Applied Surface Science 421 (2017) 120–127

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Applied Surface Science

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Full Length Article

Artificial patina formation onto copper-based alloys: Chloride and

sulphate induced corrosion processes
G. Di Carlo a,∗ , C. Giuliani a,∗ , C. Riccucci a , M. Pascucci a , E. Messina a , G. Fierro b ,
M. Lavorgna c , G.M. Ingo a,∗
a
Institute for the Study of Nanostructured Materials, National Research Council (ISMN-CNR), Via Salaria km 29,300, 00015 Monterotondo (RM), Italy
b
Istituto per lo Studio dei Materiali Nanostrutturati, National Research Council (ISMN-CNR), c/o SAPIENZA – Università di Roma, Dipartimento di Chimica,
Piazzale A. Moro 5, 00185 Rome, Italy
c
Institute of Polymers, Composites and Biomaterials, National Research Council (IPCB-CNR), Piazzale Fermi 1, 80055 Portici (NA), Italy

a r t i c l e i n f o a b s t r a c t

Article history: Naturally grown patinas are typically detected onto the surface of modern copper-based artefacts and
Received 15 October 2016 strictly affect their surface reactivity and appearance. The production of representative patinas is a
Received in revised form 8 January 2017 key issues in order to obtain model systems which can be used for the development and validation
Accepted 9 January 2017
of appropriate conservation materials and methods. In this study, we have prepared different artificial
Available online 11 January 2017
representative patinas by using a quaternary Cu-Sn-Zn-Pb alloy with chemical composition and met-
allurgical features similar to those of valuable modern works of art. In order to produce degradation
Keywords:
products usually observed onto their surface, chloride and sulphate species were used to induce corro-
Artificial patinas
Copper-based alloys
sion processes. Different patinas were produced by changing the nature of corrosive species and the set-up
Copper hydroxychlorides for the accelerated degradation. The composition and structural properties of the patinas were investi-
Copper hydroxysulphates gated by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray diffraction, optical
Modern works of art microscopy and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. The
results allow to identify degradation products and to distinguish copper hydroxychloride polymorphs
and copper hydroxysulphates with similar structure. Our findings show that patina composition can be
tailored by modifying the degradation procedure and patinas representative of modern artefacts made
of quaternary Cu-Sn-Zn-Pb alloy can be obtained.
© 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction corrosion process. This degradation process can significantly com-

Modern copper-based artefacts are typically characterized by
the presence of naturally grown surface patinas, whose compo-
sition can be complex and depends on several parameters, such
as alloy composition, metallurgical features and environmental
conditions [1–10]. The growth of surface patinas is induced by
degradation processes occurring on the metal surface and leading
to the formation of alteration products and reactive compounds,
such as oxides, carbonates, chlorides, hydroxychlorides, nitrates,
sulphides and sulphates [1–4]. Among these species, particular
attention has to be payed to chlorides, which in the presence of
moisture and oxygen, are extremely harmful since are responsi-
ble for the “bronze disease”, based on an inexorable cyclic copper
∗ Corresponding authors.
E-mail addresses: gabriella.dicarlo@ismn.cnr.it (G. Di Carlo),
chiara.giuliani@ismn.cnr.it (C. Giuliani), gabriel.ingo@ismn.cnr.it (G.M. Ingo).
promise the conservation status of valuable works of art and modify
the object surface appearance transforming it in a greenish pow-
der. However, stable degradation products can be also formed on
the metal substrate thus creating a passive protective layer, known
as “noble” patina. Therefore, it is important to identify the chem-
ical composition of surface patinas since they can strictly affect
both surface reactivity and appearance of the metal artefacts, which
have to be considered in the identification of the most appropriate
conservation materials and methods.
The conservation of modern copper-based works of art needs
the development of novel corrosion inhibitors that can fulfil the
always most demanding protective, aesthetic and safety require-
ments. For the assessment and optimization of corrosion inhibiting
materials, the viability of reference Cu-based alloys that can be
sacrificed represents a key issue. Different studies have been
performed on different artificially achieved chemical patinations
mainly with the aim to obtain protective layers or to investi-
gate degradation mechanisms and the attention has been focused

