gas afterwards. The lusters are non-metallic red
ruby copper or green with brown spots silver when developed
over alkaline glazes, while they appear coppery and golden
metallic when developed over mixed alkaline-lead glazes. SR-
XRD, optical absorption and microprobe chemical analysis of
the lusters indicate that the total amount of copper and silver,
and the nature and size of the nanoparticles, are similar in both
cases. Further work is needed to clarify the origin of these dif-
ferences.
PACS 81.05.Pj; 81.07.b; 81.16.Be; 78.67.Bf; 42.50.Fx
1 Introduction
1.1 The nature of luster
Luster is a ceramic design with a golden or cop-
pery metallic shine first produced in early Islamic times (9th
century AD in Iraq) that extended all over the Mediterranean
and lasted until the first half of the 20th century AD [1]. Lus-
ter designs were painted over glazed ceramics (in most of
the cases over white tin glazes) and sometimes show blue iri-
descences. Transmission electron microscope cross section
preparations showed that in all cases examined, the luster
appeared to be a nanosized metal-glass composite (metallic
copper and/or silver nanoparticles appear embodied in the
glassy matrix) [2–4]. The metal particle sizes range between
5 nm and 50 nm and form a layer with a thickness varying be-
tween 100 nm to 1 µm [4]. A wide range of Cu to Ag ratio
u Fax: +34-935521129, E-mail: Trinitat.Pradell@upc.edu
Applied Physics A
Materials Science & Processing
has been observed in the luster layers, ranging from pure sil-
ver to pure copper luster decorations, and even in the same
design. Roughly speaking the Cu/Ag ratio is related to the
color, yellow and green for silver rich lusters, and orange,
brown and red for copper rich lusters [2–5]. However, green
copper lusters or dark brown silver lusters also exist. EXAFS
data indicate that the presence of ionic silver and/or copper
(Ag+ , Cu+ and Cu2+ ) and their gradient distribution in the lus-
ter layer are also responsible for the different colors [6–9].
The exact reasons for the colors and some of the peculiar
optical properties (blue iridescences) shown by the luster dec-
orations result from the nanosize of the particles. An approach
to these particular optical properties through the analysis of
the optical spectra has been attempted in [10]. Nanoparticles
in glazes are known to show some peculiar optical proper-
ties such as the presence of surface plasmon resonance (SPR)
in the optical absorption spectra. Such plasmons appear as
absorption peaks with a characteristic maximum absorption
wavelength which depends on the nature, size distribution and
shape of the nanoparticles, and the nature of the glassy me-
dia, and a SPR peak width mainly related to the size of the
nanoparticles [11–13]. In particular, spherical silver nanopar-
ticles between 2 nm and 80 nm show a SPR peak between
400 nm and 490 nm [11], and spherical copper nanoparticles
at about 500 – 600 nm.
1.2 The production of luster
Luster is produced by direct application of a raw
paint over a glazed ceramic which after firing (at temperatures
between 500 and 600 ◦ C) in a reducing atmosphere results in
the formation of the luster layer. The remaining paint (called
cosela) is washed off revealing the luster beneath [1, 5]. The
luster is therefore a reaction layer obtained from the interac-
tion between the luster paint and the glaze [14]. The com-
position of the luster paint is therefore different from that of
the final luster layer. Typical recipes are a water suspension
of a powder mixture containing a clay, copper or/and silver
compounds, and a sulfur containing compound. In particular,
cinnabar (HgS) was found in the 13th century AD Hispano
Moresque workshop from Paterna (Valencia) [5]; the exact
mixture contained 40% of the workshop clay, 7.5% quartz,
7.5% of iron oxides (hematite), 13% copper oxide (tenorite),
2% silver sulfide (Ag2 S) and 30% cinnabar. Sulfur is respon-
sible for generating a sulfo reducing atmosphere necessary
to reduce the silver and copper. The role of cinnabar in the
204 Applied Physics A – Materials Science & Processing

