Corrosion Science 47 (2005) 663679

www.elsevier.com/locate/corsci

Reduction of silver tarnishing and

protection against subsequent corrosion
M.C. Bernard, E. Dauvergne, M. Evesque,
M. Keddam, H. Takenouti *
UPR 15 of CNRS Laboratoire Interfaces et Syste`mes Electrochimiques,
Universite P&M Curie, C.P. 133, 4 Place Jussieu, 75252 Paris Cedex 05, France
Available online 20 August 2004

Abstract
The kinetics of tarnishing formation was examined on a polished silver dipped in a 10 mM
Na2S. The recovery of an initial bright surface was then obtained by cathodic reduction of the
tarnish layer in a 5% sesqui-carbonate solution. Two protection methods to prevent a further
formation of a dark deposit were tested: an electrodeposited poly(amino-triazole) lm and the
surface treatment in hexadecane-thiol. The protection by poly(amino-triazole) is not reliable
for all nuances of silver. In contrast, the lm formed with hexadecane-thiol showed satisfactory properties. The formations of tarnish and protective lms were examined by electrochemical methods, the reectance measurements, and the quartz crystal microbalance.

2004 Elsevier Ltd. All rights reserved.
Keywords: Poly(amino-triazole); Reduction; Sulphide; Thiol; Self-assembling membrane

1. Introduction
Silver is applied in various elds, for example, jewelleries for its softness, electronic industries for its high electrical conductivity, cutlery, and photography. Many

Corresponding author. Tel.: +33 1 4427 4158; fax: +33 1 4427 4074.
E-mail address: ht@ccr.jussieu.fr (H. Takenouti).

0010-938X/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2004.07.015

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M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

objects of cultural heritage constituted of bulk or plated silver or alloys are known,
and they are often displayed in a museum show-window. However, the silverworks
tarnish with time by combining with atmospheric pollutant elements. The blackish
lm thus formed made these artefacts inappropriate to display. At this moment,
the method most frequently used is a mechanical polishing or a chemical stripping
of the silver surface. An electrochemical reduction by galvanic coupling with an aluminium piece (anode) or an external current source is also employed. The rst two
methods do remove a part of the silver from the surface, even a small amount.
But the ethics of curators and conservators requires:

keep the initial aesthetics;

harmless and stable so that the applied treatment do not alter silverworks;
integrity of materials, that is, not to remove any material from the object;
legibility, in the case of restoration, the modied parts should be readily recognisable;

reversibility of treatments allowing the recovery of the initial state, if it is found to
be necessary after the realisation.
This paper is aimed to devise a method that allows the recovery of a metallic silver
surface from the tarnished surface, and then apply an anticorrosion procedure to
avoid a subsequent tarnishing.

2. Experiments
The protective eectiveness of two procedures were tested: an electropolymerised
poly(3-amino 1,2,4-triazole) and hexadecane-thiol [13]. Both protections were applied on a clean silver surface, and then a silver specimen was transferred into a sodium sulphide solution. The experiments were performed as the following sequence:
1. A polishing of the silver surface.
2. The rst tarnishing test without protection, which served as the reference for the
protective eect of the subsequent protection, and also permitted to produce tarnished silver.
3. The cathodic reduction of tarnish layer.
4. The applications of protective coating.
5. The tarnishing of protected specimen.
The dierent experimental conditions are presented below.
2.1. Electrodes
Two kinds of the silver electrode were used, the one for the tarnishing test with
bulk silver plate, and the other for the electrochemical quartz crystal microbalance
(EQCM) measurements with electrodeposited silver.

