AP°YPO¶OY§OY TELOS 30-01-08 11:01 ™ÂÏ›‰·58

Corrosion of Silver Alloy Artefacts in Soil

J. Novakovic, P. Vassiliou
School of Chemical Engineering,
National Technical University of Athens
Iroon Polytechniou St. 9
15780, Athens, Greece
e-mail: pvas@chemeng.ntua.gr

Corrosion of silver-alloy artefacts in soil is a well-known phenomenon. In particular, archaeological artefacts

which may remain in the soil for thousands of years are subjected to severe corrosion. In this work, we try to
specify the types of attack on the silver metal alloy surface in soil. Silver drawn sheet coupons were artificially
aged and then submitted to Attica soil corrosion conditions to simulate the corrosion patina of real artefacts
before excavation. An extensive study of the produced patina layers was performed by Glancing Angle X-ray
Diffractometry (GAXRD), scanning electron microscopy (SEM) and EDS surface analysis as well as optical
microscopy. The silver coupon examination shows the same type of attack as the one reported on original
artefacts.

Keywords: silver corrosion, artificial patina

1. INTRODUCTION water layers, by introducing irregularities into the oxide

Silver is normally malleable, ductile and easily fabricat-
ed. However, some archaeological silver objects can be
brittle, as a long-term consequence of corrosion and mi-
crostructural changes [1-5]. Being a noble metal, silver
does not react readily with oxygen: at ordinary tempera-
ture in dry air, it remains apparently unoxidized. Like all
metals, however, silver absorbs molecules of oxygen, which
attract first only electrons from the metal [6] and accord-
ingly are partially converted into oxygen ions (O2-). An
electrostatic potential is thus set up across the oxygen lay-
er, which is strong enough to pull metal ions through that
layer outwards. Combination between metal cations and
oxygen ions then results in the formation of an oxide. If the
oxide assumes a similar crystalline structure to the metal
upon which it is growing, and if it occupies a volume larger
than that of the metal destroyed for its formation, it acts
protectively.
Certain other conditions related to the crystalline
structure of the oxide and to the mobility of the ions and
electrons determine whether growth will become very slow
or not. If the silver oxide is created in dry conditions at
room temperature, it is in fact outstandingly protective.
Water, however, introduced by condensation or from oth-
er sources, participates, together with the oxygen mole-
cules, in the capture of electrons from the metal, which was
confirmed by recent investigations [7]. In high humid con-
ditions, more than two layers of absorbed water act as bulk
water and electrochemical reaction in bulk solution is ex-
pected [8]. However, the low corrosion rate in low humid
conditions is thought to be due to less than a monolayer of
adsorbed water, which has more difficulty in conducting
protons as described in the Zn-H-2-S system [9]. Adsorbed
58
structure promote the penetration of corrosive substances.
Chloride and sulfide ions, likewise, tend to enlarge crys-
talline defects. Chloride ions easily permeate oxide films
leading to corrosion by means of local cells. Sulfide ions, by
formation of silver sulfide, gravely distort the crystal struc-
ture of silver oxide. Silver sulfide is a better electrical con-
ductor than silver oxide and its cations diffuse with ease
through the corrosion film, which, under these conditions,
grows following a parabolic relationship with time.
In the framework of the PROMET project aimed at
systematically investigating the corrosion of silver arte-
facts, some silver coupons were artificially pre-aged and
submitted to Attica soil corrosion conditions in order to
simulate the corrosion patina of aged artefacts. An exten-
sive study of the produced patina layers was performed by
X-ray diffractometry, scanning electron microscopy and
EDS surface analysis as well as optical microscopy.
2. EXPERIMENTAL
To simulate archaeological type of patina silver sheet
coupons (92.5 % Ag, 7.5 % Cu) with dimensions 2cm x
5cm x 0.04cm, were artificially pre-corroded and embed-
ded in typical Attica soil containing plastic boxes for six
months. The silver coupons were pre-corroded following
three different accelerated corrosion procedures [10].
Accelerated corrosion procedure 1 (ACC1): Silver
coupons were immersed in hot aqueous solution of CuCl2
50 g/l (50–60 oC) for 20 min. The corrosion-patination lay-
er developed gradually and the color changed to brownish
purple. The samples were removed, washed in warm water
and allowed to dry in air. An even corrosion layer consist-
ing mainly of AgCl was produced.
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Corrosion of Silver Alloy Artefacts in Soil
Accelerated corrosion procedure 2 (ACC2): The sam-
ples were immersed in cold (RT) BaS 5 g/l solution for 24
hours, producing a slightly uneven dark brown corrosion
layer. On the sample surface it can be differentiated areas
of the almost clean metal, the areas of silver rich and cop-
per rich corrosion products.
Accelerated corrosion procedure 3 (ACC3): The ingre-
dients 20 g CuSO4x5H2O and 20 g ZnCl2 were grinded to a
thin creamy paste with a little water, using a pestle and
mortar. The paste was applied sparingly to the sample us-