http://dx.doi.org/10.1016/j.apsusc.2017.01.080
0169-4332/© 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.
0/).
 G. Di Carlo et al. / Applied Surface Science 421 (2017) 120–127
especially on archaeological artefacts [9–14]. In this frame, the pro-
duction of reference Cu-based alloys with chemical composition
and metallurgical features similar to modern works of art is still
an important challenge. To this aim, it is first necessary to select a
representative alloy and then to induce the formation of artificial
patinas with composition comparable to those grown on modern
works of art. According to the literature [1–3], valuable modern
artefacts (as from Rodin, Epstein, Herbert, Giacometti, etc.) have
been truly characterized to get information about the composition
of the metal alloy and surface patina. The results have shown that
the investigated copper-based alloys contain different amounts of
alloying elements, mainly Sn, Zn and Pb.
Concerning the surface patinas, they have been formed sponta-
neously due to corrosion processes or could have been created by
the artist for aesthetic reasons [15,16]. The naturally grown pati-
nas confer to the copper-based alloy different colours depending
on the nature of degradation products. For example, a greenish
patina can be obtained due to the formation of atacamite and its
polymorphs Cu2 (OH)3 Cl, nantokite CuCl, antlerite Cu3 (OH)4 SO4 ,
malachite Cu2 (OH)2 CO3 , and it can be lightened by lead carbonate
PbCO3 or tin oxide SnO2 [2,11]. The metal surface can be red-
dened by an underlayer of cuprite Cu2 O, whereas a blueish colour
is typically due to some copper hydroxysulphates, as posnjakite
Cu4 SO4 (OH)6 ·(H2 O) and brochantite Cu4 SO4 (OH)6 , and to azurite
Cu3 (OH)2 (CO3 )2 [2,11].
The most frequently identified compounds in the patina of
modern indoor and outdoor bronze sculptures are Cu2 (OH)3 Cl
polymorphs and cuprite. Since chloride species are the most dan-
gerous for copper-based artefacts, great attention is payed to
their characterization and in particular to the identification of
Cu2 (OH)3 Cl polymorphs. The phases typically found in the patinas
are the orthorhombic atacamite, the monoclinic clinoatacamite, the
monoclinic botallackite and the recently discovered triclinic anat-
acamite [17,18]. Other aggressive degradation products are copper
hydroxysulphate compounds produced in the presence of sulphate
species. The most common phases are the orthorhombic antlerite,
the monoclinic brochantite and the hydrated monoclinic posnjakite
[11,19,20].
The present work is aimed to the production of representative
artificial patinas on copper-based alloys with chemical composition
and metallurgical features similar to modern copper-based works
of art, which can be used as model systems for the optimization
and validation of protective materials and methods.
To this purpose, we have prepared different artificial patinas
by using a quaternary copper-based alloy (Cu-Sn-Zn-Pb) as metal
substrate and by inducing the formation of degradation products
with chloride and sulphate species. The patina composition was
modified by changing the nature of corrosive species (i.e. HCl,
CuCl2 , CuCl2 /HCl and CuSO4 , in the presence of H2 O/O2 ) and the
set-up used for the accelerated corrosion procedures (i.e. inter-
action with acidic vapours, soaking or wetting with corrosive
solutions). The composition and structural properties of the patinas
were investigated by attenuated total reflectance Fourier transform
infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), opti-
cal microscopy and scanning electron microscopy combined with
energy dispersive X-ray spectroscopy (SEM-EDS).
2. Experimental
2.1. Copper-based alloy
