Copper Alloys and Weathering Steel

Used in Outdoor Monuments:

Weathering in an Urban-marine Environment
Paola Letardi* Monica Albini Emilio Cano Edith Joseph
CNR, Institute of Marine Sciences Laboratory of Microbiology, Centro Nacional de Investigaciones Laboratory of Microbiology,
Via de Marini 6 University of Neuchâtel Metalúrgicas (CENIM)-CSIC University of Neuchâtel
16149 Genova, Italy Rue Emile-Argand 11 Avda. Gregorio del Amo 8 Rue Emile-Argand 11
[email protected] 2000 Neuchâtel, Switzerland 28040 Madrid, Spain 2000 Neuchâtel, Switzerland
[email protected] [email protected] Haute Ecole Arc
Blanca Ramírez-Barat
Pierluigi Traverso Conservation-restauration
Centro Nacional de Investigaciones
CNR, Institute of Marine Sciences University of Applied Sciences
Metalúrgicas (CENIM)-CSIC
Via de Marini 6 Western Switzerland
Avda. Gregorio del Amo 8
16149 Genova, Italy Espace de l’Europe 11
28040 Madrid, Spain
[email protected] 2000 Neuchâtel, Switzerland
[email protected]
[email protected]
* Author for correspondence

Abstract
We exposed metal coupons to natural weathering for 18 months followed by Cu2Cl(OH)3 polymorphs and copper sulfates, mainly
at the Experimental Marine Station (SMS) inside Genoa Harbour. brochantite on CU. On WS a thicker corrosion layer than on
Four different compositions related to metals used in outdoor copper alloys had grown, mainly composed of iron oxyhydroxides
monuments were selected: copper (CU), ternary bronze (TB), lepidocrocite and akaganeite, with a higher corrosion rate in
quaternary bronze (QB), and weathering steel (WS). For each respect of copper alloys. The patina composition on 18 months
alloy, subsets of samples were monitored in situ for colour weathered coupons corresponds to the main composition
variation at regular intervals. To fully characterise the natural generally reported for outdoor artworks. These coupons would
urban-marine patina growth and its chemical-physical thus be useful to test the performance of treatments on complex
properties, several analytical techniques have been used. For a patina layers.
more effective comparison with patinas on metal monuments
and ornamentations, both portable Non-destructive Techniques Keywords
(NdT) and classical laboratory methods were adopted. First corrosion, natural ageing, bronze, copper, weathering
results showed a generally slower growth rate and evolution steel, X-Ray Diffraction (XRD), Electrochemical
of the properties of patinas after 12-14 months. The patina on Impedance Spectroscopy (EIS), Fourier Transform Infrared
bronzes and pure copper showed the early formation of cuprite Spectroscopy (FTIR)

Introduction and research aims

We present the experimental design and first results of surface required to compare many different parameters
an inter-laboratory research activity aimed at a deeper (Pilz 1997, Joseph 2013). Nonetheless, to recreate speci-
understanding of the properties of natural patinas, mens representing the surface structure that is the result
further development of in situ characterisation of metal of past technologies and of complex interactions with
monuments and ornamentations and an improvement the changing environments for many years may be quite
of metal conservation-restoration treatments based on difficult. However, copper, bronze and steel coupons with
clear scientific and ethical criteria. This initial charac- patinas as similar as possible to the ones commonly found
terization aims to establish the best understanding of the in outdoor monuments (Selwyn 2004) are necessary in
composition and corrosion behaviour of coupons to be order to evaluate the efficiency of novel treatments, which
used for testing corrosion protection treatments. depend also on the interaction with the patina (Otieno-
Alego 1998, Chiavari 2010). Despite extensive studies
Extensive analytical studies on conservation strategies on atmospheric corrosion, knowledge of many relevant
(e.g. cleaning and protective treatments) can be performed parts is still lacking (Odnevall 2014). To elucidate this
only on artificial coupons, due to the wide homogeneous topic, experiments on weathering of coupons in standard
2 ICOM-CC | METAL 2016 | NEW DELHI, INDIA SCULPTURE

