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Copper Alloys And Silver Artefacts Protection By Coatings

With Nano-Alumina Pigments
P. Vassiliou, J. Novakovic and Kl. Samara
School of Chemical Engineering, National Technical University of Athens,
9, Iroon Polytechniou Str,
15780, Athens, Greece
e-mail: pvas@chemeng.ntua.gr

In the framework of safeguarding movable cultural heritage artefacts, a study of copper alloys and silver ob-
jects is undertaken to find a protective system that could be safely employed, following the ethics of conserva-
tion. For this purpose, silver drawn sheet coupons and cast copper alloy coupons were tarnished by different
chemical methods to simulate the corrosion patina of aged artefacts. An extensive study of the produced corro-
sion layers was performed by X-ray diffractometry, scanning electron microscopy, and surface analysis as well
as optical microscopy. The nano-alumina pigmented acrylic polymer coatings were tested on the clean and ar-
tificially aged metal coupons. The linear polarization method was employed as well as electrochemical imped-
ance spectroscopy to check on the integrity of the protective coating. The results show that the organic protec-
tive system is quite sufficient to protect the metal surface from the corrosive ions of the solution without com-
promising the aesthetic aspect of the metal/coating system.

Keywords: silver corrosion, protective coatings, nano-alumina pigment

1. INTRODUCTION that could be safely employed on bronze and silver objects

The archaeological and artistic value of objects of cop-
per and silver alloys found in archaeological sites makes
their preservation of primarily importance. These objects
undergo soil corrosion and, after excavation, atmospheric
corrosion processes leading to the formation of corrosion
products termed patinas. The patina is formed sponta-
neously with a long time exposure to the environment sur-
rounding these items. The structure and the composition
of patina are specific to each object. Silver metal artefacts
tarnish readily in urban atmospheres. Tarnishing is the for-
mation of Ag2S on the surface of silver when exposed to a
wide range of sulphur containing environments and it is ac-
celerated by humidity.
Synthetic or artificial patina layer can be obtained by
appropriate surface treatment on bronze or silver alloys
[1]. In that way a reproducible patina, simulating the corro-
sion patina of aged artefacts can be obtained at any mo-
ment within a reasonable time.
Many publications concerning patina are devoted to
the chemical characterisation and to the crystallographic
structure in relation either to the environment to which the
metals have been exposed [2] or the consequence of the at-
mosphere, of soil [3] or marine corrosion [4]. Because of a
substantial increase of pollutant concentration in urban at-
mosphere, the protective patina formed during a long peri-
od of time appears not to be stable, and the patina forma-
tion or its dissolution (corrosion process) has been restart-
ed in various sites. It is therefore important to find
solutions, which protect metal objects covered by patina.
The aim of this work was to obtain a protective system
132
following the ethics of conservation. The proposed method
of protection, based on nano-alumina pigmented acrylic
resin, seems to be quite sufficient to protect metal surface
without compromising the aesthetic aspect of the metal/
coating system.
2. EXPERIMENTAL
2.1 Materials & Preparation of the bronze samples
The coin resembling samples (26mm diameter and
3mm height) of bronze alloy with a composition: Cu 92.3%
Sn 7.5% and Pb 0.2%, similar to the ancient one and a
structure typical to the one induced by casting was em-
ployed in order to investigate the corrosion behavior of an-
cient copper-based objects.
Accelerated corrosion procedure: Complete immersion of
the copper based specimens in a CuCl2 solution leads to
the production of CuCl, nantokite on the surface of the
sample according to the following reaction [5]:
Cumetal + Cu2+(aq) + 2Cl (aq) ⇒ 2CuCl(s)
-
(1)
The subsequent exposure of cuprous chloride to moisture
and air results in the formation of basic copper trihydroxy-
chloride, Cu2(OH)3Cl, [6]
4CuCl + O2 + 4H2O ⇒ 2Cu2(OH)3Cl + 2H+ + 2Cl
-
(2)
2.2 Materials & Preparation of the silver samples
Silver drawn sheet coupon (2cm x 5cm x 0.04 cm) with a
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Copper Alloys And Silver Artefacts Protection By Coatings With Nano-Alumina Pigments

