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Corrosion behavior and preservation of Islamic Silver Alloy Coins

Ziad Al-Saad and Manar Bani Hani
Faculty of Archaeology and Anthropology, Yarmouk University
Yarmouk University
Irbid-Jordan
e-mail: zalsaad@yu.edu.jo

The corrosion behaviour of a collection of Islamic silver-based coins from Museum of Jordanian Heritage at
Yarmouk University was investigated by using a combination of non-destructive analytical techniques includ-
ing scanning electron microscope with energy dispersive X-rays (SEM-EDX) and Energy Dispersive X-ray
Fluorescence Analysis (ED-XRF). The results of this study have been used to devise the proper conservation
approaches and methods that should be adopted to preserve these important cultural heritage materials.

Keywords: Islamic Silver Coins, Corrosion, Conservation

1. INTRODUCTION sulfide forms thick black layers of patina. The presence of

Coins are important historical documents as they pro-
vide valuable information about the various aspects of an-
cient civilization used them. Coins are usually found in
large numbers in archaeological excavations, because they
have high survival rate when compared to other types of
metal artefacts.
The analysis of elemental composition of ancient coins
has generated a lot of interest in recent years as it can pro-
vide valuable information on various aspects of human
past civilizations particularly the political socio-economic
and technical aspects. [1].
These important historical records, especially those
made of copper and silver, can suffer from various forms
of corrosion caused by various natural and human fac-
tors. Corrosion may in some cases be so extensive that it
may lead to complete mineralization of coins with the
consequent loss of important historical information.
Identifying and understanding the causes and mecha-
nisms of corrosion is a key step toward designing and im-
plementing effective conservation measures to preserve
these coins.
This paper focuses on the study of the corrosion be-
haviour of silver coins. A collection of Islamic silver alloy
coins from the collection of the Museum of Jordanian
Heritage at Yarmouk University is used for this purpose.
Corrosion behavior of silver alloy coins
In general silver can be found in a native state com-
bined with gold, tin, copper, and platinum. It is completely
stable in aqueous solutions of most pHs as long as oxidiz-
ing agents or complexing substances are not present. In
addition, silver is not appreciably affected by dry or moist
air that is free from ozone, halogens, ammonia, and sulfur
compounds [2]. Silver is readily tarnished by hydrogen sul-
fide, which is an atmospheric contaminant: a thin layer of
dark silver sulfide (Ag2S) is formed. Occasionally silver
177
chlorides in solids where silver is buried causes the forma-
tion of stable, gray silver chloride (AgCl) which may,
through the great expansion accompanying the change
from metal to mineral, cause severe deformation of the
original object [3]. In the case of silver alloys with signifi-
cant amount of copper, the copper corrodes preferentially
forming cuprous oxide, cupric carbonate, and cuprous
chloride [4].
Silver corrosion processes vary according to the origi-
nal composition of the silver alloy and the conditions to
which it has been subjected. Therefore, corrosion behav-
ior of silver is a function of the surrounding environmental
conditions.
All metals undergo corrosion, but the chances for
propagation of the corrosion process are determined by
the structure of the oxide layer growing on the metal con-
cerned. With silver, the oxide is formed by insertion of
oxygen into the octants of the face centered cubic silver
lattice, and the resulting film is oriented with respect to
the metal. Silver oxide should, therefore, be highly protec-
tive. But despite this compatibility of silver oxide, silver
becomes easily tarnished. The causes of tarnishing are dis-
cussed below [5].
In the moist air, the adsorption of oxygen on silver is
accompanied by simultaneous adsorption of water mole-
cules. This combined adsorption gives rise to hydrogen
peroxide which, in its turn, generates and also promotes
lattice defects in the thus formed silver oxide. This then
leads to a non-stoichiometric model of metal oxide. The
passages pierced thus through the oxide film are open to
the silver cations, which then drawn by the electrostatic
potential already set up across the oxide film, move from
the metal phase, through the oxide phase, to the inter-
phase oxide/atmosphere. A subsequent contact of the sil-
