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This paper is based on a presentation at Even though kept in cultural institutions, artefacts can be
the 8th international conference of the
subjected to accelerated deterioration due to high concen-
Infrared and Raman Users’ Group
(IRUG) in Vienna, Austria, 26-29 March tration of pollutants in closed spaces. Potentially harmful
2008. conditions have been evaluated by electrochemical reduc-
Guest editor: tion of corrosion products formed on metallic coupons
Prof. Dr. Manfred Schreiner which have been exposed in selected places. In the case of
1. Laboratoire Interfaces et Systèmes silver coupons, this technique allowed chemical identifica-
Electrochimiques, CNRS, UPR15-LISE, tion of the tarnish layer (sulphides and chlorides), as well
Université Pierre et Marie Curie-Paris 6,
4 Place Jussieu, 75005 Paris, France.
as determination of the amount in which they are present
on individual coupons. Extension of this approach to lead
2. IRRAP- Institut de Restauration et de
Recherches Archéologiques et
raises some difficulty as identification of the reduction
Paléométallurgiques, 21 rue des peaks is more complex. In this work we combined electro-
Cordeliers, 60200 Compiegne, France chemical reduction of corrosion products with in-situ
corresponding author: Raman spectroscopy to unambiguously correlate the reduc-
suzanne.joiret@upmc.fr tion peaks with the compounds present on the surface of
coupons previously exposed in different French institu-
tions. Raman analysis carried out prior to the electrochem-
ical reduction in a sodium sesquicarbonate solution
revealed that the corrosion layer contains lead oxides,
hydroxycarbonates and carbonates and in some cases for-
mates and acetates.
1 Introduction
key words: This work suggests the use of lead coupons as sensors, which, after
Lead corrosion, Raman spectroscopy, reaction with the environment, will be analysed by Raman spec-
oxide reduction, organic acids, electro-
chemistry
troscopy, XRD (x-ray diffraction analysis) and electrochemical reduc-
101
www.e-PRESERVATIONScience.org
tion in order to characterize them qualitatively and per coupons were also exposed for another pur-
quantitatively. This quantitative approach based pose. The right image in Figure 1 depicts the dif-
on electrochemistry has already been successfully ferences in the aspect of the coupons before and
applied to silver by one of the author. 1,2 after exposure.
3 Results
102 Raman spectroscopy for the characterization of lead corrosion, e-PS, 2009, 6, 101-106
© by M O R A N A RTD d.o.o.
Raman spectroscopy for the characterization of lead corrosion, e-PS, 2009, 6, 101-106 103
www.e-PRESERVATIONScience.org
litharge massicot
hydro-
lead
lead On the surface of the specimen PP1 only litharge
sample cerussite acetate, could be found (Figure 7a), but some spectra show
α-PbO β-PbO formate
/cerussite basic
also the presence of massicot with the typical
A1 - - x x x
band at 285 cm -1 in isolated places. The laser
BN1 x - x x x
power was decreased to the minimum level as the
BN2 X - X - x thermal transformation of lead oxide is a well
PP1 x x - - - known process, but the characteristic bands of
PP2 X - X X x massicot were still appearing in the spectrum.
Table 2: Corrosion products formed in the various samples.
Nevertheless, only lead(II) oxides are encountered
on this sample.
104 Raman spectroscopy for the characterization of lead corrosion, e-PS, 2009, 6, 101-106
© by M O R A N A RTD d.o.o.
Figure 6: Raman spectra of the sample BN1. a) ex-situ; b) in borate Figure 8: Current versus potential (voltammogram) at 5 mV/sec in
solution at open circuit potential; c) in borate solution at -1.3 V/SSE. borate solution for PP1, PP2, BN1 and BN2 coupons.
corrosion rate
sample (nm PbO/year)
A1 -
BN1 1.2
BN2 1.1
PP1 0.36
PP2 2.4
Raman spectroscopy for the characterization of lead corrosion, e-PS, 2009, 6, 101-106 105
www.e-PRESERVATIONScience.org
same institution. Moreover, the relative amount of changes of historical lead objects as a result of the use of elec-
trolytic reduction as a stabilization treatment, Anal. Chem., 2006,
organic salts detected in the corrosion products
78, 8319-8323.
was particularly high for the most corroded sam-
ple. Further work is in progress aiming to improve
the method in order to be able to reduce the car-
bonate layer, and in this way, evaluate its thick-
ness.
5 References
1. V. Costa, Electrochemical techniques applied to metals conser-
vation, Materials Research Society Symposium Proceedings, 2005,
852, 89-96.
106 Raman spectroscopy for the characterization of lead corrosion, e-PS, 2009, 6, 101-106