A commercial bronze alloy, labelled 555, with nominal compo-
sition of 85% Cu, 5% Sn, 5% Pb, 5% Zn and produced by casting, was
used as representative Cu-based alloy. The 555 alloy disks have
been polished by using SiC papers at 1200 grit and diamond pastes
121
up to 1/4 ␮m in order to obtain a flat and smooth surface with a
mirror-like finish. After polishing, the Cu-based alloys have been
cleaned with ethanol.
2.2. Production of artificial patinas
In the case of chloride-induced patina, artificially corroded
samples have been prepared by accelerated corrosion treatments
induced by chloridric acid and/or CuCl2 in the presence of water.
The patinated alloy A, labelled as PA-A, was prepared by treating
the bare 555 alloy with acidic water vapours (HCl 5 wt%/H2 O) in a
closed vessel for 3 days.
The patinated alloy B, labelled as PA-B, was obtained by immer-
sion of the bare 555 alloy disk into a CuCl2 1 M aqueous solution
for 24 h and subsequent exposure to water vapours for 24 h by
using a procedure similar to the one reported in the literature by
Faltermeier [21].
The patinated alloy C, labelled as PA-C, was prepared by treating
the bare 555 alloy with a cotton swab embedded with an aque-
ous solution containing CuCl2 0.5 M and HCl 0.1 M and subsequent
exposure to water vapours for 3 days.
In the case of sulphate-induced patina, a patinated alloy D,
labelled as PA-D, was prepared by immersion of the bare 555 alloy
disk into a CuSO4 17 mM aqueous solution at 200 ◦ C for 2 h and sub-
sequent immersion into a CuSO4 50 mM aqueous solution at room
temperature for 15 days.
2.3. Micro-chemical, morphological and structural analysis by
SEM-EDS, OM, ATR-FTIR and XRD
Micro-chemical and morphological characterisations were per-
formed by means of a scanning electron microscope (SEM)
Cambridge 360 equipped with a LaB6 filament equipped with an
energy dispersive X-ray spectrometer (EDS) INCA 250, and a four
sectors back-scattered electron (BSE) and secondary electron (SEI)
detectors.
Optical microscopy (OM) investigations were performed by
using a Leica MZFLIII microscope equipped with a digital camera
(Leica DFC 320).
Attenuated total reflectance Fourier transform infrared (ATR-
FTIR) spectroscopy was used for the surface characterization of
patinas. The infrared spectra were collected using a Nicolet iS50
spectrometer (Thermo Fisher) equipped with an ATR accessory.
The measurements were recorded using a diamond crystal cell ATR
using typically 32 scans at a resolution of 4 cm−1 . The samples were
all measured under the same mechanical force pushing the samples
in contact with the diamond crystal. No ATR correction has been
applied to the data.
XRD patterns were recorded by Siemens 5000 X-ray powder
diffractometer using a Ni-filtered CuK␣ radiation (␭ = 1.5418 Å).
Angular values with a step size of 0.05◦ and a sampling time of
2 s were the experimental parameters used for data acquisition.
In order to identify the crystalline phases, the analysis of X-ray
diffraction patterns was carried out by using electronic databases.
3. Results and discussion
Within this study, we have selected a quaternary copper-based
alloy (Cu-Sn-Zn-Pb, 555 alloy) as representative of modern copper-
based works of art on the basis of literature data obtained from
the analysis of several modern bronze sculptures [1–3]. The met-
allurgical structure and chemical composition of the selected 555
alloy were investigated by SEM-EDS. A representative SEM image
in Fig. 1 confirms that the selected alloy has a dendritic structure
which is typical of cast bronze artefacts. The results of EDS analysis
reported in Table 1 indicate that the surface chemical composition
122 G. Di Carlo et al. / Applied Surface Science 421 (2017) 120–127