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

665

2.1.1. Bulk silver-electrodes

The electrode was made of a pure silver plate (Goodfellow, 99.95%) of 1 mm
thick. Square pieces of 10 10 mm2 (1 cm2) were cut out, and a brass contact was
brazed on one side. Fig. 1a presents the schematic drawing of the electrode. The electrode was then embedded in a thermoplastic allylic-resin. Before experiments, the
electrode surface was polished with alumina powder on a rotating felt sheet to obtain
a mirror surface.
For the experiments of electropolymerised poly(amino-triazole) coated electrode,
a cylinder rod of silver was used. The lateral part of the silver rod was coated by a
thick epoxy resin.
2.1.2. EQCM electrode
A 9 MHz nominal frequency quartz-blade oscillator was used. A quartz-blade
with key-hole shape gold deposit on both sides was then mounted on epoxy-board.
The electrical contact with current tracks of the epoxy-board was ensured with silver
glue. The quartz-blade and the epoxy-board were then covered with silicon mastic
except for the central disk of gold. On this gold electrode, silver was electrodeposited
from cyanide bath (The silver deposit was performed by the courtesy of Conventhia
Co.). The thickness of silver was ca. 3 lm. The electrode surface was polished with a
cotton-tip soaked by alumina powder suspended in water. Fig. 1b presents the schematic drawing of EQCM electrode.
2.1.3. Reference and counter electrodes
The HgjHg2SO4jsat-K2SO4 reference electrode (saturated mercurous sulphate
electrode: SME) was used. The electrode-tip was a sintered glass disk, and located
far from the working electrode. Platinum gauze of a large surface area compared
with the silver working electrode was used as the counter electrode.
2.2. Solutions
Below, the four solutions used in this study are presented.

9MHz

epoxy
glue
Quartz
Ag

Ag

Epoxy-glass fibre board

A-A

Au

9MHz

Allylic resin

(a)

(b)

Fig. 1. The schematic drawing of (a) the plate and (b) the EQCM silver electrode.

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M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

2.2.1. Tarnishing solution

A 10 mM Na2S aqueous solution was used as the tarnishing solution. The concentration of S2 was therefore 320 ppm, much higher than frequently encountered in
polluted media, ca. 1 ppm. This high concentration accelerated considerably the tarnishing process, and 1 h dipping in this solution was sucient to obtain a blackish
surface when no protection was applied as can be seen below [1,3].
2.2.2. Solution of the cathodic reduction of tarnished layer
The reduction of tarnish layer was performed electrochemically in an aqueous carbonate solution, as reported by Degrigny et al. [4,5]. The solution was 5% sesqui-carbonate (Na2CO3 NaHCO3 2H2O), i.e. 22 mM solution. The carbonate medium was
recommended by these authors because their experiments concerned a silver coated
brass, and this medium is mild for this alloy.
2.2.3. Electropolymerising solution
The electropolymerised 3-amino 1,2,4-triazole (pATA) was obtained in 0.2 M
amino-triazole with 0.1 M sodium acetate in methanol solution. The anodic polymerisation was performed by ve potential scan cycles between 0.4 and 0.6 VSME
at the scan rate of 10 mV s1. After the electropolymerisation, the lm thus formed
was cured at 120 C for 30 min.
2.2.4. Thiol self-assembling membrane
It is largely admitted that an alkyl-thiol forms a self-assembling membrane on
various surfaces. The hexadecane-thiol (C16H33SH) in isopropanol solution at the
concentration of 0.15 M at 30 C was used. The thiol concentration was much higher
than usually used [6] allowing the fast formation of a protecting layer.
The formation of thiol-lm was performed as follows in a mildly stirred solution
with a magnetic bar.
The degreasing of silver surface was performed by a successive dipping of the electrode in hexane, acetone, and ethanol for 3 min each. Then, the silver surface was
activated by dipping in 10% H2SO4 for 3 min. After rinsing the surface thoroughly
with demineralised water, the silver electrode was dipped in the hexadecane-thiol
solution for 1 h at 30 C, followed by the rinsing in pure isopropanol to remove
the excess of thiol. Finally, the specimen was set into an oven heated at 50 C for
3 min. It was found that the hexane dipping can be omitted, if the silver surface
was not greasy, to avoid the use of toxic substance.
2.3. Reectance measurements
The degree of tarnishing was determined by the reectance measurements, and
Fig. 2 presents the experimental setup used. The UVvisibleIR spectrometer used
(Hitachi, U-4001) had two light sources, a halogen-tungsten lamp (WL) for IR to
visible beam and a deuterium light (D2) for UV beam. In our experiments, the wavelength used was 600 nm from WL. The monochromator, simplied in this drawing,
allowed the wavelength scanning. The monochromatic beam was then split into two

