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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


chlorides in solids where silver is buried causes the forma-
Coins are important historical documents as they pro- tion of stable, gray silver chloride (AgCl) which may,
vide valuable information about the various aspects of an- through the great expansion accompanying the change
cient civilization used them. Coins are usually found in from metal to mineral, cause severe deformation of the
large numbers in archaeological excavations, because they original object [3]. In the case of silver alloys with signifi-
have high survival rate when compared to other types of cant amount of copper, the copper corrodes preferentially
metal artefacts. forming cuprous oxide, cupric carbonate, and cuprous
The analysis of elemental composition of ancient coins chloride [4].
has generated a lot of interest in recent years as it can pro- Silver corrosion processes vary according to the origi-
vide valuable information on various aspects of human nal composition of the silver alloy and the conditions to
past civilizations particularly the political socio-economic which it has been subjected. Therefore, corrosion behav-
and technical aspects. [1]. ior of silver is a function of the surrounding environmental
These important historical records, especially those conditions.
made of copper and silver, can suffer from various forms All metals undergo corrosion, but the chances for
of corrosion caused by various natural and human fac- propagation of the corrosion process are determined by
tors. Corrosion may in some cases be so extensive that it the structure of the oxide layer growing on the metal con-
may lead to complete mineralization of coins with the cerned. With silver, the oxide is formed by insertion of
consequent loss of important historical information. oxygen into the octants of the face centered cubic silver
Identifying and understanding the causes and mecha- lattice, and the resulting film is oriented with respect to
nisms of corrosion is a key step toward designing and im- the metal. Silver oxide should, therefore, be highly protec-
plementing effective conservation measures to preserve tive. But despite this compatibility of silver oxide, silver
these coins. becomes easily tarnished. The causes of tarnishing are dis-
This paper focuses on the study of the corrosion be- cussed below [5].
haviour of silver coins. A collection of Islamic silver alloy In the moist air, the adsorption of oxygen on silver is
coins from the collection of the Museum of Jordanian accompanied by simultaneous adsorption of water mole-
Heritage at Yarmouk University is used for this purpose. cules. This combined adsorption gives rise to hydrogen
peroxide which, in its turn, generates and also promotes
Corrosion behavior of silver alloy coins lattice defects in the thus formed silver oxide. This then
In general silver can be found in a native state com- leads to a non-stoichiometric model of metal oxide. The
bined with gold, tin, copper, and platinum. It is completely passages pierced thus through the oxide film are open to
stable in aqueous solutions of most pHs as long as oxidiz- the silver cations, which then drawn by the electrostatic
ing agents or complexing substances are not present. In potential already set up across the oxide film, move from
addition, silver is not appreciably affected by dry or moist the metal phase, through the oxide phase, to the inter-
air that is free from ozone, halogens, ammonia, and sulfur phase oxide/atmosphere. A subsequent contact of the sil-
compounds [2]. Silver is readily tarnished by hydrogen sul- ver cations with the sulfide ions from the polluted atmos-
fide, which is an atmospheric contaminant: a thin layer of phere air produces the insoluble black silver sulfide,
dark silver sulfide (Ag2S) is formed. Occasionally silver which is responsible for the tarnishing of silver [5, p.184].
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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) Coin 1
2Ag + OCS → Ag2S +CO (2) ø = 23.84 nm
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 Coin 2
than silver oxide and its cations diffuse with ease through ø = 24.49 nm
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 Coin 1


Silver is normally malleable, ductile and easily fabri- ø = 27.86 nm
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- Figure1 - The obverse (left) and reverse (right)
duced embrittlement is a consequence of selective corro- of three coins selected from the study sample.
sion that penetrates the metal and eventually fragments it.
This occurs whether or not the object is acted upon by ex- 2.2 Previous treatment of coins
ternal loads or forces, although they may accelerate the The selected coins were previously chemically cleaned
process. Micro-structurally induced embrittlement causes using thiourea and formic acid. However, mild silver dip
apparently pristine metal to crack and fracture under the solution that consists of 5 percent thiourea and 5 percent
action of external loads or forces. However, it is important formic acid was prepared to remove outer silver tarnish
to note that corrosion-induced and micro-structurally in- and copper corrosion products. The solution was applied
duced embrittlement can act synergistically, and that mi- locally using cotton swab in order to avoid future risks and
cro-structural features are involved in both kinds of em- to keep the cleaning process under control. After clean-
brittlement [6]. ing, the coins were thoroughly washed using distilled wa-
Recognition and determination of corrosion-induced ter in order to remove the remains of the added chemicals
and micro-structurally-induced embrittlement, and also and the soluble products that they carry. After that, the
their synergy, are important for conservation of ancient coins were dried using acetone. No coating were applied
and historic silver alloys [7]. to protect them, they were displayed in the museum show-
cases with no environmental control.

