Studies in Conservation

ISSN: 0039-3630 (Print) 2047-0584 (Online) Journal homepage: http://www.tandfonline.com/loi/ysic20

A novel method for conservation of copper-based

artifacts

M.C. Ganorkar, V. Pandit Rao, P. Gayathri & T. A. Sreenivasa Rao

To cite this article: M.C. Ganorkar, V. Pandit Rao, P. Gayathri & T. A. Sreenivasa Rao (1988)
A novel method for conservation of copper-based artifacts, Studies in Conservation, 33:2,
97-101, DOI: 10.1179/sic.1988.33.2.97

To link to this article: http://dx.doi.org/10.1179/sic.1988.33.2.97

Published online: 19 Jul 2013.

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 A NOVEL METHOD FOR CONSERVATION OF COPPER-BASED
ARTIFACTS
M~ C. Ganorkar, V. Pandit Rao, P. Gayathri and T. A. Sreenivasa Rao

Abstract-A new method was developed for
removing bronze disease and for the conservation of
ancient copper and copper-based artifacts. An
or~a~ic compound, 2-amino-5-mercapto-l,3,4-
thladlazole was found to be a good inhibitor. It
removes the bronze disease completely and forms a
protective polymeric complex layer on the surface of
the metal artifacts, which is resistant to corrosion.
Downloaded by [University of Birmingham] at 15:32 15 May 2016
chemicals are not removed completely, they con-
tinue to react with the metal, causing further
deterioration. Moreover, the bronze disease will
not be removed completely.
Different methods have been reported for the
stabilization of well-patinated bronzes, with
very little or no metal core. These include the

sodium sesquicarbonate treatment [3], exposure

1 Introduction to vapours of ammonia [4], or filling the cavities
with silver oxide paste after removing the dis-
Corrosion of coins and other artifacts made of ease mechanically [5]. A few organic inhibitors
copper and copper-based alloys has become a like benzotriazole have also been employed to
great problem for archaeologists, numismatists arrest the corrosion [6-14]. The treatment by
and archaeological chemists. Cuprous chloride benzotriazole forms a layer of Cu- BTA poly-
is one of the main corrosion products of copper meric complex over the corroded surface of art i-
and its alloys; it is most damaging and unstable. facts which arrests further corrosion. The green
Ancient copper and bronze artifacts can survive insoluble polymeric complex can cover details of
in burial conditions for centuries without appre- the coins and artifacts. The main requirement of
ciable deterioration because an equilibrium is the archaeologist and numismatist is that
established between the corroded metal and its inscriptions and die-stamps which were origi-
nally on the coins should be visible and pre-
surroundings. The equilibrium will be disturbed
served even after treatment. Generally these
by the excavation of the object. The unstable
cuprous chloride can react immediately with free markings are under the corrosion layers and a
suitable cleaning and stabilization method
oxygen to form cupric chloride which later
should be selected to make the details clear
reacts with fresh copper metal to form unstable
without damaging the remaining part of th~
cuprous chloride.
metal. With this aim the cleaning and conser-
2Cu2Cl2 + [0] ~ CU20 + 2CuCl2
CuCl2 + Cu ~ Cu2Cl2
3Cu2Cl2 + 3[0] + 4H20 ~
[CuCI2 . 3Cu(OH)2 . H20] + 2CuCl2
[1]
Attempts have been made to clean excavated
bronzes with different chemicals such as formic
ac~d, alkaline glycerol, Rochelle salt, sulphuric
aCId and EDTA solutions [2]. These com-
pounds, acidic/basic in nature, have been found
to be defective as they leach out some of the
alloying metals during treatment. The soluble
reaction products have to be removed after the
treatment by lengthy washing procedures which
can leach out some more metal. If these treated

Received 21 May 1987 Figure 1 Corroded Muslim coins before treatment.