ver cations with the sulfide ions from the polluted atmos-
phere air produces the insoluble black silver sulfide,
which is responsible for the tarnishing of silver [5, p.184].
AP°YPO¶OY§OY TELOS 30-01-08 11:03 ™ÂÏ›‰·178
Z. Al-Saad and M. Bani Hani
The reactions between silver and hydrogen sulfide (H2S),
and silver and carbonyl sulfide (OCS) in the atmosphere
are simplified by the following overall reactions [6]:
2 Ag + H2S + 1/2 O2 → Ag2S + H2O (1)
2Ag + OCS → Ag2S +CO (2)
An aggravating factor in the tarnishing of silver is that
the already formed film of silver sulfide upon the film of
silver oxide has a type of lattice in which the arrangement
of the sulfide anions is perfect, while the silver cations are
disarranged and also free to move through the film. In
addition, silver sulfide is a better electrical conductor
than silver oxide and its cations diffuse with ease through
the corrosion film, which under these conditions grows
following a parabolic relationship with time. Such disor-
ders contribute eventually to the growth of spongy silver
sulfide [5].
Silver embrittlement
Silver is normally malleable, ductile and easily fabri-
cated metal. However, some archaeological silver objects
can be brittle, as a long-term consequence of corrosion
and micro-structural changes [6].
There are many types of embrittlement. Corrosion-in-
duced embrittlement is a consequence of selective corro-
sion that penetrates the metal and eventually fragments it.
This occurs whether or not the object is acted upon by ex-
ternal loads or forces, although they may accelerate the
process. Micro-structurally induced embrittlement causes
apparently pristine metal to crack and fracture under the
action of external loads or forces. However, it is important
to note that corrosion-induced and micro-structurally in-
duced embrittlement can act synergistically, and that mi-
cro-structural features are involved in both kinds of em-
brittlement [6].
Recognition and determination of corrosion-induced
and micro-structurally-induced embrittlement, and also
their synergy, are important for conservation of ancient
and historic silver alloys [7].
2. SAMPLE AND EXPERIMNTAL PROCEDURES
2.1 The Sample
Ten silver-based coins that are dated to the Islamic pe-
riod (Abbasid) are selected for the purpose of this study.
The coins are part of Islamic coins collections of the Mu-
seum of Jordanian Heritage. The selected coins were
minted in a short time span (43 years) in the period: A.D.
769 – A.D.812 (A.H. 152 - A.H.196) during the reigns of
five prominent Abbasid caliphs: Mansur, Mehedi, Hadi,
Harun er-Rashid, and Amin. The collection is a typical ex-
ample of the Islamic coinage traditions during the Ab-
basid period. A selected example from the study collection
is shown in Figure 1.
178
Coin 1
ø = 23.84 nm
Coin 2
ø = 24.49 nm
Coin 1
ø = 27.86 nm
Figure1 - The obverse (left) and reverse (right)
of three coins selected from the study sample.
2.2 Previous treatment of coins
The selected coins were previously chemically cleaned
using thiourea and formic acid. However, mild silver dip
solution that consists of 5 percent thiourea and 5 percent
formic acid was prepared to remove outer silver tarnish
and copper corrosion products. The solution was applied
locally using cotton swab in order to avoid future risks and
to keep the cleaning process under control. After clean-
ing, the coins were thoroughly washed using distilled wa-
ter in order to remove the remains of the added chemicals
and the soluble products that they carry. After that, the
coins were dried using acetone. No coating were applied
to protect them, they were displayed in the museum show-
cases with no environmental control.
2.3 Condition Assessment
Visual examination combined with optical microscopic
and SEM investigation was employed to assess and evalu-
ate the general preservation condition of the coins.
2.4 Chemical Analysis
Chemical analysis was carried out to identify the
chemical composition of both the metal core and the cor-
rosion products formed. This enables the determination
of the extent of damage of the artifact and the under-
standing of the corrosion causes and mechanisms. These
are essential prerequisites for the development and imple-
mentation of effective and suitable conservation treat-
ments [8].
Chemical analysis of corrosion products was made us-
ing two analytical techniques: XRF (XRF: PANalytical,
MiniPal 2) and SEM-EDX. Energy dispersive X-ray Fluo-
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Corrosion behaviour and preservation of Islamic silver alloy coins