luster production was investigated in a time resolved high

temperature XRD experiment in ESRF [15]. Synthetic mix-
tures containing sulfur or cinnabar and either copper or sil-
ver were investigated. The main conclusions obtained from
the study indicate that cinnabar decomposes at temperatures
above 400 ◦ C and releases S which produces the sulfo reduc-
ing atmosphere that transforms tenorite (CuO) into cuprite
(Cu2 O) and the formation of silver or copper sulfates and sul-
fides. The release of sulfur and the new phases formed are
delayed for temperatures above 400 ◦ C while using cinnabar
instead of sulfur. Moreover, the presence of mercury vapors
during the decomposition of cinnabar impedes the reduction
of silver to its metallic state, which otherwise, even in oxidiz-
ing conditions, is achieved at temperatures as low as 300 ◦ C.
Although the reduction of silver and copper to their metal-
lic state is the final issue, the introduction of silver and/or
copper into the glaze may only be obtained by the diffusion
of silver and/or copper ions from the paint into the glaze,
where they are reduced to achieve its metallic state. There-
fore ionic silver and copper compounds must be formed in
the paint during the firing and, only after copper and sil-
ver are introduced in the glaze may they be reduced to the
metallic state. The diffusion coefficients of silver and/or cop-
per ions into the glaze must be high enough, and for this,
attainment of temperatures close to the glass transition tem-
perature is necessary. For typical glaze compositions (either
high alkali, mixed and high lead glazes) used in the pro-
duction of Medieval luster, temperatures between 500 ◦ C and
600 ◦ C are expected. Therefore, the role of cinnabar in the
development of luster, is the production of a sulfo reducing
environment at temperatures between 500 ◦ C and 600 ◦ C, to
help the reduction of copper to Cu+ , and to avoid the reduc-
tion of silver to its metallic state before it has entered the
glaze [15].
From the analysis of medieval lusters, some interesting
trends and information is obtained concerning the driving
force responsible for the diffusion of silver and copper ions
into the glaze; that is the “ionic exchange” of Ag+ and
Cu+ with Na+ and K+ . The ionic exchange is a very well
known mechanism in glasses and glazes. While immersing
the glasses in a copper and/or silver containing molten salt
(typically sulfates or nitrates), the atomic exchange and re-
placement of the alkalis (K+ and Na+ ) of the glaze by Ag+
and Cu+ is obtained. In fact, accurate chemical analysis of
medieval lusters showed a clear inverse correlation between
the metal components of the luster decorations (Cu and Ag)
and that of Na and K in the glaze. This correlation has been FIGURE 1 (a) Line profile chemical composition (in wt.%) measured di-
found for early Islamic lusters from Iraq (10th AD) as seen in rectly over the glaze surface crossing an Islamic luster design from Iraq (10th
AD). A clear decrease in the total amount of sodium and potassium is found
Fig. 1, as well as for late Hispano Moresque lusters from Pa- linked to the increase in silver and copper in the luster design. (b) at.%
terna [16], indicating a common manufacture technique. The (Na + K) versus at.% (Cu + Ag) corresponding to the Islamic luster. The
formation of sulfates seems therefore, an important issue, and atomic substitution of the alkalis by the metals is clearly seen
gives a good reason for the use of a sulfur containing com-
pound in all the luster recipes from historical textbooks [1], this, we present the results obtained from laboratory reproduc-
as well as in the archaeological findings [5]. Moreover, the tions of luster following the original medieval recipe found
use of modern recipes in the luster production give rise to the in the Hispano Moresque workshop from Paterna (13th AD),
development of molten sulfates which appeared to be the ve- which will give insight into the exact mechanisms involved in
hicle for ionic exchange between the luster paint and the glaze the luster development. Our goal is to find the experimental
surface [16]. conditions (paint and glaze composition, thermal paths and at-
The present paper deals with the physical and chemical mosphere) needed to reproduce the coppery and gold metallic
mechanisms involved in the formation of the luster layers. For lusters.
PRADELL et al. Luster decoration of ceramics : Mechanisms of metallic luster formation 205

Glaze SiO2 Na2 O K2 O B2 O3 Al2 O3 PbO CaO MgO ZnO Sb2 O3 TiO2

Ga1 48.5 12.0 7.1 23.2 7.2 0.9 0.1

Ga2 63.9 6.5 6.4 8.2 4.3 6.0 0.5 4.1
Gh1 32.6 0.2 0.4 3.6 61.4 0.4 0.9
Gm 43.5 3.5 2.9 11.0 5.7 31.8 1.0 0.1 TABLE 1 Chemical composition in wt.% of
the glazes and glasses selected

Atmosphere Gas Heating ramp Tmax Time Cooling ramp

Oxidizing Synthetic air

(40 ml/min)
Neutral Argon
(40 ml/min) 50 ◦ C 500–600 ◦ C 30 min 100 ◦ C/min
Reducing Varigon (93%AR + 7%H2 )
(1.6 l/min)
Neutral + Reducing Argon + Varigon 10 min
(40 l/min + 1.6 l/min) +20 min
TABLE 2 Luster reproduction thermal paths