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

WL

Sector
Mirror

M
M

667

D2

Chopper

Reference
beam

Sample
beam

WE

RE CE

Integrating
sphere

M
Monochromater

Electrochemical
cell
PbS/MPT

Fig. 2. Experimental setup of the reectance measurement.

pathways; reference and sample beam. The reference beam entered directly into the
integrating sphere, and reected at the wall whereas the sample beam hit the silver
surface.
The silver electrode was set close to the cell window, whereas the counter (CE)
and the reference (RE) electrodes were located behind the working electrode
(WE). A small tilt 8 with incident beam allowed the collection of the whole reected
beam. Before lling the tarnishing solution in the cell, the position of the electrode
was adjusted so that almost the whole silver surface was enlightened. The experiments started by lling the sodium sulphide electrolyte.

3. Results and discussion

The results relative to the initial tarnishing, then the cathodic reduction of tarnished layer will be described below. In general, more than three replica measurements were performed, and the most representative cases were presented below.
3.1. Initial tarnishing
The tarnishing process was followed by reectance measurements, the mass
change by EQCM experiments, and by chronopotentiometry.
3.1.1. Reectance
The reectance change of two independent measurements on the silver tarnishing
without any protection is presented in Fig. 3. The silver surface loses its brilliance
with time with an exponential-like law. The kinetics of tarnishing is faster for the
electrode #2 but reaches almost the same reectance value at 1 h immersion, and
valued ca. 25%. The surface state of the electrode #1 is presented in Fig. 4a. At this
tarnishing stage, the surface is almost blackish. As stated above, the 10 mM Na2S

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M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

1.0
1st step
without protection

Reflectance

0.8
0.6

Electrode 1
0.4
Electrode 2
0.2
0.0
0

10

20

30

40

50

60

Time (min)
Fig. 3. Tarnishing of two silver electrodes without protection in 10 mM Na2S solution.

Fig. 4. The surface state at the end of dierent steps of tarnishing in 10 mM Na2S (electrode #1 of Fig. 3).
(a) Unprotected silver after 1 h immersion, (b) after the reduction, (c) thiol protected silver after 1 h
immersion.

solution is suciently aggressive to obtain a well advanced tarnished surface within

1 h.
3.1.2. Mass change during the tarnishing
The mass change of two independent experiments during the tarnishing process is
presented in Fig. 5. It is worth to recall that these experiments were performed with
silver plated EQCM electrode, instead of the bulk silver-plate electrodes in the former experiments. The mass change was evaluated according to Sauerbrey relationship from the resonant oscillation frequency of the quartz electrode. In contrast to
the tarnishing process, the mass continues to increase even after 1 h immersion,
and no saturation was observed as shown in Fig. 3. At this moment, the mass gain
was ca. 4 lg cm2. This mass change is the dierence between the mass gain by the
formation of Ag2S and the mass loss due to the dissolution of Ag. It is impossible to

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

669

Mass density (g cm-2)

Mass change with time

4

3
2

Experiment 1
Experiment 2

1
0

10

20

30

40

50

60

Time (minute)
Fig. 5. The mass change during the tarnishing of unprotected silver electrode in 10 mM Na2S solution by
the EQCM measurement (two independent experiments).

