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the Science of the

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ELSEVIER SCIENCE
IRELAND The Science of the Total Environment 143 (1994) 127-129

Chemistry and the conservation of archaeological metals

Francois Schweizer
Laboratoire du Mus~e d'art et d'histoire, 9-11, rue du Clos, 1207 Gen~ve, Switzerland

Abstract

The conservation of archaeological metals is a complex problem which has attracted the attention of chemists since the second
half of the 19th century. Important progress has only been made after the corrosion behaviour of metals under 'archaeological'
burial conditions has been fully understood. The paper illustrates the role of chemistry for the preservation of our cultural heritage.

Key words: Archaeology; Metals; Corosion; Chemistry

1. Introduction and we must accept that in some thousands of

Hidden in the earth for hundreds to thousands
of years, archaeological metal artifacts undergo
changes which alter the entire structure of the
metal and alloys.
Attacked by corrosive agents of the soil, the
metal is transformed partially or even totally into
the corresponding corrosion products. Ancient
bronze alloys often reveal the presence of cuprite
(CuO), malachite (Cu2(OH)2CO 3) and azurite
(Cu2(OH)2(CO2)2), as well as more complex ba-
sic cuprous chlorides such as atacamite
(Cu2(OH)3C1), when they corrode under oxidizing
conditions. Bronze finds from anaerobic water-
logged soils show the presence of chalcopyrite
(CuFeS 2) or covellite (CuS). These corrosion
products are in fact almost identical to the min-
eral from which the metals have been extracted.
When we are developing conservation methods
for the preservation of ancient metallic artifacts
we are in fact interrupting the natural life cycle of
the metal or alloy. It has been extracted from
minerals, shaped into objects, which after use
underwent chemical transformations for hun-
dreds or thousands of years. All metals have a
strong tendency to revert to their original state
years our metallic cultural heritage will have dis-
appeared.
What are we expecting chemistry to do in this
field? We hope to find suitable methods to retard
the natural transformations by inhibiting corro-
sion processes and by extracting corrosive agents
from the metal artifacts. Suitable chemicals are
also used to selectively remove corrosion products
to reveal the original surface of the metal, to
consolidate fragile structures and to protect the
remaining metal from further atmospheric corro-
sion.
Here I shall discuss some aspects of this wide
field of applications.
2. The removal of chlorides from archaeological
iron artifacts
Many metal objects excavated from archaeolog-
ical sites are in very corroded and unstable condi-
tions. This is especially true for iron objects which
suffer severe corrosion. Often, it is no longer
possible to distinguish the original shape of the
object. It can be revealed only by a radiography
where the original shape of the objects appears

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128
clearly. The iron is normally transformed into
iron-hydroxyoxides of a complex and unstable na-
ture.
Archaeological iron objects, containing a re-
maining metal core and thick layers of corrosion
products, are very difficult to stabilize due to the
presence of chlorides at the interface metal-cor-
rosion layer. If they are left without proper con-
servation treatment, they disintegrate completely
after some months.
This problem was realized by the end of the
last century and with the pioneer work of
Friedrich Rathgen of the Berlin Museum Labora-
tory a long series of research projects attempting
to find a suitable method to stabilize the iron
artifacts began. Most of the early washing tech-
niques were unsuccessful and it was only after
Keller [1] showed the water insoluble nature of
iron-hydroxychloride compounds that appropriate
treatments were developed. North and Pearson
showed that by immersing the iron artifacts in a
solution of alkaline sodium sulfite [2] the chloride
can be removed to a safe level.
Washing times are, however, long (from several
weeks to 1 year). So far all attempts to use
inhibitors for the stabilization of archaeological
iron have not really been successful. In the last
few years a promising new technique, the reduc-
tion in a hydrogen plasma, has had a new impact
in this field [3]. This technique gives excellent
results as far as the removal of corrosion layers is
concerned; it fails, however, to reduce the resid-
ual chloride level to an acceptable level (about
200 p.p.m.).
3. Corrosion inhibitors and corrosion stabilizers
Corrosion inhibitors, which are widely used in
industrial applications, have also given some re-
markable results in the field of conservation of
ancient metals [4]. One of the most impressive
example is the stabilization of the so-called
'bronze disease'. Ancient copper alloys, when
buried for long periods of time, develop very
complex corrosion layers composed of the succes-
sive layers of cuprite and malachite. In the pres-
ence of chloride ions, cuprous chloride (CuC1) is
formed at the interface metal-corrosion layer. As
F. Schweizer/Sci. Total Environ. 143 (1994) 127-129
long as this corrosion product is 'sealed', no reac-
tion occurs. With the presence of water and oxy-
gen diffusion through micro-cracks the cuprous
chloride is converted into atacamite. At the same
time new chloride ions are released which reat-
tack the underlying metal.
Early conservation techniques consisted in at-
tempts to convert the cuprous chloride into more
stable silver chloride [5], or to extract it by
immersing the object in a sodium sesquicar-bonate
solution [6]. In 1967 the Danish conservator Mad-
sen [7] suggested for the first time the use of
benzotriazole (3% in water or ethanol).
The stabilizing effects were so good that this
technique has since been used widely for cuprous
alloys [8]. The failure of some treatments can be
attributed to the fact that the benzotriazole
molecule is not able to diffuse through the thick
corrosion layers down to the cuprous chloride.
4. Agents to remove corrosion products
Most private art collectors and museum cura-
tors like to keep a corrosion layer, which is nor-
mally called patina, on their bronze objects. There
are, however, situations where we are forced to
remove these corrosion layers partially in order to
see the original shape of the surface of an object.
This is especially true for ancient coins, where the
archaeologist is mainly interested in the inscrip-
tions. Coins found during an excavation are of
invaluable importance for dating the archaeologi-
cal levels.
The conservation and restoration of coins is
normally done manually under a binocular mi-
croscope. It is a long, delicate and painstaking
task. This work can greatly be facilitated by using
appropriate chemical agents. They must be care-
fully chosen in order to selectively dissolve the
corrosion products only and not the remaining
metal core. It is often necessary to first identify by
X-ray diffraction the chemical nature of the cor-
rosion products and to examine carefully the de-
gree of deterioration of the coins.
On silver-copper coins dilute formic acid selec-
tively removes copper-corrosion products without
attacking the silver-alloy. Chelating and complex-
ing agents such as buffered solutions of EDTA
F. Schweizer/Sci. Total Environ. 143 (1994) 127-129
(ethylendiaminetetra-acetic acid) are useful for
the treatment of copper and bronze coins. Silver
corrosion products, such as silver chloride, are
effectively removed with dilute solutions of am-
monium thiocyanide.
Finally, electrolysis can be very helpful in sepa-
rating the corrosion layers of silver coins from the
metal core and spectacular results can be ob-
tained.
5. Conclusion
These few remarks show how important chem-
istry has become for the conservation of archaeo-
logical metal objects. The complex nature of the
corrosion mechanism can only be understood if
they are examined in the light of recent research
in the field of electrochemistry. With the growing
threat to the cultural heritage, chemistry, cor-
rectly applied, can play a major role in saving
important artifacts from destruction.
129
. References
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2 N.A. North, and C. Pearson, Methods for treating marine
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Meeting. Zagreb (1978) 23/3 1-10.
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