Fig. 1. SEM image and EDS spectra of bare 555 alloy. The EDS spectrum on the left was recorded on the white islands and the one on the right on a large area.

Table 1
Chemical composition of bare and patinated alloy disks determined by EDS analysis.

Disk Cu (wt.%) Sn (wt.%) Zn (wt.%) Pb (wt.%) Cl (wt.%) S (wt.%)

555 alloy 86,6 6,5 4,4 2,5 n.d. n.d.

PA-A 77,6 n.d. 1,4 1,4 19,6 n.d.
PA-B 74,3 5,3 n.d. 1,2 19,2 n.d.
PA-Cgreen area 76,2 n.d. n.d. 2,4 21,4 n.d.
PA-C red area 71,2 11,2 2,3 5,9 9,4 n.d.
PA-D 84,4 1,8 n.d. 1,4 n.d. 12,4

n.d.: not detectable.

is Cu 86.6 wt.%, Sn 6.5 wt.%, Zn 4.4 wt.% and Pb 2.5 wt.%, whereas the
spectra in Fig. 1 clearly show that the white islands mainly consist
of Pb.
Different artificial patinas have been prepared by inducing the
surface degradation with chloride and sulphate species. The first
species induce the formation of the most harmful degradation
products, found both in indoor and outdoor artefacts, whereas the
latter species are most commonly detected in outdoor works of art.
The optical images of bare 555 alloy and of disks artificially
patinated using chloride species are shown in Fig. 2 and the com-
position of the surface patinas has been investigated by ATR-FTIR
spectroscopy and complementary XRD measurements [22]. The
 G. Di Carlo et al. / Applied Surface Science 421 (2017) 120–127
Fig. 2. Optical images of bare 555 alloy (a), patinated PA-A (b), patinated PA-B (c) and patinated PA-C (d) disks.
infrared spectroscopy, useful for the identification of different cor-
rosion products [22–26], is essential for the characterization of
Cu2 (OH)3 Cl polymorphs, since their XRD patterns are usually sim-
ilar. In particular, the very closely related crystal structures of
clinoatacamite and anatacamite are not easily distinguished by XRD
and, in this case, ATR-FTIR can be used effectively in determining
the exact crystal structure of Cu2 (OH)3 Cl [17,24].
Infrared spectroscopy provides information about the inter-
action between hydroxyl groups and copper centres in the
crystal lattice, thus allowing to distinguish among Cu2 (OH)3 Cl
polymorphs. Atacamite, clinoatacamite and anatacamite have pro-
nounced peaks in two useful ranges of frequencies due to hydroxyl
stretching (3500 and 3200 cm−1 ) and deformation (1000 and
800 cm−1 ) [17]. The atacamite can be identified by the presence of
infrared bands at 3330, 946, 891 and 845 cm−1 , whereas clino- and
anatacamite polymorphs are characterized by bands at 3359, 3310,
863 and 827 cm−1 . Therefore, atacamite is typically easily identi-
fied by the presence of infrared peaks at about 950 and 890 cm−1 ,
differently from clinoatacamite. Moreover, the anatacamite can be
distinguished by the presence of a weak peak at 3400 cm−1 [17].
The ATR-FTIR spectrum of PA-A in Fig. 3 shows the presence of
all the peaks that are characteristic of anatacamite, including the
week band at 3400 cm−1 , thus indicating that the surface patina
is mainly composed by anatacamite phase. In PA-B and PA-C, it
was observed the presence of both clinoatacamite and atacamite
polymorphs, with the prevalence of clinoanatacamite phase in the
light green areas. The peaks at about 950 and 890 cm−1 , which are
peculiar of atacamite, are marked with circles. It is worth noting
that only in the PA-C was detected in the red area the shoulder at
123
about 625 cm−1 , which is attributed to cuprite [17,19]. In all the
patinated disks, infrared peaks due to botallackite phase were not
detected [27].
The patinated alloy disks were also characterized by XRD analy-
sis and the diffraction patterns are reported in Fig. 4 in comparison
with the bare 555 alloy, reference cuprite, reference Cu2 (OH)3 Cl
polymorphs (atacamite, clinoatacamite, anatacamite, botallackite)
and reference nanotokite. All the patinated disks show the pres-
ence of diffraction peaks at about 16.3, 32.4 and 39.7◦ 2␪ which
can be attributed to Cu2 (OH)3 Cl species, however on the basis
of XRD measurements it is not possible to distinguish between
these polymorphs due to the very similar crystalline structure. A
higher crystallinity was detected in PA-A, whereas the peak inten-
sity is lower in PA-B probably due the presence of more amorphous
species or to a thinner patina layer. The peak at about 36.5◦ 2␪,
typical of cuprite, is clearly observed in PA-C, in agreement with
FTIR data, and probably with a lower extent in PA-B. For the most
heterogeneous patinated PA-C disk, the diffraction patterns were
recorded in two different areas, the greenish and reddish ones. The
profiles in Fig. 4 show that the Cu2 (OH)3 Cl peaks are not detectable
in the reddish area, where the cuprite signal is predominant. Fur-
thermore, XRD results reveal that peaks due to botallackite and
nantokite were not detectable in all the patinated disks.
In Fig. 5, the optical image and the ATR-FTIR spectrum of PA-
D are reported. The visual observation shows the presence of a
reddish substrate with greenish and blueish areas. The peak inten-
sity and position in the ATR-FTIR spectrum can be attributed to
copper hydroxysulphate species [19,23,26]. Indeed, the bands at
about 1100–1050 cm−1 are typical of sulphate groups and the
124 G. Di Carlo et al. / Applied Surface Science 421 (2017) 120–127

(a) PA-A
* Anatacamite
0,10

PA-A

In te n s it y ( a .u .)
0,08
PA-B
Absorbance (a.u.)