distinguish the contribution of each one of these processes from this measurement
only.
3.1.3. Potential change during the tarnishing
The open-circuit potential, determined simultaneously to the mass change, during
the tarnish formation on non-protected silver electrode is presented in Fig. 6. Before
the immersion of the electrode in the test solution, the potential was ca. 0 VSME but
this value has no signicance, since the electrical connection was not yet established
between the WE and the RE. As soon as the electrode was dipped into the tarnishing
solution, the potential becomes ca. 1.12 VSME and remained essentially constant,

0.0

Immersion of specimen

Potential (VSME)

-1.120

-0.2
-0.4
-1.125

-0.6
-0.8
-1.130
90

95

100

105

-1.0
-1.2

110

115

120

Zoom
0

30

60

90

120

150

180

Time (min)
Fig. 6. The potential change during the tarnishing of the unprotected EQCM silver electrode in 10 mM
Na2S solution.

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M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

though uctuations of a few mV were maintained all through the experiment, as can
be seen in the zoomed graph.
The standard equilibrium potential of the Ag2S formation is:
2Ag S2 () Ag2 S 2e

E0 1:29 VSME

The experimental open-circuit potential is therefore more than 0.15 V more positive.
This dierence may be explained by a parallel cathodic reaction associated with the
reduction of the dissolved oxygen.
3.2. Cathodic reduction of the tarnish layer
It was found by preliminary experiments that the current density of 0.5 mA cm2
gave a satisfactory result for the reduction of tarnish layer. Before these experiments,
the voltammetric curve for the reduction of the tarnish layer was recorded.
3.2.1. Reduction of tarnish layer by voltammetric experiment
A previously tarnished silver electrode without protection was transferred in the
carbonate solution, and the voltammetric experiments were performed at a potential
scan rate of 10 mV s1. Fig. 7 showed the voltammogram obtained. There is a reduction current peak at 1.3 VSME corresponding well to the equilibrium potential of
Eq. (1). During the backward scan (more anodic direction), no current peak was observed, and after the experiment, it was found that the surface layer became bright.
The cathodic polarisation reduced tarnish layer in a carbonate medium.

Current density (mA cm-2)

3.2.2. Reectance measurements

After the formation of Ag2S tarnish layer on the unprotected silver electrode, the
reectance change due to the cathodic reduction at j = 0.5 mA cm2 for the electrode #1 was followed, and Fig. 8 presents the result. As can be seen in Fig. 3,

0
Start
-2
-4
-6
-8
-10

-1.6

-1.4

-1.2

-1.0

-0.8

-0.6

Potential (VSME)
Fig. 7. Voltammogram of the cathodic reduction of tarnish layer formed in the rst step in
Na2CO3 NaHCO3 2H2O solution.

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

671

1.2

Reflectance

1.0
0.8
0.6
0.4
0.2
0

Cathodic reduction
Electrode 1

Time (min)
Fig. 8. The reectance change during the cathodic reduction of tarnished layer. The tarnish layer formed
previously in 10 mM Na2S solution upon the silver plate electrode without protection. The cathodic
reduction in 5% Na2CO3 NaHCO3 2H2O solution at j = 0.5 mA cm2.

the reectance was 25% after the initial tarnishing step. The reectance increased
steeply to reach 0.99 at 1 min reduction. The reectance decreased slightly with a
longer cathodic polarisation. At this stage, the electrode surface was very slightly
milky, and the surface state is presented in Fig. 4b. Except for the very border of
the electrode, the cathodic reduction was realised almost on the whole surface area.
3.2.3. Mass and potential changes during the reduction
The mass and the potential changes during the galvanostatic polarisation for the
reduction of Ag2S performed with the EQCM electrodes are presented in Fig. 9. It is
important to note that the initial mass of these experiments was set to zero. For the
mass change, the reduced Ag metal remained at the electrode surface whereas S2
would be released to the solution; therefore a net mass loss is expected. However,
the maximum in the mass change was observed at about 40 and 50 s for two
independent measurements, and even the maximum value is positive for one of
them.
The potential change recorded simultaneously with the mass change for two independent experiments are presented in Fig. 9b. The potential plateaus at 1.25 or
1.35 VSME were observed. At about 40 s, the potential decreased markedly and
reached to ca. 1.7 VSME corresponding to the hydrogen evolution reaction. The
electrode mass continued to decrease after reaching to the hydrogen evolution domain.
The mass increase will be likely due to the precipitation of carbonate salt, due to
the pH increase at the electrode interface induced by the hydrogen evolution reaction. This process makes the surface slightly milky. A light wiping with cotton-tip
is sucient to remove this layer.
The apparent mass M was calculated according to the following equation for both
electrodes, and presented in Fig. 10.

