Appl. Phys.

A 83, 681684 (2006)

Applied Physics A

DOI: 10.1007/s00339-006-3547-7

Materials Science & Processing

a. galli1,u
m. martini1,2
e. sibilia1,2
c. montanari1,2
l. panzeri1

Photoluminescence emissions of ceramics:

a marker of production technology
1

CNR-INFM and Dipartimento di Scienza dei Materiali, Universit di Milano Bicocca,

via R. Cozzi 53, 20125 Milano, Italy
2 INFN, Sezione di Milano, via Celoria 16, 20133 Milano, Italy

Received: 15 June 2005/Accepted: 18 January 2006

Published online: 7 March 2006 Springer-Verlag 2006

Photoluminescence (PL) measurements have been

performed on different sets of ceramic shards; the results obtained from the ceramic bodies of lustred majolicas produced
in Iraq, Italy and Spain are reported. Non-lustred samples are
analysed for comparison. The spectra obtained from all the lustred samples show PL emission bands that are attributed to the
presence of -quartz and diopside. The photoluminescence of
the lustre-decorated ceramics is possibly a fingerprint of the
particular production technology of lustre.

ABSTRACT

PACS 81.05.Mh;

78.55.Hx

Introduction

The ceramics examined in this study are mainly

majolicas characterised by the presence of reduced-pigment
lustre decorations. The lustre technique, introduced in Iraq in
the VIII century, spread to Egypt, Persia and Spain following
the expansion of Arabian culture during the Middle Ages. By
the XIII century lustre was extensively produced in Moorish
Spain, from where it was exported to France and Italy. Since
the XIV century the Italian towns of Deruta and Gubbio became the main centres of lustre production. In 1557 Cipriano
Piccolpasso from Casteldurante reported, in The three books
of the art of the potter [1], the recipe to make lustred ceramics. According to him, the object, shaped in the desired form,
was firstly fired at about 1000 C to obtain the base biscuit.
Once cooled down, it was immersed in the glaze, decorated,
sprayed with transparent paint and refired at 900 C. The final lustre effect of reflection and iridescence was achieved
by covering the glazed surface with a special and secret mixture of copper and silver salts, clays and ochre, and firing it
again at a temperature between 500 and 600 C in reducing
atmosphere using special kilns purposely made.
There are therefore three firing steps: one at 1000 C to
obtain the biscuit, one at 900 C for the glaze and a third, in reducing atmosphere, for the lustre formation. The glaze layer is
typically 100 300 m thick while the lustre is 0.1 2 m.
Studies of the HispanoMoresque production technology [2] showed that the use of calcareous clays was necessary
to avoid or limit the reddish hue associated with iron oxide
u Fax: +390264485400, E-mail: anna.galli@mater.unimib.it

formation at high temperature. The final closure of the kiln,

adopted to guarantee a slow cooling down, furthermore diminished the re-oxidation at the pots surface assuring a final
creamy colour of the paste.
Several studies have been recently carried out to characterise the lustred majolicas and their production technology,
especially concerning the lustre layer [3]. Focusing instead on
ceramic pastes, we started to investigate their luminescence
properties, which seemed to be influenced by the thermal
treatment the lustred ceramics are submitted to [4].
The present paper deals with the photoluminescence (PL)
emission of the ceramic bodies of lustred Italian and Spanish Renaissance samples, compared with those of non-lustred
pottery and bricks from two excavation sites, one Israeli and
one Italian, previously dated by thermoluminescence (TL)
and covering a wide age range.
2

Experimental

The analysed samples are listed in Table 1. The

lustre-decorated majolica shards come from private collectors, museums and excavation sites and are of heterogeneous
provenance. Their chemical and mineralogical compositions
also differ, even if the main component was found to be silicon
dioxide [5].
The Israeli site was inhabited from the Roman to the
Umayyad period, and the selected ceramics cover its whole
time span. The Italian bricks came from a medieval settlement
in northern Italy (San Benedetto Po, Mantova), characterised
by a diffuse reuse of Roman bricks.
All the samples have been submitted to X-ray diffraction
analysis using a BraggBrentano diffractometer (STEIFFERT ID 3000) equipped with a Ge focusing primary
monochromator ( = Cu K ). The diffractograms have been
acquired on powdered ceramic.
Photoluminescence spectroscopy is a contactless method
of probing the electronic structure of materials. Light is directed onto the sample, where it is absorbed and causes photoexcitation that is promptly dissipated through the emission of
light, or photoluminescence. The amount of photoluminescence and its dependence on the level of photo-excitation and
temperature are directly related to the dominant recombination processes.
The PL measurements are obtained with a Varian Eclipse
fluorescence spectrometer, equipped with a xenon lamp and

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Sample

Applied Physics A Materials Science & Processing

Provenance and age

Lustred majolicas
LIr1
Iraq, VIII century
LIr2
Iraq, XI century
LSp1
Spain, XII century
LSp2
Spain, XIII century
LSp3
Spain, XV century
LSp4
Spain, XVII century
LSp5
Spain, XVIII century
LIt1-LIt3
Italy, XIV century
LIt4-LIt6
Italy, XV century
LIt7-LIt12
Italy, XVI century
LIt13-LIt14
Italy, XVII century
LIt15
Italy, XVIII century
Non-lustred ceramics
NL1
Israel, domestic pottery, II century BC
NL2
Israel, pottery, VI century
NL3
Israel, pottery, VI century
NL4
Israel, pottery, VII century
NL5-NL7
Israel, pottery, VIII century
NL8
Italy, brick, I century
NL9-NL10
Italy, brick, IV century
NL11
Italy, brick, II century
NL12
Italy, brick, VII century
NL13
Italy, brick, VI century/
NL14
Italy, brick, VII century
NL15
Italy, brick, IV century
NL16
Italy, brick, I century
TABLE 1