rescence Analysis (ED-XRF) in order to determine the

Ag content as well as minor constituents (Cu, Pb) and
trace elements. In addition, the presence of chloride or
sulfide ions gives an indication about the presence of cor-
rosion, its type and extent within the surface of the metal
artifact.
Energy dispersive X-ray microanalysis with a scanning
electron microscope was used to assess the extent and na-
ture of the corrosion of the coins. The first EDX-SEM
analysis was done in four different but neighboring points
on coin 3 as shown in Figure 2, as well as the results of the
analysis in Table 1. Further analysis was carried out on a
corrosion area for coin 3 as shown in Figure 3 and analyti- Table 1 - Chemical Compositions of Points on Coin 3
cal results given in Table 2.
Using SEM-EDX Analysis (percent error = 0.01%).

Element wt.%
O 29.9
Zn 0.6
Na 0.3
Mg 0.8
Al 4.4
Si 24.2
P 0.4
Au 0.9
Hg 0.6
S 0.5
Cl 8.0
Ag 27.4
K 4.1
Total≅ 100

Table 2 - Chemical Compositions of a Corrosion Area

on Coin 3 Using SEM-EDX Analysis
Figure 2 - The Four Analyzed Points (percent error = 0.01%).
on the Surface of Coin 3.

Figure 3 - Corrosion Point Analyzed.

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Z. Al-Saad and M. Bani Hani

Table 3 - Corrosion Forms using different techniques of analysis for the coins.

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Corrosion behaviour and preservation of Islamic silver alloy coins

Table 4 - Chemical Composition of the Coins Using XRF Analysis. (Percent error =0.1% ).

3. RESULTS AND DISCUSSION
3.1 Visual and Microscopic Examination
The results of the visual and microscopic investiga-
tions are given in Table 3. The results show that the coins
are generally in good condition. However, all the coins
have a thin general corrosion layer formed. Some of the
coins suffer from localized corrosion and some others
have slight embrittlement problems.
of copper. Condition assessment of the coins shows clear
correlation between lead content and degree of embrittle-
ment of these coins.
The analysis of the corrosion products reveals a rela-
tively high chloride content in some of the coins with very
low content of sulfide. This indicates that silver chloride
rather than silver sulfide is the major corrosion product of
these coins. It can be concluded that the coins were exca-
vated from a chloride rich burial environment.

3.2 XRF Analysis 3.3 SEM-EDX Analysis

The results of the XRF analysis are presented in Table Examination using SEM revealed corrosion and em-
4. The results show that all the coins have a high silver brittlement phenomenon that are present in most of the
content which indicates the high quality control of the studied coins. SEM investigation shows localized corro-
manufacturing process of these Islamic coins. sion that penetrates the silver and enables embrittlement
All of the coins contain copper, and most of them have due to cracking along the corrosion paths as seen clearly
appreciable amounts of lead which indicates the deliber- in Figure 4.
ate additions of these two metals in the alloy used for the
manufacturing of the coins. Copper could have been de-
liberately added to debase the silver coins and save the
more expensive silver. In addition, there is a technical rea-
son for the addition of copper to silver. Pure silver is nor-
mally considered too soft to be used for coinage and could
relatively easily be worn in circulation. The addition of
copper considerably increased the strength, hardness and
wear-resistance of silver without leaving a deleterious ef-
fect on its ductility and formability. The chemical analysis
results show an appreciable amount of lead present in the
coins. This indicates that the silver used in the coins was
produced by the cupelation process. The complete re-
moval of lead in this process seems never to have been
achieved. Silver coins can be embrittled in the course of
time due to the remains of lead left from cuppelation. It Figure 4 - Corrosion Induced Embrittlement in Coin 1
has been found that it is particularly bad in the presence (SEM image)