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M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

Mass density (A cm-2)

(a)

2
0
-2

EQCM 2

-4
-6
-8

EQCM 1
0

30

Time (s)

60

90

-1.1

(b)

Potential (VSME)

-1.2
-1.3
-1.4
-1.5
-1.6

EQCM 1
-1.7
EQCM 2
-1.8
0

30

60

90

Time (s)

Apparent gram equivalent (g)

Fig. 9. Cathodic reduction of tarnished layer on EQCM electrode in 5% Na2CO3 NaHCO3 2H2O
solution at j = 0.5 mA cm2. (a) The mass, (b) the potential changes.

400
EQCM 1

300
200
100

M = 16 g.eq

EQCM 2

0
-100
0

30

60

90

Time (min)
Fig. 10. The apparent gram-equivalent calculated during the cathodic reduction of the tarnish layer in 5%
Na2CO3 NaHCO3 2H2O solution at j = 0.5 mA cm2.

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

M F Dm=DQ

673

where Dm and DQ stand respectively for the mass and the charge changes calculated
from each data collection, at the time interval of 1 s.
Unfortunately, it is not possible to identify the chemical entities involved in reactions taking place during the cathodic reduction of tarnish layer by applying the Faraday law. Because in parallel to the reduction of tarnish layer, the precipitation
(t
25 and 30 s respectively for the EQCM 1 and 2) and the dissolution (t
32
and 42 s) processes in the early stage may take place. The results presented in Fig.
8 were realised with the electroplated silver electrode, therefore it is very possible that
the kinetics of the reduction are dierent. The tarnish layer would then be reduced at
about 20 s in this case. The theoretical gram-equivalent is evaluated according to the
following reduction reaction:
Ag2 S 2e ! 2Ag S2

The Ag atoms of the left-hand equation remains on the electrode surface i.e. are
converted in the right-hand equation, therefore only S2 is released in the solution.
The gram-equivalent of 16 g is then expected, and is indicated by the dotted line in
the gure. No limiting value corresponding to this theoretical value was observed
experimentally for any of the two electrodes. Instead, the equivalent mass greater
than 16 was observed. During this period, a small amount of silver may leave the
electrode surface. The thickness of silver layer involved in this period is negligible
as will be evaluated in Section 3.5.2.
3.3. The protection by an electropolymerised lm
The protective eectiveness of pATA lm was rst veried. The experiments were
performed without a previous tarnish layer formation, but directly on the polished
electrode. The application of thiol layer was, in contrast, applied after the reduction
of tarnished layer presented in the above section.
3.3.1. Protection by a poly(3-amino 1,2,4-triazole) lm
Fig. 11 presents the voltammogram obtained during the lm formation in methanol solution of 3-amino 1,2,4-triazole (ATA) in presence of acetate as the supporting electrolyte. At the rst anodic scan, a marked current peak was observed at ca.
0.35 VSME. During the rst and also during subsequent back scans, the current density decreased monotonically indicating the irreversibility of the lm formation process. The second anodic scan showed a small anodic current peak whereas no such a
peak was observed for the subsequent anodic scans, that indicates the formation of
an insulating polymer layer by the anodic polarisation. The lm thus obtained is
named pATA, poly(amino-triazole), for the sake of simplicity. In a previous work,
it was shown that pATA lm formed on a copper electrode is highly protective because of the formation of pATA and cuprous oxide complex [2].
Fig. 12 presents the surface state which illustrates the protective eectiveness for
two pure silver electrodes. As can be seen in this gure, its performance depends on

