Project: Study of the composition and structure of ... - Eu-ARTECH

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MOLAB User Report
Project: Study of the composition and structure of lustre decorations on
original Italian Reinassance lustreware
User Group Leader: Lucia Burgio
Location: Victoria and Albert Museum, London, United Kingdom
The origin of the lustre decoration technique is one of the most complex issues in the history of
ceramics. Lustre preparation is described by Cipriano Piccolpasso in the second book of “Li tre
libri dell'arte del vasaio”: a mixture of silver, copper and iron salts or oxides, together with red
ochre and vinegar, was applied onto the surface of the glaze, the kiln’s temperature was raised to
approximately 600 o C, and smoking organic substances were added to create a reducing
atmosphere in the kiln [1,2].
Recent works demonstrated that lustre consists of a heterogeneous metal-glass composite film,
some hundreds of nanometres thick, analogous to that present in the modern metal-glass
nanostructured composites synthesised for high technology applications [3]. In lustre, separate
silver and copper nanoparticles appear dispersed within the outer layers of the glaze [4].
However, an extended study on the original lustre wares executed by the ancient masters has not
been attempted to date. This is the report on a fully non-destructive study carried out on eleven
Italian Renaissance plates belonging to the V&A collections.
Fig.1 The three Graces, a plate by Mastro Giorgio Andreoli
at the V&A.

Three techniques were used: energy dispersive X-ray fluorescence (EDXRF), Raman spectroscopy
and visible and near-infrared spectroscopy (Vis-NIR). The use of a portable EDXRF spectrometer
allowed the detection of copper and silver, which can be related to the colour of the decoration.
Portable fiber-optic Vis-NIR spectroscopy equipment allowed the quantification of colour and, at
the same time, the qualitative detection of copper and silver nanoparticles. This identification can
be carried out by way of the Surface Plasmon Resonances (SPR), typical of nanoparticles
dispersed in a transparent medium [4-6]. Finally, the glassy network of the glaze was studied by
portable micro-Raman spectroscopy. Raman spectra from many different areas of the lustre
decoration were recorded, making it possible to compare spectra taken from different decorations
of the same dish or analogous decorations in different dishes.
The XRF results on the plate “The three Graces” by Mastro Giorgio Andreoli (see Fig. 1) are
reported in Table 1.
Table 1 – Cps (counts per second) values of the elements detected on the plate “The three Graces”.
Colour Description Si K Ca Mn Fe Co Ni Cu Pb Ag Sn Sb
01 Red lustre Cloth 0.04 0.31 0.07 0.34 0.23 0.18 1.92 16.02 0.16
03 Red lustre Cloth 0.03 0.19 0.06 0.21 1.12 10.02 0.10
02
04
Gold
lustre
Gold
lustre on
red
Floor tr 0.23 0.07 0.24 0.57 9.89 0.02 0.11
Leaf tr 0.25 0.08 tr 0.26 0.37 9.65 0.02 0.15
08 Brown Hair tr 0.29 0.10 0.42 0.32 0.33 0.72 10.66 0.19 0.09
07 Blue Palms 0.03 0.33 0.12 1.10 1.52 0.62 2.09 8.96 0.65
06
05
Greenyellow
Fleshcoloured
Ground 0.04 0.28 0.08 0.40 1.17 10.80 0.18 0.09
Belly tr 0.25 0.09 0.25 0.27 9.84 0.22
The data in Table 1 show that the red lustre of the cloth near the Graces is characterized by the
presence of a relatively high value of copper, besides the elements of the glassy matrix. Moreover,
in the same point (01), the characteristic elements of blue smalt are present. The X-ray beam is
larger than 4 mm, due to the geometrical configuration of the alignment, and it is probable that the
investigated area included part of the blue zone nearby.
The gold lustre (point 02) on the floor is characterised by the presence of silver and copper.
Point 04, located on a decorative leaf made by a gold lustre applied close to a red lustre, shows the
presence of both silver and copper.
The brown pigment investigated on the hair of one of the Graces is characterised by the
presence of antimony. The antimony-based pigment is the so-called lead antimonate yellow, also
known as “giallo dei vasari”, which can be characterised by a colour ranging from yellow to
orange. It is worth noting that the lead concentration is higher than in the other areas, apart from
the green-yellow zone.
The blue pigment used to decorate the palms shows, in addition to the elements belonging to
the glaze, the elements typical of smalt (cobalt and nickel).
As for the brown area, the ground has been decorated with a copper-based pigment in the
green areas (ramina) and a lead antimonate yellow in the yellow areas, respectively.

Gold and red lustre show the typical SPR of silver and copper, respectively.
Int./arbitr. units
Si-O stretching
780 cm -1
636 cm -1
Si-O bending
1200 1000 800 600 400
Raman shift (cm -1 )
Fig.2 A typical Raman spectrum of the glaze
of one the investigated plates (The Charity) .
As far as the Raman measurements are concerned (see Fig. 2), the vibrational spectrum of the
glassy phase shows two very broad bands around 490 and 1000 cm-1, which are the sum of all
silicate phases. The first envelope at ca. 490 cm-1 corresponds to the bending vibration in the SiO 4
tetrahedra, the ν 2 mode. The second corresponds to the Si-O bond stretching of the different
vibrators coupled in an ordered structure giving ν 1 and ν 3 modes. The peaks at 780 and 636 cm-1
are related to the vibrational modes Sn-O of cassiterite.Using a curvefit procedure, Raman spectra
of the glassy phases have been deconvoluted into the Qn components. Further analysis is in
progress.
References
[1] A. Caiger-Smith, Luster Pottery. Technique, Tradition and Innovation in Islam and the
Western World. (Faber & Faber, London, UK, 1985)
[2] C. Piccolpasso, Li Tre Libri dell'Arte del Vasaio, 1557 (Edizioni all'Insegna del Giglio,
Firenze, 1976)
[3] R. H. Magruder III, D. H. Osborne Jr., R. A. Zuhr, J. Non-Crystalline Solids 176, 299 (1994).
[4] G. De, M. Gusso, L. Tapfer, M. Catalano, F. Gonella, G. Mattei, P. Mazzoldi, G. Battaglin, J.
Appl. Phys. 80, 6734-6738 (1996).
[5] S. Padovani, C. Sada, P. Mazzoldi, B. Brunetti, I. Borgia, A. Giulivi, A.Sgamellotti, F.
D’Acapito, and G. Battaglin, J. Appl. Phys. 93, 158 (2003)
[6] F. d'Acapito, S. Mobilio, G. Battaglin, E. Cattaruzza, F. Gonella, F. Caccavale, P. Mazzoldi, J.
Regnard, J. Appl. Phys. 87, 1819 (2000).