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Z. Al-Saad and M. Bani Hani
In addition, visually undetected scratches probably
caused by mishandling or improper cleaning were seen in
the surface of many coins (as depicted in Figure 5)
Figure 5 - Scratches in the Surface of Coin 1
(SEM image)
Using SEM we were able to relate uncorroded regions
with the non-inscribed regions whereas it appears that
corrosion and embrittlement are concentrated in the in-
scribed regions where the corrosive agent are trapped as
shown in Figure 6. In addition, the coins greatly suffer
from the rims with some parts totally lost. This may be a
result from the synergistic action of plane of weakness
that results from the continuous downfall on the rim and
corrosion that increase the weakness of this part of the
coin as shown in Figure 7.
Figure 6 - Corrosion and Embrittlement
in the Inscriptions Region of Coin 1 (SEM image)
182
Figure 7 - Lost Part from the Rim of Coin 1
(SEM image)
4. CONSERVATION CONSIDERATIONS
The conservation requirements of the selected coins
vary to large degree based on the nature and state of cor-
rosion and on the nature of the contaminants. Some of the
coins need cleaning to remove the localized disfiguring
corrosion at the rims. Some of them need only cosmetic
cleaning to remove some of the copper corrosion that ob-
structs some of the details and for aesthetic reasons.
Chlorides need to be removed to stabilize the coins and to
reduce their damaging effect on the copper component of
base silver alloys [4].
The crucial factor guiding decisions about cleaning
and/or consolidation of an object is its stability. Priority
should be given to stabilization and only later can questions
about appearance and legibility, which are generally more
subjective, be addressed. In some cases, the preservation of
details such as evidence of manufacturing techniques may
guide the selection of methods of treatment [9].
5. CONCLUSIONS
Microscopic and chemical analysis enables the deter-
mination and understanding of the corrosion behaviour of
silver coins under various surrounding conditions. Effec-
tive conservation and stabilization treatments of such ob-
jects are only possible when this behaviour is well under-
stood.
REFERENCES
[1] Al-Saa’d, Z.: “Chemical Analysis of some Umayyad
Dirhems Minted at Wasit,” Journal of Economics
and Social History, Vol. 42, No. 3, pp. 351-363
(1999).
AP°YPO¶OY§OY TELOS 30-01-08 11:03 ™ÂÏ›‰·183
Corrosion behaviour and preservation of Islamic silver alloy coins
[2] Plenderleith, J. and Werner, A., “The Conservation
of Antiquities and Works of Arts,” London: Oxford
University, pp. 239 (1971).
[3] Goffer,Z., Archaeological Chemistry. New York:
John Wiley and Sons.Gold and silver mines (1980).
[4] Hamilton, D.: “Conservation of Metal Objects from
Underwater Sites: a Study in Methods,” Austin:
The Texas Memorial Museum, pp.15 (1976).
[5] Stambolov, T.: “The Corrosion and conservation of
Metallic Antiquities and Works of Arts,” Amster-
dam: CL Publication, pp. 182-184 (1985).
[6] Wanhill, R., et al.: “Damage Assessment and Preser-
vation of an Egyptian Silver Vase (300-200 BC),” Ar-
183
chaeometry, Vol. 40, No. 1, pp. 123-137 (1998).
[7] Wanhill, R.: “Brittle Archaeological Silver: a Frac-
ture Mechanisms and Mechanics Assessment,” Ar-
chaeometry, Vol. 45, No.4. pp. 625-636(2003).
[8] Linke, R., Schreiner, M., and Demortier, G.: “The
Application of Photon, Electron and Proton Induced
X-ray Analysis for the Identification and Characteri-
zation of Medieval Silver Coins,” Nuclear Instru-
ments and Methods in Physics Research B, Vol. 226,
pp. 172–178(2004).
[9] Costa, V.: “The Deterioration of silver Alloys and
some Aspects of their Conservation,” Reviews in
Conservation, Vol. 2, pp. 19-35 (2001).