composition Ag 92.5 % and Cu 7.5 % were tarnished by sion procedure (immersion in CuCl2 1M and exposure at
different chemical methods so as to produce corrosion lay- 100%RH) resulting in the formation of the light green,
ers similar to the ones produced on the metal artefacts ei- powdery, voluminous basic chlorides of copper, which dis-
ther by saline environment, containing mainly AgCl or ur- rupt the surface and may disfigure the object (Fig.1). The
ban environment, containing Ag2S [1] presence of the isomers paratacamite, Cu2(OH)3Cl, and at-
AgCl silver ageing: Silver coupons were immersed in the acamite, Cu2Cl(OH)3, on the surface of the samples is con-
hot solution of CuCl2 50 g/l (50–60 oC) for 20 min. The cor- firmed by the XRD analysis of the surfaces (Fig. 2 refer-
rosion-patination layer developed gradually and the color ence sample).
changed to brownish purple. The samples were removed,
washed in warm water and allowed to dry in air. An even
corrosion layer consisting mainly of AgCl has been pro-
duced.
Ag2S silver ageing: The silver samples were immersed in
cold (RT) BaS 5 g/l solution for 24 hours, producing a
slightly uneven dark brown Ag2S corrosion layer.

2.3 Protective coatings

The applied coatings consist of an acrylic resin as the
binder, the solvent and the pigment. Paraloid® B-72 100%
acrylic resin (a copolymer of ethyl methacrylate and methyl
acrylate, produced by Rohm and Haas) was tested as a
binder. The pigment added in the Paraloid coatings was g-
Al2O3 nanopowder (40-47nm). Toluene was used as the
solvent. A 15% wt Paraloid®B-72 solution in toluene was x100
brushed onto the metal surface, and after the solvent evap- Figure 1 - Photomicrographs of the surface of the bronze
oration, a film formed with thickness 5 – 10 Ìm. Alumina alloy reference sample, accelerated corrosion
nano-powder was added at 5%, 10%, and 25% weight per-
cent vs. Paraloid® B-72.

2.4 Electrochemical Linear Polarization measurements

The measurements were performed in a three-electrode
cell. The counter electrode was Pt foil and the reference
electrode was saturated calomel electrode. The electrolyte
was 0.1M Na2SO4 and the measurements were performed by
a Gamry CMS100 computer controlled potentiostat with
commercial software for the analysis.
2.5 Electrochemical Impedance Spectroscopy
The characterization of the Paraloid-alumina system,
in terms of the electrical properties of the film has been
evaluated through impedance measurements. A three-
electrode cell was used for the EIS measurements. The
counter electrode was Pt foil and the reference electrode
was saturated calomel electrode. The EIS was performed
by a Gamry CMS300 computer controlled system with
commercial software for the data analysis. Impedance
spectra were recorded in the frequency range from 5000 to
0.06 Hz by applying a sinusoidal signal of 10mV amplitude
at the open circuit potential, Eoc, as a function of the pig-
ment load in the 0.1M NaCl solution.
3. RESULTS & DISCUSSION
3.1 Accelerated bronze ageing
The laboratory contemporary produced copper alloy is
similar in composition and in structure to the ancient one.
Bronze coupons were submitted to the accelerated corro-
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Figure 2 - XRD diagrams of the bronze alloy
(p: paratacamite, a: atacamite, Cu: copper)
3.2 Accelerated silver ageing
AgCl silver ageing: By immersing silver coupons in the
hot CuCl2 solution, a relatively even 3-3.5 Ìm thick corro-
sion layer has been produced. Main corrosion products
identified by XRD analysis are chloroargyrite, AgCl and
probably nantokite, CuCl. Table 1 presents SEM images
and XRD diffractograms of the AgCl aged silver coupons.
Ag2S silver ageing: After immersion in the BaS solution,
slightly uneven dark brown 2-6Ìm thick corrosion layer is
created on the silver coupon surface. On the back scattered
electron image (Tab. 2) three different areas can be no-
ticed: white one of the almost clean metal, gray one of sil-
ver rich and black one of the copper rich corrosion prod-
ucts. The results of EDS analysis disclose that apart from
Ag2S, on the sample surface the presence ofCuS as well as
Ag2O and/or Cu2O can not be excluded. In the Table 2 are
presented SEM images and XRD diffractogram of the
Ag2S aged silver coupons.
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P. Vassiliou et al.