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M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

Current density (mA cm-2)

0.5
1st cycle

0.4
0.3
0.2
0.1

2ndcycle
3rd cycle
4th cycle

0.0
-0.1

5th cycle

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

Potential (VSME)
Fig. 11. The cyclic voltammogram during the formation of pATA lm on silver electrode in 0.2 M 3amino 1,2,4-triazole + 0.1 M CH3COONa methanol solution. dE/dt = 10 mV s1.

Fig. 12. The protective eectiveness of pATA lm against the tarnishing of the silver. (a) The initial state:
polished surface. (bd) After the dipping in 10 mM Na2S + 0.5 M NaCl during 1 h (b) without protection
(cd) with a pATA lm. (d) was obtained with a dierent silver electrode from (a) to (c).

the electrode examined. This protection method is therefore not suciently reliable,
thus no further experiments were performed.
3.4. The protection by hexadecane-thiol adsorption
After reducing the tarnish layer, the silver surface was wiped with a cotton-tip if
necessary, and then the application of hexadecane-thiol was performed as presented
in Section 2.2.4.
3.4.1. EQCM experiments
Fig. 13 presents two independent measurements of the mass change during the
lm formation. The initial mass, just after the immersion of electrode, was set as
zero. At the end of dipping period, the mass increased ca. 80 20 lg cm2, almost
three times as high as that observed on the freshly polished silver EQCM electrode

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

675

100

Mass density (g cm-2)

EQCM 2
80
60
EQCM 1
40
20
0

10

20

30

40

50

60

Time (min)
Fig. 13. Mass gain during the formation of thiol-lm in isopropanol solution of 0.15 M C16H33SH at
30 C.

[3]. The increase of the surface roughness due to initial tarnishing followed by reduction steps would promote the adsorption of thiol.
This step was followed by the rinsing in pure isopropanol, which removes the major part of thiol layer, as presented in the next paragraph.
3.5. Tarnishing of thiol coated silver plate
After rinsing the electrode in isopropanol and drying it in an oven at 50 C for
3 min, similar tarnishing experiments were repeated to the second step.
3.5.1. Reectance
The reectance change after the application of thiol-lm is presented in Fig. 14.
The reectance decreased from 0.97 to 0.96 only compared with 1.00 to 0.25 without
protection. The thiol-lm actually protected against the tarnish formation of silver.
A small decrease of the reectance before the tarnish formation is due to the incomplete recovery of the reectance by the cathodic reduction, and also to the surface
roughening. The surface state, after this period is presented in Fig. 4c. As expected
from the reectance data, no tarnishing can be detected. Even more, the tarnish remained at the border of the electrode after the cathodic reduction (Fig. 4) disappeared during the surface treatment by thiol.
3.5.2. The overall reectance and the mass change
Fig. 15 recapitulates the variation of the reectance from the initial tarnishing
(step 2, as dened at the beginning of Section 2), that recorded during the cathodic
reduction (step 3), and the tarnishing with the thiol-lm protection (step 5). No
reectance measurements were carried out during step 4, therefore, no data are presented in this time domain. One can notice a small loss of the reectance at this procedure (0.004).

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M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

1.00
With protection by thiol

Reflectance

0.99
0.98
0.97
0.96
0.95
0

10

20

30

40

50

60

Time (min)
Fig. 14. The reectance change in 10 mM Na2S solution with the thiol-lm formed by dipping after the
reduction reaction.