Studies in Conservation 33 (1988) 97-101 97

 M. C. Ganorkar, V. Pandit Rao, P. Gayathri and T. A. Sreenivasa Rao
vation of corroded copper coins of the Muslim
dynasty (Figure 1) and the head of a god were
carried out with an organic compound,
5-amino-2-mercapto-l,3,4-thiadiazole (AMT)
(Figure 2).
Figure 2 Structure of 5-amino-2-mercapto-l,3,4-
thiadiazole.
Downloaded by [University of Birmingham] at 15:32 15 May 2016
2 Experimental
The heterocyclic compound, 5-amino-2-
mercapto-l,3,4-thiadiazole (AMT) has been
synthesized as per the reported procedure [15].
The compound is a pale yellow coloured crys-
talline solid with a melting point of 238C and is
soluble in hot water and alcohol. In the initial
experiment, 15 corroded coins of the Muslim
dynasty were. obtained from the Birla Archae-
ological and Cultural Research Institute
Museum (BACRI), Hyderabad, India. The cor-
rosion products were studied by X-ray
diffraction, using a Philips PW-lOI0 X-ray
diffractometer with CuKe<radiation.
. These coins, and the head of a god, were first
washed several times with distilled water to
remove soluble chlorides and other superficial
impurities. The cleaned coins were then
immersed in 150ml of 001M aqueous solution
of the AMT compound. In order to speed up the
reaction a few drops of nitric acid (1:1) were
added and later the solution was heated to about
60C. It was observed that a pale yellowish-
green curdy precipitate was formed on the dis-
eased areas of the coins. After one hour, the
coins were removed and washed with distilled
water. This procedure was repeated until the dis-
appearance of the precipitate was obtained. The
reaction was also carried out under vacuum in
order to remove the air bubbles and to allow the
AMT compound to enter into the micropores of
the coin. After this procedure, the coins were
washed with distilled water and dried. These
treated coins were kept in a humidity chamber
with temperature control to check for the pres-
98
ence of bronze disease, if any, at high RH. In the
case of reappearance of disease the above treat-
ment was repeated.
A modified method was adopted for the
copper and bronze coins obtained from the
excavation section of BACRI as these coins
were highly corroded and thin, with less metal
core. The inscriptions and other details were
completely covered by the patina. These were
first subjected to washing to remove superficial
clay matter and dirt, then treated with OOlM
AMT solution. Treatment was carried out until
the surface details were clear. As the coins are
highly corroded, with less metal core, there is a
need to stabilize the internal remaining corroded
crust. The coins were then immersed in 3% ben-
zotriazole solution under vacuum until no more
bubbles from the micropores occurred. After-
wards the coins were removed and tested in a
humidity chamber.
Another corroded coin, after preliminary
cleaning, was stabilized with benzotriazole for
comparison with the AMT treatment. IR
reflectance studies of the coin surface were also
carried out with the help of a Perkin-Elmer
model 283 IR spectrophotometer to observe the
formation of any complex coating.
3 Discussion
The X-ray diffraction data (Figure 3) of the cor-
roded material revealed the presence of ata-
camite (Cu2(OH)3CI) and botallacite, and
showed that these coins and the head of a god
were affected by bronze disease. The above
experiments showed that the AMT compound
forms a complex species with ionic copper
present in bronze disease. The complex comes
out as a pale green-yellow coloured precipitate
from the diseased areas, thereby making the
coin free of disease. This process was continued
until the bronze disease was entirely removed
from the micropores and from underlying metal.
After complete removal of the bronze disease,
AMT forms a fine thin polymeric complex film
over the metal surface. The formation of this
film was confirmed with the help of IR
reflectance spectral analysis.
The IR spectrum of AMT shows a sharp band
at 2520cm - 1 assigned to v S - H, which is
absent in the spectrum of coating material, indi-
cating the deprotonation of the S - H group
Studies in Conservation 33 (1988) 97-101
 A novel method for conservation of copper-based artifacts

Major: CuCI23[Cu(OH)2J
Cu2(OH)3C1
Minor: Cu20

Traces: CuC03Cu(OH)2
CuCI LO
N
N
Downloaded by [University of Birmingham] at 15:32 15 May 2016

Figure 3~ X-ray diffraction data of patina of Muslim period coinage.