Samples description

a photomultiplier (excitation range 200 900 nm, emission

range 200 900 nm, 1 nm).
Measurements were performed on the internal, nonglazed surface of the shards, without any treatment.
3

during heating into calcium oxides and carbon dioxide. The

temperature at which this occurs in pottery varies according to the oxidisingreducing atmosphere, the grain size and
the heating regime, but normally it happens between 700 C
and 900 C.
The formation of calcium compounds being nevertheless
accelerated in reducing atmosphere [6], it can be hypothesised
that CaCO3 has reformed during the third firing, favoured by
the reducing atmosphere in the kiln.
In Fig. 2 the PL spectra of samples LIt15, LSp1, NL10 and
NL1 are reported. The first two are lustred majolicas. Spectra
are obtained under excitation at 386 nm that was found to be
the most effective in producing PL in these samples.
The PL peaks overlap a background monotonically increasing with the energy, due to the effect of light diffusion by
the sample. Moreover, in all spectra there is a small peak at
460 nm due to the absorption edge of the optical filters of the
instrument.
In all the samples, regardless of their provenance, age or
manufacturing technique, the emission bands at 438, 486 and
570 nm, characteristic of -quartz, are present, as expected
due to the composition of the constituent clays. Moreover, all
the majolicas showed systematically higher PL sensitivity and
the presence of all the bands related to -quartz: 443446,
482, 528 and 570 nm [7].
In Fig. 3 the PL spectra of a crystal of natural smoky quartz
is reported for comparison with those of the two majolicas
of Fig. 2, again obtained under excitation at 386 nm. The two
majolica spectra are very similar, even if they show reason-

Results and discussion

In Fig. 1 there is reported the diffractogram of the

majolica sample LIt15, well representative of the main composition of the other lustred shards we measured.
Besides the strong signal due to -quartz, those of diopside (CaMg(SiO3 )2 ) and calcite (CaCO3 ) were also observed.
As the diopside phase forms at T > 1000 C, its presence is
a confirmation of the high temperature reached during firing. Diopside was not found in bricks and non-lustred pottery.
Less obvious is the presence of the peaks of calcite that should
instead be absent for the same reason: it, in fact, decomposes
FIGURE 2 LIt15, LSp1, NL1 and NL10 shards: PL emission spectra. (Excitation wavelength: 386 nm. The first two shards are lustred)

FIGURE 1 Lustred sample LIt15: X-ray diffraction patterns (dot = quartz,

full square = calcite, empty square = diopside)

FIGURE 3 Smoky quartz, LIt15 and LSp1 shards: PL emission spectra.

(Excitation wavelength: 386 nm)

GALLI et al.

Photoluminescence emissions of ceramics: a marker of production technology

able differences due to the different structuralmorphological

compositions of the original pastes [5]. In both ceramics, the
emission band at 435 450 nm is evidently the overlap of few
peaks.
The emissions of quartz are related to the presence and
concentration of [AlO4 ]0 hole centres [7]. In particular, the
concentration of these centres increases with the thermal
treatments experienced by the mineral, and could be used as
an indicator of the temperature at which it was formed [8].
The intensity of the signal associated with [AlO4 ]0 centres
in the majolicas we examined is systematically greater that
those of the non-lustred pastes, and even than that of smoky
quartz itself (Fig. 3).
This could simply mean that quartz crystals in all the
clays underwent a geological formation at very high temperature. On the contrary, all the non-lustred samples should
contain quartz formed at lower temperature. This hypothesis therefore seemed unlikely, just considering the differ-

683

ent provenances, ages and typologies of the pottery. We

would rather suggest that it is the triple heating required
to produce the lustre that determined the high concentration of hole centres responsible for the high PL quartz
signals.
Figure 4 reports the PL emissions at different excitation
energies in the emission range 430 450 nm for the lustred
samples LIt15 a and LSp1 b, for smoky quartz c and for a diopside standard d.
The comparison of the different spectra allowed us to assign the emission observed at 435 nm in LIt15 and LSp1 to
SiO2 . Concerning the emissions at about 441 and 446 nm, they
are instead those of diopside, even if they are also present in
quartz, but at different excitation energies.
It must be outlined that the PL emission of calcite, which
occurs in the orangered wavelength range [9], is below the
detection limit of our instrument, and its signal is indistinguishable from the background.

FIGURE 4 PL emission spectra under different excitation wavelengths. Details of the 430450 nm emision bands: (a) sample LIt15, (excitation) =
375394 nm; (b) sample LSp1, (excitation) = 380399 nm; (c) smoky quartz, (excitation) = 368387 nm; (d) diopside standard, (excitation) =
375395 nm

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Applied Physics A Materials Science & Processing

Conclusions

We presented a successful attempt to study ancient pottery samples by means of photoluminescence. This
application gave interesting results towards the characterisation of the ceramic bodies, and the preliminary results
obtained on lustred ceramics are encouraging, even for the
identification of technological features. Characteristic PL
emissions have been associated with the particular manufacturing technology of the lustre, being independent of
the type of clay. The emissions related to the presence of
-SiO2 [AlO4 ]0 hole centres, typical of smoky quartz, indicate that the samples have been submitted to high temperatures, as also confirmed by the presence of the bands of
diopside.

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