PA-C green
0,06 PA-C red
Bare 555 alloy
Cuprite
0,04 *
Atacamite
* *
* * Clinoatacamite
0,02 * * Anatacamite
Botallackite
* Nantokite
10 20 30 40
0,00
3600 3400 3200 3000 1000 900 800 700 600 2 theta (°)
-1
Wavenumber (cm )
Fig. 4. XRD patterns of patinated alloy disks (PA-A, PA-B, PA-C green area, PA-C red
area) and bare 555 alloy. The diffraction profiles of cuprite, Cu2 (OH)3 Cl polymorphs
and nantokite are reported as reference.
(b) * Clinoatacamite PA-B green area
0,10 PA-B green-grey area
° Atacamite

0,08
Absorbance (a.u.)

Absorbance (a.u.)
0,06

0,04
green-blue
* area
*
0,02 * * *°
* * ° red area

0,00

3600 3400 3200 3000 1000 900 800 700 600

-1
Wavenumber (cm )
3600 3400 3200 3000 1200 1000 800 600
-1
(c) Wavenumber (cm )
* Clinoatacamite PA-C light green area
0,20 PA-C green area Fig. 5. Optical image and ATR-FTIR spectrum of sulphate-induced patina, PA-D
° Atacamite
* PA-C red area green-blue and red areas. (For interpretation of the references to colour in this figure
+ Cuprite
* legend, the reader is referred to the web version of this article.)
0,15 *
*
Absorbance (a.u.)

* *
* ° °
*
0,10
° * °°
* *
*° * °
*° * *°
* *° *
0,05 ° PA-D
I n t e n s it y ( a .u . )

+
Bare 555 alloy
0,00 Cuprite
* * *
° * * *
3600 3400 3200 3000 1000 900 800 700 600
Brochantite
Wavenumber (cm )
-1 °
° °° °
°
Antlerite
Fig. 3. ATR-FTIR spectra of chloride-induced patinas: PA-A (a), PA-B (b) and PA-C
Posnjakite
(c).
10 20 30 40 50 60
2 theta (°)
sharped peaks at 3571 and 3484 cm−1 mainly suggest the pres-
ence of antlerite, even if on the basis of only infrared analysis Fig. 6. XRD patterns of PA-D, bare 555 alloy and reference cuprite and copper
antlerite, brochantite and posnjakite cannot be easily distinguished hydroxysulphates.
[19,23,26]. The ATR-FTIR spectrum of the reddish area is also
reported in Fig. 5 and it is very similar to the one of greenish-blueish
patina, thus suggesting that copper hydroxysulphate species are posnjakite). In the PA-D pattern, it was clearly observed the pres-
uniformly distributed on all the surface patina. ence of peaks attributed to antlerite and brochantite, beside the
Insights into the patina composition were obtained by means of presence of cuprite. On the contrary, peaks due to posnjakite phase
XRD characterization. The diffraction pattern of PA-D is reported in were not detectable. In the case of sulphate-based degradation
Fig. 6 and it was compared with bare 555 alloy, reference cuprite products, XRD measurements are very useful and allow to obtain
and reference copper hydroxysulphates (antlerite, brochantite and more detailed information on copper hydroxysulphate compounds.
 G. Di Carlo et al. / Applied Surface Science 421 (2017) 120–127 125

(a) co-existence is shown by the small component of the O 1s band

centred at about 529.8 eV, which suggest the presence of O-Metal
12000 O 1s bonds, a weak component peaked at 533.0 ± 0.2 eV attributed to
adsorbed water and by a third component assigned to hydroxylated
P h o to e m is s io n in te n s it y ( a .u .)

species peaked at 532.0 eV [30].

10000 Further information on the artificial patinas were obtained by
optical analysis at higher magnification and the images in Fig. 8
shows that the patina surface changes significantly depending on
8000
the preparation procedure. In PA-A, a high amount of green degra-
dation products grow on a red underlayer, whereas in PA-B they
are more scarcely present onto a red-greyish substrate. The simul-
taneous presence of green, red and mixed areas is observed in
6000
PA-C which is the most heterogeneous patina produced from chlo-
ride species. The image of PA-D show the presence of green-bluish
degradation products on a slightly red substrates, as previously
4000 observed in Fig. 5.
524 526 528 530 532 534 536 538 For sake of comparison, an example of heterogeneous patina
Binding energy (eV ) naturally grown onto the surface of a modern bronze artefact is
reported in Fig. 9. The considered work of art is made of a qua-
ternary Cu-Sn-Zn-Pb alloy with a chemical composition similar to
(b) the selected reference 555 alloy. The natural patina on the arte-
fact is highly heterogeneous and comparable especially with the
Sn 3d5/2 - Sn 3d3/2 artificially prepared PA-C patina.
16000
P h o to e m is s io n in te n s it y ( a .u .)