ing a soft brush. The surface darkened as the paste was ap-
plied. The residual paste was washed away after about an
hour, and the sample was air-dried. A thin, even, blue-
green corrosion layer was formed.
The interaction between some soil constituents (Cl, P,
Si, Fe, Ca) and degradation products is investigated. Soil
properties are of primary importance to the surface condi-
tion of buried metals [11], so the selected soil was treated
according to the reference method ISO 11464 and then
analysed. The soil is characterized by alkaline pH, thus it is
not acting as a highly corrosive en-vironment for the silver
alloys.
The surface morphology and chemical composition as
well as the micro-chemical structure of the corrosion prod-
ucts grown on the silver coupons were studied by means of
the combined use of optical microscopy (OM), scanning
electron microscopy (SEM) and energy dispersive spec-
trometry (EDS). Both SEM and EDS characterizations
were carried out by using a Quanta 200 FEI scanning elec-
tron microscope equipped with a tungsten filament and
solid state back scattered electron detector. The surface
morphology of the coupons has been also observed by us-
ing a stereoscopic microscope: Olympus SZ-60 equipped
with a digital camera.
Glancing angle X-ray diffraction (GAXRD) patterns
were recorded at 2o, 5o and 10o low incident angles by
SIEMENS X-ray Diffractometer 5000 with Cu Ka x-ray
source.
3. RESULTS AND DISCUSSION
General corrosion in high-silver –content alloys results
in the slow conversion of the metal surface to silver chlo-
ride [3, 12, 13]. The silver chloride forms a brittle finely
granular layer, but does not affect the remaining metal.
However, unfavourable conditions may result in an object
being completely converted to silver chloride [3, 12]. Base
silver containing much copper undergoes general corro-
sion whereby copper diffuses out of the alloy and becomes
fixed on the surface as green corrosion products [3].
To simulate the corrosion patina of aged artefacts, sil-
ver coupons were artificially pre-aged and submitted to At-
tica soil corrosion conditions. The knowledge gained from
detailed examination of such coupons can be important in
determining the best ways to restore and conserve archae-
ological silver objects. Table 1 presents some SEM and
OM photographs as well as GAXRD patterns of silver
59
coupons pre-aged by immersion in a CuCl2 solution and
extracted from the Attica soil after six months of burial.
The back scattered electron images and ED spectra
show the separation of copper and silver with the forma-
tion of copper islands dispersed on the silver alloy surface.
EDS results, also, disclose the presence of chlorine that the
GAXRD diffraction pattern assigns to chloroargyrite. The
presence of the copper islands in the silver alloys is a com-
mon feature of the silver–copper alloys due to the low solu-
bility of Ag in Cu and vice versa at room temperature [14].
The occurrence of the copper and silver separation is al-
ways observed on a micro-scale in the archaeological silver
coins as well as macroscopically on the coin surface as have
been recently reported by Ingo et al. [15].
Table 2 presents SEM and OM morphological details,
as well as GAXRD patterns of the silver coupons pre-aged
by immersion in a BaS solution and extracted from the At-
tica soil after six months of burial. The EDS spectra dis-
close the formation of silver-sulfide with traces of soil ele-
ments (Si, Al, Mg, Ca, Fe), thus demonstrating the interac-
tion between soil components and corrosion products. The
formation of silver sulphide may simulate post-burial
degradation of the archaeological silver objects. Apart
from silver-sulphide the GAXRD analysis reveals the pres-
ence of cuprite, Cu2O and silver oxide, Ag2O on the artifi-
cially aged silver coupon surface.
Table 3 similarly shows SEM/EDS, OM photographs
and GAXRD pattern of the silver coupons pre-aged by
CuSO4/ZnCl2 paste and extracted from the Attica soil after
six months of burial. The ED spectra show evidence of the
presence of silver-chlorine species, chloroargyrite, and
copper-chlorine compounds on the silver coupon surface
as well as the active localized corrosion phenomenon com-
monly defined as "bronze disease". Cuprous-chloride is es-
sential in the maintaining this cyclic corrosion reaction,
which occurs in the copper enriched areas and is induced
by, oxygen and humidity.
The exposed copper would act as an anode, i.e., to go
into solution, whereas silver would behave cathodically.
Silver would therefore undergo attack by copper(II) ions in
the presence of chloride ions and dissolve according to the
equation 1 [16]:
Cu2+ + 2Cl- + Ag = AgCl + CuCl (1)
Several factors render this reaction decisively corro-
sive, since silver chloride, although insoluble in water does
not grow on silver as a protective coating. Moreover, owing
to its poor solubility, the precipitated silver chloride de-
presses the Ag+ ions concentration. This shifts reaction (1)
to the right, a displacement signifying increased rate of sil-
ver disintegration to ions. The extent of the corrosion is
subjected to many variables, among which are the chemi-
cal-physical parameters of the burial context, the presence
and nature of the electrolyte, and the micro-chemical
structure of the alloy.
AP°YPO¶OY§OY TELOS 30-01-08 11:01 ™ÂÏ›‰·60

