Raman Spectroscopy - Art Application Note - Horiba

deposited below the glaze. This quartz layer is
at the origin of the high gloss and very powerful
colored décor. Note that the technique of a
white α-quartz slip to mask the red color of the
body was already used for Vietnamese
porcelain and stoneware.
Intensity / arbitr. units
Iznik
515
465
465
545
550
515 650
MNC 8408
615
645
780
785
785
1055
985
1065
1065
990
blue
MNC 15472
blue
blue
white
500 1000 1500
Wavenumber / cm -1
Figure 7: As-recorded spectra for Iznik glazes. Note the
very strong quartz fingerprint for white glaze due to the
characteristic quartz slip deposited on the body, below
the glaze layer.
Strongly colored regions give a strong Raman
signature, nearly free of any background
(Figure 7). The ways to obtain a blue glaze are
rather limited: copper in alkaline silicate
(turquoise), cobalt (blue) and lapis lazuli
(ultramarine blue), whatever the fluxing agent
[7]. The last pigment has a very typical
resonance Raman signature when excited with
the 532nm laser. If small amounts of cobalt
(copper) dissolve in the glaze, no specific
Raman signature is expected. Saturation leads
to cobalt mixed silicates or to cobalt aluminate.
Cobalt-containing Mn-rich ores (spinels) can
also be used as blue pigments, if the firing is
conducted in a reducing atmosphere. The
observed color excludes the use of lapis lazuli
and Cu. In most blue regions analyzed, we only
observed the Raman signature of the glaze,
(All HORIBA Jobin Yvon companies were formerly known as Jobin Yvon)
Art 02
which indicates that cobalt is dissolved within
the glaze network.
In conclusion, this work has shown that Raman
microanalysis is invaluable in assisting in the
characterization of all types of ceramic artifacts.
The information obtained on the composition of
the glaze and pigments can yield important
information on the fabrication and processing of
these ancient artifacts and may even help
putting to rest many controversies about the
provenance of certain pieces.
References:
1. Ph. Colomban, Glasses, Glazes and Ceramics – Recognition
of the Ancient Technology from the Raman Spectra, chapter in
Raman Spectroscopy in Archaeology and Art History, Edwards
HGM and Chalmers JM (Eds), Royal Society of Chemistry,
London, 2005, ch13.
2. Ph. Colomban, F. Treppoz, Identification and Differentiation
of Ancient and Modern European Porcelains by Raman Macro-
and Microspectroscopy, J. Raman Spectr. 32 (2001) 93-102
3. Ph. Colomban, Polymerisation Degree and Raman
Identification of Ancient Glasses used for Jewellery, Ceramics
Enamels and Mosaics, J. Non-Crystalline Solids 323 [1-3]
(2003) 180-187.
4. Ph. Colomban, O. Paulsen Raman Determination of the
Structure and Composition of Glazes, J. Amer. Ceram. Soc. 88
[2] (2005) 390-395.
5. Ph. Colomban Recent Case studies in the Raman Analysis
of Ancient Ceramics: Glaze Opacification in Abbasid Pottery,
Medici and 18 th century French Porcelains, Iznik and Kütahya
Ottoman Fritwares and Unexpected Lapis Lazuli Pigment in
Lajvardina Wares, Mater. Res. Soc. Symp. Proc. 2005 vol 852,
P. Vandiver, J. Mass & A. Murray Eds. OO8.4.
6. Ph. Colomban, C. Truong, A Non-destructive Raman Study
of the Glazing Technique in Lustre Potteries and Faiences (9 th -
14 th centuries) : Silver ions, Nanoclusters, Microstructure and
Processing, J. Raman Spectrosc. 35 [3] (2004) 195-207.
7. Ph. Colomban, V. Milande, L. Le Bihan, On-site Raman
Analysis of Iznik pottery glazes and pigments, J. Raman
Spectrosc. 35 (2004) 527-535.
8. Ph. Colomban, R. de Laveaucoupet, V. Milande, On Site
Raman Analysis of Kütahya fritwares, J. Raman Spectroscopy
36 [9] (2005) 857-863.
9. Ph. Colomban, V. Milande, On Site Analysis of the earliest
known Meissen Porcelain and Stoneware, J. Raman Spectrosc.
37 (2006).
10. Ph. Colomban, A. Tournie, L. Bellot-Gurlet, Raman
Identification of glassy silicates used in ceramic, glass and
jewellry : a tentative differentiation guide, J. Raman Spectrosc.
37 (2006) 841-852.
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