Table 1- SEM and XRD analysis of the AgCl aged silver coupons
SEM XRD

SE image x2000 Cross-section x800

Table 2 - SEM and XRD analysis of theAg2S aged silver coupons

SEM XRD

SE image x1000 BS image x1000

Cross-section x600
3.3 Protective coatings
3.3.1 Electrochemical Linear Polarization results
The results of the Electrochemical Linear Polarization
measurements for clean bronze samples coated with plain,
5% and 25% pigmented alumina Paraloid® B-72 immersed
in 0.1M Na2SO4 electrolyte for 1h (initial condition) are list-
ed in Table 3. The comparative illustration of the polariza-
tion curves is shown in Fig. 3. It is obvious from the Table 3
that Icorr decreases with the increasing pigment concentra-
tion, while Ecorr shifts to more positive values. Furthermore,
the higher pigment load of the film results to significantly
higher polarization resistance values, Rp. All these parame-
ters indicate better protective properties of nano-alumina
pigmented Paraloid® B-72 coatings than the plain one.
After 7-day electrolyte immersion the corrosion rate of
the plain B-72 and 25 % alumina pigmented coating in-
creases, while corrosion rate of the 5 % pigmented coating
remains practically unaffected. In the case of the 25 %
nano-alumina pigmented coating, it is possible that, into the
electrolyte, two different phenomena can take place; on the
one part, the higher the pigment load ⇒ the better protec-
tion that the coating offers to the metal substrate, which was
confirmed at initial conditions; on the other part the higher
the pigment load ⇒ the poorer the cohesion of the film,
which after 7 day immersion results in the significant reduc-
tion of the coating corrosion resistance, so it seems that
pigment load in the film should not exceed 10%.

Table 3 - Electrochemical Linear Polarization results for the clean bronze samples coated with plain, 5% and 25% alumina
pigmented Paraloid® B-72 after 1h and 7 day immersion in 0.1M Na2SO4 electrolyte
Pigment load Ecorr Icorr ‚c ‚a Rp CorrRate
(alumina/B72) mV mA/cm2 mV/Dec mV/Dec kø cm2 mm/yr
1 hour immersion - Initial condition
plain 0% -163.8 0.1866 346.8 779.7 558.5 0.002
5% -142.8 0.04709 301.7 362.9 1190 0.001
25% -124.1 0.004416 298.7 275.0 14080 0.000
7 day immersion
plain 0% -128.4 0.5170 127.1 134.4 548.9 0.004
5% -117.4 0.0614 277.8 442.3 1205 0.001
25% -118.3 0.1409 128.6 165.9 223.4 0.002

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Copper Alloys And Silver Artefacts Protection By Coatings With Nano-Alumina Pigments

1 — plain B-72 (0%)

2 — B-72 + 5% alumina
3 — B-72 + 25% alumina

Figure 3 - Electrochemical Linear Polarization curves of the clean bronze samples coated with plain, 5% and 25% alumina
pigmented Paraloid® B-72 immersed in 0.1M Na2SO4 electrolyte for 1h

3.3.2 Electrochemical Impedance Spectroscopy
The impedance measurement were performed in the
0.1M NaCl solution for plain and 10 % alumina pigmented
Paraloid® B-72 protective coatings on the clean, Ag2S and
AgCl aged silver surface. The samples were first left at the
open circuit potential for one hour before starting the ex-
periments. In order to interprate the data and to evaluate
the role of the alumina pigment in the overall performance
of the coating, the data were fitted to the equivalent elec-
trical circuit presented in Fig. 4. The results are presented
in Table 4.
The proposed equivalent circuit takes into account dif-
fusion processes within pores in the paint film, which are
modeled by the inclusion of a Warburg or pseudo imped-
ance placed in series with polarization resistance. Diffusion
control is a very common process in electrochemistry and
since the coating impedes the movement of chemical
species, not unexpected with coatings. The chemical species
associated with diffusion in coatings are oxygen and ions
(from the electrolyte) diffusing toward the metal and corro-
sion products diffusing away from the metal. It can be no-
ticed (Tab. 4) that warburg impedance of the 10 % nano-
alumina pigmented Paraloid® B-72 is higher than that of
the plain coatings and both of them exhibit superior values
on the clean Ag than on the Ag2S and AgCl aged silver sur-
face. Also, B-72-Al2O3 coatings show significantly lower
coating capacitance as well as double layer capacitance on
the all substrates than plain Paraloid® B-72 coatings.

Rs: solution resistance (electrolyte), (ø)

Rpo: pore resistance, is the resistance of ion conducting
paths in the film, (ø)
Rp: polarization resistance of the corrosion process on the
metal substrate, (ø)
W: Warburg impedance describing diffusion-controlled
1/2
electrochemical process (øs ).
Cco: Coating capacitance describing the capacitance of the
intact film (Farad)
Cdl: Double layer capacitance of the areas of the film where
there has been a penetration of the electrolyte (Farad)

Figure 4 - Equivalent electrical circuits for modelling the behaviour of the tested coatings.

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P. Vassiliou et al.

Table 4 - Analysis of the EIS spectra for the plain and 10% nano-alumina pigmented B-72 coating recorded after 1 hour i
mmersion in the 0.1 M NaCl solution.