The mass changes all through the experiments were regrouped in Fig. 15b. At the
end of the step 2, the mass was decreased by 21.9 lg cm2 from the beginning of the
experiments (t = 0). If the remaining carbonate layer on the electrode was neglected
at this stage, the tarnishing followed by the reduction of silver sulphide lead to the
loss of this amount of silver, corresponding to the loss of about 20 nm of the silver
layer according to the Faraday law, and may be considered as negligible.
A marked decrease of oscillation frequency was observed when the EQCM electrode was transferred into the lm-formation solution. It is important to recall that
the change of solution viscosity may introduce a bias error in the evaluated mass
density by EQCM. But, the evaluated mass increase as great as 150 lg cm2 indicates
that a considerable amount of hexadecane-thiol agglomerated around the electrode.
During the immersion of the silver electrode in Na2S solution with the thiol-protected electrode, the variation of mass is irregular, compared with that recorded at
the rst step (without any protection). It is likely that the excess of thiol agglomerated around the electrode surface, remained even after rinsing in isopropanol, and is
leaving from the silver surface during this period.
3.5.3. Impedance spectra
The impedance spectra collected just after the immersion of the bulk silver electrode in 10 mM Na2S solution, without and with the protective lm are presented
in Fig. 16.
In absence of protection, for all impedance spectra collected, an inductive behaviour at the low frequency side and two capacitive loops, for frequencies higher than 1
Hz, were recorded though not clearly separated. In contrast, three capacitive loops
were necessary to reproduce experimental impedance spectra by an electric equivalent circuit.
In absence of protective layer, the highest frequency loop was constituted of a
capacitance of 2070 lF cm2 in parallel with a resistance of some tens X cm2.

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

(a)

1.0

Reflectance

677

cathodic
reduction
(Step 3)

0.8

Thiol-film
formation
(Step 4)

0.6

Tarnishing
with
protection
(Step 5)

No reflectance
measurements
performed

0.4
0.2
0.0
0

Tarnishing
without
protection
(Step 2)
60

120

180

Time (min)

Mass density (g.cm-2)

250

(b)
200

Cathodic
reduction

150
100
50

Thiol-film
formation

Tarnishing
without
protection

Tarnishing
with
protection

60

120

180

Time (min)
Fig. 15. The variation of (a) the reectance and (b) the mass all through the experiments for the silver
plate electrode 1 in 10 mM Na2S solution.

The origin of this loop is unclear, but may be attributed to the powdery surface
lm formed by Ag2S. The second capacitive loop is represented by a capacitance
of 45100 lF cm2 and a resistance of 300500 X cm2. This couple will be likely
attributed to the double layer capacitance in parallel with the charge transfer resistance.
When the silver specimen was protected by a thiol-lm, the highest frequency loop
can be reproduced by a capacitance of 14 lF cm2 in parallel with a resistance of
1020 X cm2. This couple is attributed to the thiol-lm, which covers the silver electrode surface. The value of the capacitance corresponds to one or two thiol layers,
that suggests the formation of SAM (self-assembling membrane). The EQCM measurements, however, did not indicate such a small mass change. The surface lm may
thus be constituted of a compact inner layer, of one to two molecules, and a badly
organised outer layer. The second capacitive loop is constituted of the double layer
capacitance of 1020 lF cm2 and the charge transfer resistance of 1.52.5 kX cm2.

678

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

- Imaginary part (k cm2)

1.0

Protected by
thiol-film

0.5

0.1

10

0.0

-0.5
0.0

0.01

No protection
0.1
0.01

0.5

1.0

1.5

2.0

Real part (k cm2)

Fig. 16. The impedance spectra recorded just after the immersion of bulk silver plate electrode in 10 mM
Na2S solution with or without the protective thiol-lm.

From the Rt value with and without thiol treatment, the protective eectiveness of
ca. 80% was evaluated.