J. Novakovic and P. Vassiliou

Table 1 - SEM/EDS and XRD analysis of the silver coupons pre-aged by immersion in a CuCl2 solution and extracted
from the Attica soil after six months of burial

60
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Corrosion of Silver Alloy Artefacts in Soil

Table 2 - SEM/EDS and XRD analysis of the silver coupons pre-aged by immersion in a BaS solution and extracted
from the Attica soil after six months of burial

The OM photographs and GAXRD analysis given in
Table 3 show the corrosion product structure consisting
largely of copper-oxide (Cu2O) and chloroargyrite with a
small amount of cuprous chloride, which form a crust with
traces of Si, Ca, Al and Mg originating from the soil. The
61
presence of the cuprite (Cu2O) is due to selective corrosion
of the main alloying element, which is redeposited after
dissolution onto the surface of the silver coupon, thus
forming a copper enriched layer.
AP°YPO¶OY§OY TELOS 30-01-08 11:01 ™ÂÏ›‰·62

J. Novakovic and P. Vassiliou

Table 3 - SEM/EDS, OM and XRD analysis of the silver coupons pre-aged by CuSO4/ZnCl2 paste and extracted
from the Attica soil after six months of burial

62
AP°YPO¶OY§OY TELOS 30-01-08 11:01 ™ÂÏ›‰·63
Corrosion of Silver Alloy Artefacts in Soil
4. CONCLUSION
A reference silver sheet alloy containing 7.5 wt.% Cu
has been employed for carrying out three different acceler-
ated degradation tests to simulate as best as possible, the
specific corrosion conditions of the archaeological silver
objects. The use of SEM-EDS, OM and GAXRD analyti-
cal techniques have provided good insight into the nature
of the created surface corrosion products, which were quite
similar to the ones grown on silver objects during archaeo-
logical burial. GAXRD is used to record the diffraction
pattern of the produced corrosion layers with minimum
contribution from the metal substrate. The knowledge
gained from detailed examination of such reference
coupons can be very useful in determining the optimum
procedure to restore and conserve archaeological silver
objects.
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