2 Luster reproductions wavelength, 200 microns spot size and recorded by a CCD
2.1 Materials and methods detector. Optical absorption spectra were taken with a spec-
trophotometer Shimazu UV-Vis 2401 PC either in transmis-
Several parameters are important in order to re- sion or reflection mode. The average cluster diameters are
produce luster layers: the composition of the raw paint, the calculated from the full width half maximum of the absorption
composition of the glaze, the thermal paths and the atmo- peak [17].
sphere. We will use the same raw synthetic paint composi-
tions developed in [14] to study the role of cinnabar in luster 2.2 Results
production, based on the Medieval recipe found in the His-
pano Moresque workshop from Paterna (13th AD) [5]. Two The effect of different atmospheres has been ad-
basic compositions are studied, one with copper (S1c: 50% dressed. The ionic exchange atom by atom between the al-
illitic clay, 10% hematite, 30% cinnabar, 10% CuO) and the
other with silver (S2c: 50% illitic clay, 10% hematite, 30%
cinnabar, 10% AgNO3 ).
As lusters were developed on glasses and glazed ceram-
ics in medieval times, the range of glaze compositions is very
wide, in order to account for it we have selected three ba-
sic compositions: alkaline, high lead and mixed alkaline-lead
glazes. A commercial high Na alkaline glaze (Ga1) – frit 4292
Prodesco SL –, a commercial alkaline glass (Ga2) – Marien-
feld –, a high lead glaze (Ghl) and a mixed alkaline-lead
glaze (Gm) obtained by mixing equal ratio of Ga1 and Ghl.
The chemical composition of the glazes selected are given in
Table 1.
The range of firing temperatures from the previous stud-
ies is set between 500 ◦ C and 600 ◦ C. The atmosphere is more
complicated as there are two processes involved in luster pro-
duction, the penetration of silver and/or copper into the glaze
and the formation of the metallic nanoparticles. The first pro-
cess may not need any special atmosphere but the second
process involves the reduction of the ionic silver and copper
to metal, and therefore the need of a reducing stage at the end
is expected. Different thermal paths including oxidizing, inert
or reducing atmospheres were studied, a summary is given in
Table 2.
The chemical analysis of the luster layers were performed
FIGURE 2 at.% Cu in the luster versus at.% Na obtained after firing follow-
directly from the surface of the glazes using an electron
ing the different thermal paths at Tmax = 550 ◦ C as described in Table 2 for
microprobe CAMECA SX-50 and the measurement con- a copper containing luster paint (S1c) applied over an alkaline glaze (Ga1).
ditions were 20 kV and 15 nA probe current with a spot The ionic exchange between Cu+ and Na+ is clearly seen either firing in an
size of about 1 µm except for the measurement of Na, for oxidizing atmosphere (air) or in a inert atmosphere (Ar) but not in a reducing
atmosphere (varigon). The luster developed is yellow and copper appears in
which the probe current used was 2 nA with a spot size of the glaze as nanocrystalline cuprite (Cu2 O) and ionic Cu+ . The use of a com-
about 5 µm. SR-XRD was performed in the beamline 9.6 at bined first inert and then reducing atmosphere results in the formation of a red
SRS Daresbury laboratory, in transmission geometry, 0.87 Å ruby luster by the reduction of most of the copper to metallic copper
206 Applied Physics A – Materials Science & Processing
kalis (Na and/or K) from the glaze and the metals from the
luster paint (Cu and/or Ag) is demonstrated while firing ei-
ther in an oxidizing atmosphere or in an inert atmosphere.
Figure 2 shows the extent of ionic exchange for copper luster
paint (S1c) applied over an alkaline glaze (Ga1) in different
atmospheres. In oxidizing or inert atmospheres yellow lus-
ter is obtained. The introduction of a reducing atmosphere
after the ionic exchange is accomplished, results in the reduc-
tion of most of the copper to its metallic state and to a red
ruby colored luster layer. However, the use of a reducing at-
mosphere during the whole path does not allow development
of the ionic compounds responsible for the ionic exchange
and therefore, the luster is not formed. Figure 3a shows the
SR-XRD patterns that were obtained in transmission geom-
etry and the optical absorption spectra taken in transmission
geometry corresponding to the copper yellow and red ruby
lusters developed over the alkaline glass (Ga2). Both SR-
XRD and the optical absorption spectra show the formation
of nanocrystalline cuprite in the yellow lusters and the for-
mation of nanocrystalline metallic copper (about 15 – 20 nm),
as well as the growth of the nanocrystalline cuprite (about
15 – 20 nm) in the red ruby lusters. In the case of silver, a green
with brown spots luster is formed; Fig. 3b shows the corres-
ponding SR-XRD and optical absorption spectra. In this case
silver appears in all cases as nanocrystalline metallic silver,
with typical sizes of about 5 – 15 nm. Ionic exchange is also
found to occur for the silver luster paints and for the mixed
lead-alkaline glaze. On the contrary, luster decorations were
not developed over a pure high lead glaze because it did not