4. Conclusion
It was shown that the tarnishing of the silver surface can be realised in 10 mM
Na2S solution. This sulphide concentration (320 ppm) is much higher than that of
the surface electrolyte lm in urban atmosphere (ca. 1 ppm). But, this high concentration allowed the formation of tarnished layer in a short experimental duration.
The tarnishing of the silver surface was determined quantitatively with reectance
measurements on the silver electrode by means of a spectrometer equipped with an
integration sphere. When the reectance measured is higher than 0.8, no tarnishing
can be detected by a visual observation, which indicates a good sensibility of the
method. This technique is therefore really necessary when the protective eectiveness
to the tarnishing process will be examined.
We have shown that the tarnishing layer can be removed by the cathodic
reduction. The voltammogram showed the potential at the current peak (1.3 VSME)
in a good agreement with the standard equilibrium potential of Ag +
S 2 () Ag2S + 2e. In view of a eld application, at museum for instance, the
galvanostatic reduction method was adapted. It was found that the current density
of 0.5 mA cm2 gave a satisfactory result. However, after the reduction, sometimes,
a dull surface, instead of a bright silver surface was obtained. A slight wiping with
cotton-tip allowed the removing of this layer. From the EQCM measurements, the
precipitation of carbonate was proposed.
For the protection of silver, an electrochemically synthesised polymer layer,
poly(3-amino 1,2,4-triazole) was examined. The formation of an insulating lm on
a silver electrode was veried, but this lm seems permeable with respect to S2 or

M.C. Bernard et al. / Corrosion Science 47 (2005) 663679

679

sulphide, and for some silver specimens, the protection is eective and for other specimens, the tarnishing of the surface was observed. This method has therefore been
considered as not suciently reliable.
In contrast, the surface treatment by hexadecane-thiol is highly ecient. The silver specimen was dipped in 0.15 M hexadecane-thiol in isopropanol solution. The
concentration used is much higher than that used usually for the formation of
SAM lm, but, 1 h dipping is sucient to obtain a good protective lm. It is also
veried that the use of hexane during the preparation of the silver surface may be
discarded. In fact, this substance is toxic, and will be useful only when the specimen
surface is fatty.
The advantages of the proposed protection method are numerous:
(i) The thiol-lm formed is colourless and does not modify the visual aspect.
(ii) The cathodic reduction removes a minimum quantity of the initial silver, compared with the polishing often used.
(iii) The thiol-lm may be removed readily by heating silver artefacts, or dipping in
hot isopropanol. This substance is considered not hazardous.
(iv) Once the surface treatment realised, no particular protection is necessary for a
subsequent tarnishing in a polluted atmosphere by sulphide.
In other terms, the proposed method satises the ethics of curators and conservators, and suciently reliable.
Another medium for the reduction of tarnished silver shall be investigated, that
will avoid a precipitation on a silver surface, though a slight wiping of the surface
be an easy task. Anions with which the silver does not form insoluble salts, such
as nitrate or perchlorate salts will be a good candidate. Further, a more detailed
study on the structure of thiol-lm is necessary, for instance, to verify whether the
surface lm is really the SAM or a badly organised lm.

References
[1] M. Keddam, L. Klein, H. Takenouti, B. Trachli, 15th International Corrosion Congress, Granada,
September 2002, CD-Rom Proceedings, no. 701.
[2] B. Trachli, M. Keddam, A. Srhiri, H. Takenouti, Corros. Sci. 44 (2002) 9971008.
[3] M. Evesque, M. Keddam, L. Klein, H. Takenouti, Electrochim. Acta 49 (2004) 29392943.
[4] C. Degrigny, M. Jerome, N. Lacoudre, Progress in the understanding and prevention of corrosion,
Corrosion Australasia 18 (1993) 1618.
[5] C. Degrigny, M. Wery, V. Vescoli, J.M. Blengino, J. Int. Inst. Conservat. Historic Artistic Works
(1995) 170.
[6] T.D. Burleigh, Y. Gu, G. Donahey, M. Vida, D.H. Waldeck, Corrosion 57 (12) (2001) 1066.