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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


structure promote the penetration of corrosive substances.
Silver is normally malleable, ductile and easily fabricat- Chloride and sulfide ions, likewise, tend to enlarge crys-
ed. However, some archaeological silver objects can be talline defects. Chloride ions easily permeate oxide films
brittle, as a long-term consequence of corrosion and mi- leading to corrosion by means of local cells. Sulfide ions, by
crostructural changes [1-5]. Being a noble metal, silver formation of silver sulfide, gravely distort the crystal struc-
does not react readily with oxygen: at ordinary tempera- ture of silver oxide. Silver sulfide is a better electrical con-
ture in dry air, it remains apparently unoxidized. Like all ductor than silver oxide and its cations diffuse with ease
metals, however, silver absorbs molecules of oxygen, which through the corrosion film, which, under these conditions,
attract first only electrons from the metal [6] and accord- grows following a parabolic relationship with time.
ingly are partially converted into oxygen ions (O2-). An In the framework of the PROMET project aimed at
electrostatic potential is thus set up across the oxygen lay- systematically investigating the corrosion of silver arte-
er, which is strong enough to pull metal ions through that facts, some silver coupons were artificially pre-aged and
layer outwards. Combination between metal cations and submitted to Attica soil corrosion conditions in order to
oxygen ions then results in the formation of an oxide. If the simulate the corrosion patina of aged artefacts. An exten-
oxide assumes a similar crystalline structure to the metal sive study of the produced patina layers was performed by
upon which it is growing, and if it occupies a volume larger X-ray diffractometry, scanning electron microscopy and
than that of the metal destroyed for its formation, it acts EDS surface analysis as well as optical microscopy.
protectively.
Certain other conditions related to the crystalline 2. EXPERIMENTAL
structure of the oxide and to the mobility of the ions and
electrons determine whether growth will become very slow To simulate archaeological type of patina silver sheet
or not. If the silver oxide is created in dry conditions at coupons (92.5 % Ag, 7.5 % Cu) with dimensions 2cm x
room temperature, it is in fact outstandingly protective. 5cm x 0.04cm, were artificially pre-corroded and embed-
Water, however, introduced by condensation or from oth- ded in typical Attica soil containing plastic boxes for six
er sources, participates, together with the oxygen mole- months. The silver coupons were pre-corroded following
cules, in the capture of electrons from the metal, which was three different accelerated corrosion procedures [10].
confirmed by recent investigations [7]. In high humid con- Accelerated corrosion procedure 1 (ACC1): Silver
ditions, more than two layers of absorbed water act as bulk coupons were immersed in hot aqueous solution of CuCl2
water and electrochemical reaction in bulk solution is ex- 50 g/l (50–60 oC) for 20 min. The corrosion-patination lay-
pected [8]. However, the low corrosion rate in low humid er developed gradually and the color changed to brownish
conditions is thought to be due to less than a monolayer of purple. The samples were removed, washed in warm water
adsorbed water, which has more difficulty in conducting and allowed to dry in air. An even corrosion layer consist-
protons as described in the Zn-H-2-S system [9]. Adsorbed ing mainly of AgCl was produced.
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Corrosion of Silver Alloy Artefacts in Soil