and subsequent bonding of sulphur to the metal artifacts. Also, there was no effect with tem-
ion. Formation of an S - M bond was perature variations (25C to 100C). From these
confirmed by the appearance of a new band at stability tests it was concluded that the AMT
345cm - 1 due to S - M vibrations. The bands at compound acts as an excellent remover for
1620cm -1, 1070cm -1 and 1560cm -1 in the bronze disease and corrosion inhibitor. Due to
AMT spectrum, assigned to v C = N, v N = N the removal of the disease it was observed that
and v N - H respectively, were shifted to the inscriptions and other details on the coins
1600cm -1, 1045cm -1 and 1510cm -1. The mul- were very clear and visible. The inscriptions on
tiple bands at 2900- 3400cm - 1 of the AMT spec- the coins treated with BTA are not visible even
trum, which were assigned to the symmetric and though the bronze disease is stabilized (Figure.
asymmetric stretching of the N - H, were also
shifted to 3080-3280cm -1 in the complex spec-
trum. The band at 450cm - 1, attributed to
M - N, suggests the participation of the
nitrogen of the NH2 group in active coordi-
nation. From the IR data it is quite evident that
complex formation has taken place on the metal
surface. For further confirmation of complex
formation the AMT compound was treated with
copper salt solutions [16] and copper sheets
immersed in acidic solutions. The IR spectrum
of the complex formed in both cases resembled
that of the above data. From the humidity tests
it was observed that there was no effect on these
artifacts. If there were a trace of bronze disease
in these artifacts, humidity would have definitely
affected them. The artifacts were exposed to the Figure 4 A coin showing clear inscriptions after treat-
atmosphere for six months and it was observed ment with AMT. Another coin with blue-green patches
that there was no change over the surface of the is stabilized with BTA.

Studies in Conservation 33 (1988) 97~ 101 99

 -----_._--------- -_._---------- ---

I
M. C. Ganorkar, V. Pandit Rao, P. Gayathri and T. A. Sreenivasa Rao
I
4). For highly corroded coins with less metal Conservation of Antiquities and Works of Art,
core there is a chance of the coin becoming Oxford University Press, London (1976)
porous with the AMT due to the removal of 189-296.
bronze disease. These types of coins were first 3 ODDY, W. A., and HUGHES, M. J., 'The sta-
bilization of 'active' bronze and iron antiqui-
treated slowly with AMT until the inscriptions
ties by the use of sodium sesquicarbonate',
were visible, then internal corrosion was sta-
Studies in Conservation 15 (1970) 183.
bilized with BT A. Figure 5 shows the appear- 4 THOUVENIN, A., 'Une nouvelle methode de
ance of the head of a god after treatment with dechloruration des bronzes antiques prov-
the AMT compound. enant de fouilles', Revue Archeologique (Paris)
2 (1958) 180.
5 ORGAN, R. M., 'Aspects of bronze patina and its
treatment', Studies in Conservation 8 (1963)
1-9.
6 MADSEN, H. B., 'A preliminary note on the use of
benzotriazole for stabilizing bronze objects',
Downloaded by [University of Birmingham] at 15:32 15 May 2016

Studies in Conservation 12 (1967) 163-167.

7 MADSEN, H. B., 'Further remarks on the use of
benzotriazole for stabilising bronze objects',
Studies in Conservation 16 (1971) 120-122.
8 GREENE, V., 'The use of BTA in conservation:
problems and experiments' in ICOM Com-
mittee for Conservation, Madrid, 1972.
9 GREENE, V., 'The use of benzotriazole in conser-
vation', paper presented at the IIC-NKF Joint
International Congress, Stockholm, 1975.
10 COTTON, J. B., and SCHOLES, I. R., 'BTA and
related compounds as corrosion inhibitors for
copper', British Corrosion Journal 2 (1967)
1-5.
11 MANSFIELD, F., SMITH, T., and PARRY, E. P.,
'Benzotriazole as a corrosion inhibitor for
copper', Corrosion 27 (1971) 289-294.
12 SEASE, C., 'Benzotriazole: a review for conser-
vators', Studies in Conservation 23 (1978)
76-85.
13 ANGELUCCI, S., FIORENTINO, P., KOSINKOVA, J.,
Figure 5 Head of a god after treatment with AMT. and MARABELLI, M., 'Pitting corrosion in
copper and copper alloys: comparative treat-
ment test', Studies in Conservation 23 (1978)
4 Conclusions 147-156.
14 MERK, L. E., 'The effectiveness of benzotriazole
From the above study it was concluded that the in the inhibition of the corrosive behaviour of
compound AMT is capable of conlpletely stripping reagents on bronzes', Studies in Con-
removing bronze disease, even from the micro- servation 26 (1981) 73-76.
pores of corroded coins, and making the inscrip- 15 SANDSTROM, J., 'Cyclization of thio-
carbohydrazide and its mono-hydrazones',
tions and details quite clear. The compound
Acta Chem. Scand. 15 (1961) 1300.
AMT was also found to be an excellent inhibitor 16 GANJENDRAGAD, M. G., and AGARWALA, W.,
for copper-based coins and artifacts. 'Complex behaviour of 5-amino-l,3,4-
thiazole-2-thiol II', Bulletin of the Chemical
Society of Japan 48 (1975) I024~ 1029.
References