4. Conclusions
12000
The results of this study suggest that artificial patinas with dif-
ferent composition and distribution of degradation products can
8000
be prepared by treating a reference quaternary Cu-Sn-Zn-Pb alloy
with chloride and sulphate species.
The identification of degradation products, as copper hydrox-
ychlorides, copper hydroxysulphates and cuprite, was carried out
4000 by using complementary techniques. In particular, ATR-FTIR spec-
troscopy was used to easily distinguish Cu2 (OH)3 Cl polymorphs,
whereas XRD analysis provided useful information to identify cop-
480 485 490 495 500 505 per hydroxysulphates. The chemical composition and distribution
Binding energy (eV) of degradation products were also investigated by SEM-EDS analy-
sis, XPS and optical microscopy.
Fig. 7. XPS spectra of O 1s (a) and Sn 3d5/2 – Sn 3d3/2 (b) for different areas of the
The results reveal that the patina composition can be tailored
alloy subjected to the accelerated degradation treatment.
by changing the preparation procedure:

The chemical composition of the surface patinas was also inves-

tigated by EDS analysis and the data were compared with the - An aggressive treatment with HCl water vapour (PA-A) leads
bare 555 alloy. The results reported in Table 1 show a significant mainly to the formation of anatacamite Cu2 (OH)3 Cl onto a red
amount of chlorine and sulphur in the disks treated with chloride underlayer of cuprite Cu2 O.
and sulphate species, respectively. The heterogeneous distribu- - The corrosion treatment by immersion in a CuCl2 solution (PA-
tion of chemical elements in the PA-C is confirmed, in agreement B) is responsible for the formation of atacamite/clinoatacamite
with visual observation and with spectroscopic evidences. It polymorphs that are scarcely distributed onto cuprite.
was observed that the surface chemical composition significantly - By treating the alloy with a cotton swab embedded with an aque-
changes after patination. A dezincification was observed in differ- ous CuCl2 solution (PA-C), an heterogeneous patina has been
ent patinated disks, indeed Zn completely disappears in PA-B, in formed. In this case, green and red areas mainly consisting of
the green areas of PA-C and in PA-D. A disappearance of Sn was atacamite/clinoatacamite popymorphs and cuprite, respectively,
also observed in PA-A and in the green areas of PA-C. were obtained.
ATR-FTIR and XRD characterizations have revealed that the cop- - By soaking the metal alloy in a CuSO4 aqueous solution (PA-D),
per species predominate in the corrosion products. Complementary the surface patina mainly consists of antlerite, brochantite and
information have been obtained by XPS analysis, which was used cuprite.
to investigate the chemical state of the alloying elements. In agree-
ment with EDS results, Zn compounds have been not detected in
different patinated disks due to the pronounced dezincification Since the composition of natural patinas is complex and depends
phenomenon [28,29] and Sn is scarcely present. The XPS analysis on several parameters, the selection of the most representative
revealed that Sn forms hydrated Sn(IV) oxide [28,29] and represen- patina has to be carried out on the basis of the specific case study.
tative spectra of different areas are shown in Fig. 7. The hygroscopic However, by considering a modern artefact made of a common qua-
nature of corrosion products is confirmed by the study of the O 1s ternary Cu-Sn-Zn-Pb alloy, the heterogeneous artificial PA-C patina
peak and the XPS spectra reported in Fig. 7 reveal both the pres- can be considered as the most representative and is a suitable sub-
ence of anhydrous and hydrated compounds at the surface; their strate for the optimization of corrosion inhibiting materials.
126 G. Di Carlo et al. / Applied Surface Science 421 (2017) 120–127

Fig. 8. Optical images of PA-A (a), PA-B (b), PA-C (c) and PA-D (d).

Acknowledgements

The work has been carried out within the NANORESTART project
funded by the European Union’s Horizon 2020 Research and inno-
vation programme under the grant agreement No 646063. The
authors kindly thank Dr. Francesco Giordano and Claudio Veroli
for X-ray diffraction measurements and phase identification.

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with a naturally grown patina.
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