Accelerated corrosion procedure 2 (ACC2): The sam- coupons pre-aged by immersion in a CuCl2 solution and
ples were immersed in cold (RT) BaS 5 g/l solution for 24 extracted from the Attica soil after six months of burial.
hours, producing a slightly uneven dark brown corrosion The back scattered electron images and ED spectra
layer. On the sample surface it can be differentiated areas show the separation of copper and silver with the forma-
of the almost clean metal, the areas of silver rich and cop- tion of copper islands dispersed on the silver alloy surface.
per rich corrosion products. EDS results, also, disclose the presence of chlorine that the
Accelerated corrosion procedure 3 (ACC3): The ingre- GAXRD diffraction pattern assigns to chloroargyrite. The
dients 20 g CuSO4x5H2O and 20 g ZnCl2 were grinded to a presence of the copper islands in the silver alloys is a com-
thin creamy paste with a little water, using a pestle and mon feature of the silver–copper alloys due to the low solu-
mortar. The paste was applied sparingly to the sample us- bility of Ag in Cu and vice versa at room temperature [14].
ing a soft brush. The surface darkened as the paste was ap- The occurrence of the copper and silver separation is al-
plied. The residual paste was washed away after about an ways observed on a micro-scale in the archaeological silver
hour, and the sample was air-dried. A thin, even, blue- coins as well as macroscopically on the coin surface as have
green corrosion layer was formed. been recently reported by Ingo et al. [15].
The interaction between some soil constituents (Cl, P, Table 2 presents SEM and OM morphological details,
Si, Fe, Ca) and degradation products is investigated. Soil as well as GAXRD patterns of the silver coupons pre-aged
properties are of primary importance to the surface condi- by immersion in a BaS solution and extracted from the At-
tion of buried metals [11], so the selected soil was treated tica soil after six months of burial. The EDS spectra dis-
according to the reference method ISO 11464 and then close the formation of silver-sulfide with traces of soil ele-
analysed. The soil is characterized by alkaline pH, thus it is ments (Si, Al, Mg, Ca, Fe), thus demonstrating the interac-
not acting as a highly corrosive en-vironment for the silver tion between soil components and corrosion products. The
alloys. formation of silver sulphide may simulate post-burial
The surface morphology and chemical composition as degradation of the archaeological silver objects. Apart
well as the micro-chemical structure of the corrosion prod- from silver-sulphide the GAXRD analysis reveals the pres-
ucts grown on the silver coupons were studied by means of ence of cuprite, Cu2O and silver oxide, Ag2O on the artifi-
the combined use of optical microscopy (OM), scanning cially aged silver coupon surface.
electron microscopy (SEM) and energy dispersive spec- Table 3 similarly shows SEM/EDS, OM photographs
trometry (EDS). Both SEM and EDS characterizations and GAXRD pattern of the silver coupons pre-aged by
were carried out by using a Quanta 200 FEI scanning elec- CuSO4/ZnCl2 paste and extracted from the Attica soil after
tron microscope equipped with a tungsten filament and six months of burial. The ED spectra show evidence of the
solid state back scattered electron detector. The surface presence of silver-chlorine species, chloroargyrite, and
morphology of the coupons has been also observed by us- copper-chlorine compounds on the silver coupon surface
ing a stereoscopic microscope: Olympus SZ-60 equipped as well as the active localized corrosion phenomenon com-
with a digital camera. monly defined as "bronze disease". Cuprous-chloride is es-
Glancing angle X-ray diffraction (GAXRD) patterns sential in the maintaining this cyclic corrosion reaction,
were recorded at 2o, 5o and 10o low incident angles by which occurs in the copper enriched areas and is induced
SIEMENS X-ray Diffractometer 5000 with Cu Ka x-ray by, oxygen and humidity.
source. The exposed copper would act as an anode, i.e., to go
into solution, whereas silver would behave cathodically.
3. RESULTS AND DISCUSSION Silver would therefore undergo attack by copper(II) ions in
the presence of chloride ions and dissolve according to the
General corrosion in high-silver –content alloys results equation 1 [16]:
in the slow conversion of the metal surface to silver chlo-
ride [3, 12, 13]. The silver chloride forms a brittle finely Cu2+ + 2Cl- + Ag = AgCl + CuCl (1)
granular layer, but does not affect the remaining metal.
However, unfavourable conditions may result in an object Several factors render this reaction decisively corro-
being completely converted to silver chloride [3, 12]. Base sive, since silver chloride, although insoluble in water does
silver containing much copper undergoes general corro- not grow on silver as a protective coating. Moreover, owing
sion whereby copper diffuses out of the alloy and becomes to its poor solubility, the precipitated silver chloride de-
fixed on the surface as green corrosion products [3]. presses the Ag+ ions concentration. This shifts reaction (1)
To simulate the corrosion patina of aged artefacts, sil- to the right, a displacement signifying increased rate of sil-
ver coupons were artificially pre-aged and submitted to At- ver disintegration to ions. The extent of the corrosion is
tica soil corrosion conditions. The knowledge gained from subjected to many variables, among which are the chemi-
detailed examination of such coupons can be important in cal-physical parameters of the burial context, the presence
determining the best ways to restore and conserve archae- and nature of the electrolyte, and the micro-chemical
ological silver objects. Table 1 presents some SEM and structure of the alloy.
OM photographs as well as GAXRD patterns of silver
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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

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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 presence of the cuprite (Cu2O) is due to selective corrosion
Table 3 show the corrosion product structure consisting of the main alloying element, which is redeposited after
largely of copper-oxide (Cu2O) and chloroargyrite with a dissolution onto the surface of the silver coupon, thus
small amount of cuprous chloride, which form a crust with forming a copper enriched layer.
traces of Si, Ca, Al and Mg originating from the soil. The
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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

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Corrosion of Silver Alloy Artefacts in Soil

4. CONCLUSION vation of an Egyptian silver vase (300-200 BC)",


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