Substrate Rpo W Rp Cco Cdl

kø køs1/2 kø mF/cm2 mF/cm2
Plain B72
Clean Ag 10.47 286.2 158.4 0.133 0.181
Ag2S 3.74 88.8 12.6 0.0881 0.217
AgCl 3.40 5.80 3.7 0.862 0.859
10 % nano-alumina pigmented B72-Al2O3
Clean Ag 8.17 811.6 125.1 0.0379 0.0491
Ag2S 3.74 202.2 375.0 0.0182 0.0369
AgCl 3.40 9.32 10.1 0.153 0.756

(a) Plain B72

(b) 10% nano-alumina pigmented B72-Al2O3

Figure 5 - Comparativa EIS spectra of Modulus vs. frequency, for the plain (a) and 10%alumina pigmented
Paraloid® B-72 (b) on the clean Ag, Ag2S and AgCl aged silver surface after 1h immersion in 0.1 M NaCl
electrolyte (initial condition)

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Copper Alloys And Silver Artefacts Protection By Coatings With Nano-Alumina Pigments
In Figure 5 are presented comparative EIS spectra
(Modulus vs. frequency) for the plain and 10% alumina
pigmented Paraloid® B-72 on the clean, Ag2S and AgCl
aged silver surface after 1h immersion in the 0.1 M NaCl
electrolyte. It is obvious from the Figures 5a and 5b that
both plain and alumina pigmented Paraloid® B-72 coat-
ings exhibit greater overall impedance and consequently
better protective properties on the clean Ag than on the
Ag2S and AgCl pre-aged silver surface. It should be also
pointed out that the overall impedance of the B-72-Al2O3
coatings, at low frequencies, on the clean and Ag2S aged
silver surface is almost three fold higher than of the plain
coatings. The situation is different in the case of the AgCl
aged silver coupons. Both B-72 and B-72-Al2O3 display low
impedance values. It seems that AgCl corrosion layer on
the silver surface significantly reduce protection character-
istics of the applied protective systems in the investigated
corrosion conditions. So, it should be taken into account
that when the corrosion layers contain chlorides, the ap-
propriate cleaning process should be applied, and followed
by complementary coating, which will properly isolate and
seal the metal surface from any contact with air and mois-
ture.
4. CONCLUSION
The proposed protective system is based on the barrier
protection offered by Al2O3 nanopowder pigmented par-
aloid coatings. Preliminary results on the characterization of
the coatings efficacy through electrochemical measurements
have shown that the Al2O3 pigmented Paraloid® B-72 coat-
ings exhibit better protective properties, in the investigated
corrosion conditions, than the plain ones. The pigment en-
hances the protective ability of the acrylic vehicle by chang-
ing the polymer structure to a tighter one and probably pre-
vents the metal ions diffusion to the solid/gas interface.
The proposed protective treatment is open to further
testing, as the polymeric material may in the long run turn
137
out to be an unsatisfactory coating, largely because of wa-
ter permeability. Incorporated water may lead to swelling
that in turn may disfigure the coating structure in a way fa-
vorable for the permeability of more moisture as well as
other of the environments. Besides, the treatment is com-
pletely reversible, and therefore always accessible to more
sophisticated methods of preservation.
Any silver or bronze protection scheme that exhibits a
marked resistance to tarnishing and meets conservation
standards would find acceptance and a market.
REFERENCES
[1] Vassiliou, P. and Novakovic, J.: “Silver Metal Arte-
facts Protection By Nano-Alumina Pigmented Coat-
ings”, Proceedings of the 7th European Conference
“SAUVEUR”, Prague, Czech Republic, May, 2006,
Vol.2, pp. 863-865.
[2] Robbiola, L., Blengino, J. M., Fiaud, C.:”Morphology
and Mechanisms of Formation Natural Patinas on
Arcaeological Cu-Sn Alloys”, Corrosion Science,
Vol. 40, pp. 2083-2111 (1998).
[3] Kratschmer, A., Odnevall Wallinder, I., Leygraf, C.:
“The Evaluation of Outdoor Copper Patina“ Corro-
sion. Science, Vol. 44, p. 425 (2002).
[4] A. Climent-font, G. Demortier, C. Palacio, I. Mon-
tero, J.L. Ruvalcabasil, D. Diaz, “Characterisation Of
Archaeological Bronzes Using PIXE, PIGE, RBS
and AES spectrometries”, Nuclear Instruments and
Methods in Physics Research, B134, pp. 229-236
(1998).
[5] MacLeod I. D., “Bronze Disease: An Electrochemi-
cal explanation”, ICCM Bulletin, VII, ICC M Inc.,
Canberra, pp. 16-26 (1981).
[6] Oddy W. A., and Hyghes M. J., “The Stabilisation Of
Active Bronze Disease And Iron Antiquites By The
Use Of Sodium Sesquicarbonate”, Studies in Conser-
vation, Vol. 15, pp. 183-189 (1970).