GOFFER, Z., Archaeological Chemistry, John M. C. GANORKAR, MSc, Osmania University,

Wiley and Sons, New York (1980) 252-283. Hyderabad, India, PhD (Inorganic Chemistry), Uni-
2 PLENDERLEITH, H. J., and WERNER, A. E. A., The versity of London. Post-doctoral research fellow at

100 Studies in Conservation 33 (1988) 97-10 I

 A novel method for conservation of copper-based artifacts
Queen Mary College, London. Retired as Professor
of Chemistry from Osmania University, Hyderabad,
India, in 1985. Currently Director, The Birla Institute
of Scientific Research, Hyderabad, India. Main areas
of research: organometallics, conservation studies on
ancient artifacts, spectral studies (ESR, NMR, IR,
Mossbauer, etc.)to characterize the structures of new
synthetic compounds. Author's address: The Birla
Institute of Scientific Research, Asmangadh Palace,
Malakpet, Hyderabad 500 036, India.
V. PANDITRAo, MSc in Inorganic Chemistry from
Gujarat University, Ahmedabad, and PhD in Chem-
istry from Bhavnagar University, India (1982). At
present working as Scientific Officer at The Birla
Downloaded by [University of Birmingham] at 15:32 15 May 2016
Institute of Scientific Research, Hyderabad. His field
of interest is coordination chemistry, conservation
studies on metal artifacts and Mossbauer studies on
ancient pottery. Author's address: as for Ganorkar.
P. GAYATHRI,MSc in Organic Chemistry from
Osmania University, Hyderabad, India (1976). Pres-
ently working as Scientist in The Birla Institute of
Scientific Research, Hyderabad. Her field of research
is metallographic studies and the conservation of
ancient metal artifacts. Author's address: as for Gan-
orkar.
Studies in Conservation 33 (1988) 97-101
T. A. SREENIVASA RAo, MSc from University of
Hyderabad, India. At present he is working as Sci-
entist in The Birla Institute of Scientific Research,
Hyderabad. Presently doing research on the synthesis
of inorganic polymers for the conservation of metals
and stone. Author's address: as for Ganorkar.
Resume--L'artic1e expose une nouvelle methode pour
debarasser Ie bronze de ses produits de corrosion,
applicable aux objets anciens en cuivre ou a base de
cuivre. II s'agit de l'emploi d'un compose organique Ie
2-amino-5-mercapto-l ,3,4-thiadiazole qui s'avere etre
un bon inhibiteur: il debarasse l'objet de sa coudre de
corrosion et forme une couche protectrice d'un com-
plexe polymerise a la surface des objets de metal qui
resistent ainsi au vieillissement.
Zusammenfassung-Chloridabhangige Korrosions-
vorgange an Objekten aus Kupfer oder dessen
Legierungen konnen im Rahmen von Konservie-
rungsmaBnahmen wirksam durch den Einsatz von
2-Amino-5-mercapto-l,3,4-thiadiazol verhindert
werden. Das Thiadiazol bringt diesen Schadigungs-
mechanismus zum Stillstand und bildet einen
korrosionshemmenden, polymeren Schutzfilm auf der
Oberflache des Metallobjektes.
101