2. SAMPLE AND EXPERIMNTAL PROCEDURES 2.3 Condition Assessment


Visual examination combined with optical microscopic
2.1 The Sample and SEM investigation was employed to assess and evalu-
Ten silver-based coins that are dated to the Islamic pe- ate the general preservation condition of the coins.
riod (Abbasid) are selected for the purpose of this study.
The coins are part of Islamic coins collections of the Mu- 2.4 Chemical Analysis
seum of Jordanian Heritage. The selected coins were Chemical analysis was carried out to identify the
minted in a short time span (43 years) in the period: A.D. chemical composition of both the metal core and the cor-
769 – A.D.812 (A.H. 152 - A.H.196) during the reigns of rosion products formed. This enables the determination
five prominent Abbasid caliphs: Mansur, Mehedi, Hadi, of the extent of damage of the artifact and the under-
Harun er-Rashid, and Amin. The collection is a typical ex- standing of the corrosion causes and mechanisms. These
ample of the Islamic coinage traditions during the Ab- are essential prerequisites for the development and imple-
basid period. A selected example from the study collection mentation of effective and suitable conservation treat-
is shown in Figure 1. 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 of copper. Condition assessment of the coins shows clear
correlation between lead content and degree of embrittle-
3.1 Visual and Microscopic Examination ment of these coins.
The results of the visual and microscopic investiga- The analysis of the corrosion products reveals a rela-
tions are given in Table 3. The results show that the coins tively high chloride content in some of the coins with very
are generally in good condition. However, all the coins low content of sulfide. This indicates that silver chloride
have a thin general corrosion layer formed. Some of the rather than silver sulfide is the major corrosion product of
coins suffer from localized corrosion and some others these coins. It can be concluded that the coins were exca-
have slight embrittlement problems. 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 7 - Lost Part from the Rim of Coin 1


(SEM image)

4. CONSERVATION CONSIDERATIONS
Figure 5 - Scratches in the Surface of Coin 1
(SEM image) The conservation requirements of the selected coins
vary to large degree based on the nature and state of cor-
Using SEM we were able to relate uncorroded regions rosion and on the nature of the contaminants. Some of the
with the non-inscribed regions whereas it appears that coins need cleaning to remove the localized disfiguring
corrosion and embrittlement are concentrated in the in- corrosion at the rims. Some of them need only cosmetic
scribed regions where the corrosive agent are trapped as cleaning to remove some of the copper corrosion that ob-
shown in Figure 6. In addition, the coins greatly suffer structs some of the details and for aesthetic reasons.
from the rims with some parts totally lost. This may be a Chlorides need to be removed to stabilize the coins and to
result from the synergistic action of plane of weakness reduce their damaging effect on the copper component of
that results from the continuous downfall on the rim and base silver alloys [4].
corrosion that increase the weakness of this part of the The crucial factor guiding decisions about cleaning
coin as shown in Figure 7. 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
Figure 6 - Corrosion and Embrittlement and Social History, Vol. 42, No. 3, pp. 351-363
in the Inscriptions Region of Coin 1 (SEM image) (1999).
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Corrosion behaviour and preservation of Islamic silver alloy coins

[2] Plenderleith, J. and Werner, A., “The Conservation chaeometry, Vol. 40, No. 1, pp. 123-137 (1998).
of Antiquities and Works of Arts,” London: Oxford [7] Wanhill, R.: “Brittle Archaeological Silver: a Frac-
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Underwater Sites: a Study in Methods,” Austin: X-ray Analysis for the Identification and Characteri-
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[5] Stambolov, T.: “The Corrosion and conservation of ments and Methods in Physics Research B, Vol. 226,
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[6] Wanhill, R., et al.: “Damage Assessment and Preser- some Aspects of their Conservation,” Reviews in
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