CHARACTERISATION AND STABILITY OF ARTIFICIAL PATINA ON COPPER AND BRONZE

S. Goidanich, M. Ormellese, E.R. Perez, G. Pintaudi, M. Setti

Dipartimento di Chimica, Materiali ed Ingegneria Chimica, “G. Natta” - Politecnico di Milano, Via Mancinelli, 7, Milano, Italia – sara.goidanich@polimi.it

8º Convegno Nazionale AIMAT

Palermo (Italia) 27 Giugno 1 Luglio 2006
PATINAS are not only produced by the natural action of environment and time, but often they are
Bronze/environment Corrosion intentionally created by the artist in order to express his creativity.
interaction products/patina
It is a matter of fact the it is impossible to find any copper or bronze artefact which is not covered by
a patina, whether natural or artificial.

In order to conserve our historic and artistic patrimony it is of paramount importance to define how
Patination the materials and their patina interact with the environment and to understand the related
artificial
techniques deterioration mechanisms, which are somehow still quite unclear (1, 2). A first task is therefore to
patina
reproduce in the laboratory both natural and artificial patina.
DIFFERENT EVOLUTION AND DETERIORATION
DEPENDING ON THE ENVIRONMENT AND IN THIS WORK the characteristics of the different patinas which were obtained in the laboratory are
INITIAL COMPOSITION presented. A particular attention was paid to the patina composition and to chemical stability.

Patina production in laboratory

In order to study and analyse the patina deterioration processes, the Patina stability under different condition
first step is to reproduce the patina in the laboratory.
12 different patinas were obtained on three different copper alloys. In order to get a simplified
9 CONSERVATION problems
schema about the possible interaction with different environments, these patinas were exposed to
9 Partial or complete re-patination (RESTORATION) three different solutions simulating RURAL, URBAN rain and SEAWATER aerosol
9 Contemporary art (PROTECTION+AESTHETIC)
1.158 1.6 3.12
Patina characterisation
Hot immersion
1.118 Patinas were analysed, before and after exposure to the different
Chemical solutions, by SR micro-sample powder XRD at the 14.1 beamline of the
techniques Vapour technique Daresbury synchrotron source, SRS.
Patina B Patina 3

dabbing and wiping Stability of the different compounds and conditions which leads to their formation

Electrochemical CUPRITE (Cu2O) is obtained under almost all conditions, particularly in the presence of sulphates
techniques of earth-alkaline acids (slightly acid conditions). Generally cuprite was not obtained as a patina
Acetic Na2SO4 Acetic Const. C Const. A constituent only on very acid or alkaline condition, however, even if it was not originally present on
acid acid +
water the patina, it was always formed after the exposure to the different solutions

Most of the compound normally found on natural and SULPHATES. When patinas which contain originally cuprite and CUPRITE
artificial patina (3) were obtained nantokite (CuCl) are exposed to the rural or urban solution, Cu2O
the following sulphates are formed: antlerite, brochantite and ATACAMITE
9 Cuprite Cu2O posnjakite. Time exposure and the original patina composition Cu2(OH)3Cl
seem to be two key factors. BROCHANTITE
9 Tenorite CuO RUR
Cu4SO4(OH)6
1 week
9 Brochantite Cu4SO4(OH)6 POSNJAKITE
Cu4SO4(OH)6 H2O
9 Nantokite CuCl
ANTLERITE
9 Malachite CuCO3·Cu(OH)2 Cu3SO4(OH)4
Cuprite and
9 Copper hydroxylchlorides Cu2(OH)3Cl sulfates
CUPRITE
• Atacamite Cu2O
CUPRITE
• Paratacamite Bronze or Cu CUPRITE URB Cu2O URB ATACAMITE
+ Cu2O 24 h ATACAMITE 1 week Cu2(OH)3Cl
• Clinoatacamite
NaCl CuSO4 NANTOKITE Cu2(OH)3Cl BROCHANTITE
Cu(CH3COO)2 CuCl NANTOKITE Cu4SO4(OH)6
CuCl POSNJAKITE
Cu4SO4(OH)6 H2O

TENORITE (CuO) was obtained in strongly alkaline conditions. Its stability in other condition looks quite limited. When CUPRITE
exposed to urban or marine environment, tenorite tends gradually to convert to cuprite. SEA Cu2O
1 week PARATACAMITE
CHLORIDES. As soon as the materials are exposed to chloride containing solutions, copper chlorides compounds are Cu2(OH)3Cl
formed, regardless of the original patina composition, mostly nantokite (CuCl), atacamite (Cu2(OH)3Cl) followed by CLINOATACAMI
TE
paratacamite, clinoatacamite and connellite.
Cu2(OH)3Cl

Tenorite RUR
NANTOKITE (CuCl) when exposed to different test environments tends to be TENORITE
1 week
converted to an hydoxylchloride, in agreement with what is reported about CuO
the bronze disease mechanism Bronze or Cu (on Cu also CUPRITE Cu2O)
+ URB
TENORITE URB CUPRITE
NaOH + KMnO4 CUPRITE
CuO 24 h 1 week
Cu2O Cu2O
References (only on Cu also TENORITE TENORITE
Bronze or Cu
+ CUPRITE Cu2O) CuO CuO
1) A. Krätschmer, I. Odnevall Wallinder, C. Leygraf., Corrosion Science, 44 (2002)
2) L. Robbiola, J.M. Blengino, C. Fiaud, Corrosion Science, 40, N. 12, (1998) NaOH + K2S2O8
CUPRITE
3) Scott, David A., Copper and bronze in art, The Getty Conservation Institute (2002) Cu2O
SEA PARATACAMITE
1 week Cu2(OH)3Cl
Acknowledgments
TENORITE
Dr. E. Pantos and his colleagues at the Daresbury Synchrotron are sincerely acknowledged for the CuO
opportunity of analysing a large number of samples at the SRS 14.1 beamline and for their support
during the COST-G8 Master Class on SR in Cultural Heritage week at DL, October 2005.

POLITECNICO DI MILANO – Dipartimento di Chimica Materiali e Ingegneria Chimica “Giulio Natta”

(CMIC)