contain alkalis.
The copper and silver developed over alkaline glazes did
not show metallic reflection. On the contrary, the luster layers
developed over a mixed alkaline-lead glaze show in all cases
a fully developed metallic reflection. In the case of copper
lusters, a coppery metallic shine is obtained while for sil-
ver lusters a golden metallic shine is obtained as shown in
Fig. 4a and Fig. 4b respectively. SR-XRD and optical spec-
tra taken in reflection mode indicate that the nature (cuprite
and metallic copper for copper lusters and metallic silver for
silver lusters) and size of the nanocrystals (15 – 20 nm for cop-
per and 10 – 20 nm for silver) is similar than for the case of
the lusters developed over alkaline glazes obtained following
the same thermal paths. The optical spectrum corresponding
to the silver nanoparticles shows the typical two peak splitting
resulting from the organization of the nanoparticles forming
a string. Moreover, microprobe analysis of the lusters show
also a similar total amount of copper and silver in the luster
layers (about 5 at. % in all the cases) obtained following the
same thermal paths. Therefore, the metallic or non-metallic
nature of the luster layers developed does not seem to be re-
lated only to the nature and size of the nanoparticles, but is
also linked to other parameters such as the size distribution of
the nanoparticles, density of nanocrystals in the luster layer,
and organisation of the nanoparticles in the lustre layer form-
ing strings, etc. It is well known that the reduction of the
interparticle distance may result in an insulator–metal transi-
tion due to the collective properties of quantum dots superlat-
tices [13]. However, more detailed analysis is needed in order
to understand the role that the nature of the glaze has on this
particular behavior.
FIGURE 3 (a) Yellow and red ruby
luster layers developed while heat-
ing, at 550 ◦ C in inert (argon) and
mixed (argon+varigon) atmosphere
respectively, a copper luster paint
(S1c) over an alkaline glass (Ga2).
In the column the SR-XRD pattern
(transmission geometry, λ = 0.98 Å)
and optical absorption spectrum are
shown. (b) Green with brown spots
luster layer developed while heating,
at 550 ◦ C mixed (argon+varigon)
atmosphere, a silver luster paint
(S2c) over an alkaline glass (Ga2).
In the column the SR-XRD pattern
(transmission geometry, λ = 0.98 Å)
and optical absorption spectrum are
shown
PRADELL et al. Luster decoration of ceramics : Mechanisms of metallic luster formation
3 Conclusions
Laboratory reproductions of copper and silver lus-
ter layers have been obtained following the Medieval recipes
found in the Hispano-Moresque workshop from Paterna (13th
century AD). Different glaze compositions, thermal paths and
atmospheres have been tried. The ionic exchange between the
alkalis (Na+ and/or K+ ) from the glaze and Cu+ and Ag+
from the luster paint is demonstrated while firing in oxidizing
or inert atmospheres. The use of a reducing atmosphere after
ionic exchange is responsible for the reduction of Cu+ and
Ag+ to their metallic state. In this reducing stage nanocrys-
talline metallic copper and metallic silver are formed. Typical
sizes of the nanocrystals are 15 to 20 nm for copper and 5 to
20 nm for silver. The glaze composition is crucial in the de-
velopment of a metallic luster layer. Red ruby non-metallic
copper lusters and green with brown spots non-metallic silver
lusters are formed in alkaline glazes. On the contrary, coppery
metallic and gold metallic silver lusters are formed in mixed
alkaline-lead glazes. The total amount of copper or silver in
the luster layer and the size of the nanoparticles is similar in
both cases. Therefore, the metallic or non-metallic nature of
the luster layers developed has to be linked to other parame-
ters, in particular those related to the formation of strings of
particles and to the reduction of the interparticle distance that
is known to result in an insulator to metal transition. However,
further work is needed in order to understand the full picture.
207
FIGURE 4 (a) Coppery metallic
luster layer developed while heat-
ing (550 ◦ C in argon+varigon at-
mosphere) a copper luster paint
(S1c) over a mixed lead-alkaline
glaze (Gm). In the column the SR-
XRD pattern (transmission geom-
etry, λ = 0.87 Å) and the optical
spectrum are shown. (b) Golden
metallic luster layer developed while
heating (550 ◦ C in argon+varigon
atmosphere) a silver luster paint
(S2c) over a mixed lead-alkaline
glaze (Gm). In the column the SR-
XRD pattern (reflexion geometry,
λ = 1.40 Å) and the optical spectra
are shown
ACKNOWLEDGEMENTS This project has been partially
funded by Ministerio de Ciencia y Tecnologı́a (Spain), grant MAT2004-
01214 and Generalitat de Catalunya grant 2001SGR00190. Support of the
European Community funding through the Research Infrastructure Action
under FP6 “Structuring the European research area” program, project number
43025 at SRS Daresbury Laboratory. Dr. J. Molera is funded by the pro-
gram Ramon y Cajal (Ministerio de Educación y Ciencia) and UdG research
project number 9104071.
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