conditions are widely used (Tidblad 2012). Their surface The surface was polished with SiC grinding paper up to
characterisation by in-situ Non destructive Techniques 1200 grit size, rinsed in deionised water and air-dried
(NdT) is not a standard practice, even though it could immediately before exposure. Two unexposed samples
provide a valuable tool in the field of cultural heritage. (3 × 3 cm) of each alloy were stored in the laboratory
In fact, it would allow a straightforward comparison as reference. Two sets composed of 16 (6 × 6 cm-de-
between the measurements performed on coupons and signed as large) and 12 (3 × 3 cm-designed as small)
those on monuments in terms of patina characterization coupons for each alloy were exposed at the ISMAR-SMS
and performance of tested treatments (Letardi 2016). site inside Genoa harbour, classified in corrosivity
category C3 according to standard (ISO 9223:1992),
Among others, electrochemical techniques have raised
with a chloride deposition rate of about 30 mg/(m2d)
a growing interest in the field of metal conservation and
(ISO 9225:2012). The samples faced south and were
EIS has proved to be an effective tool to non-destructively
positioned 45 degrees from the horizontal level (ISO
characterise the corrosion behaviour of patinas and the
8565:1992) (Figure 1).
efficiency of conservation treatments (Cano 2010, Letardi
2013, Albini 2015, Sansonetti 2015). A full exploitation of
EIS data in metal conservation is not yet well established,
especially for patina characterisation (Letardi 2007),
and a deeper multi-analytical investigation will help in
reaching that goal.

We focused our attention to the patina development

on coupons exposed outdoor in a marine-urban envi-
ronment, also considering the role of composition on
corrosion. We applied NdT characterisation techniques
to coupons, preferentially using in situ methods usually
applied on artworks. Moreover, we wanted to take advan-
tage of laboratory techniques to gain a better insight on
both the effectiveness of NdT measurements on metal
artworks and the analysis of electrochemical properties
of the patinas. Finally, we addressed the use of these
weathered coupons for the testing of treatments on
outdoor monuments. Figure 1. Exposure rack at the beginning (top) and after 14 months
exposure (bottom)
This paper presents the natural weathering exposure
program of metal coupons and the first results on their
characterisation over 18 months. The large samples were intended for future treat-
ments testing and comparison; therefore, they were
Materials and methods characterised only with NdT. The small samples were
intended for monitoring patina growth and a wider use
Coupons and weathering conditions
of analytical techniques. They were removed in pairs
Four different metal/alloy compositions were chosen: at regular intervals (1-3-6-12-18 months) in order to
characterize the corrosion layer, both with portable
• Cast copper (CU).
NdT and laboratory measurements. The large coupons
• Cast ternary bronze (TB) with nominal composition showed an almost even overall appearance after 18
Cu90/Sn8/Pb2. months weathering, with a perceivable uneven texture
at smaller scale (Figure 2a). The same appearance more
• Cast quaternary bronze (QB) with nominal compo-
or less characterised the small coupons at all weathering
sition Cu85/Sn5/Zn5/Pb5.
times (Figure 2b) with more relevant border effects,
• Weathering steel (WS) Arcelor S355J2W, EN 10025–5- which is the reason why the larger coupons should be
2004 similar to CorTen steel. adopted for treatment testing.
COPPER ALLOYS AND WEATHERING STEEL USED IN OUTDOOR MONUMENTS: WEATHERING IN AN URBAN-MARINE ENVIRONMENT 3

uated Total Reflectance (ATR) mode were recorded in the

a)
range 4000-550 cm-1 with a resolution of 4 cm-1 on Perkin
Elmer Spectrum Two™ IR spectrometers as the average
of 32 scans with Spectrum software. Thermo Scientific
Omnic software was used for post-run processing. XRD
spectra were recorded on a Rigaku Geigerflex D/max-B
series diffractometer with Cu Kα radiation in the range
b) of 7°-75° 2θ.

Corrosion behaviour was characterised by Polarisation

Resistance (Rp) and EIS measurements with a Gamry
Ref600 potentiostat with two different electrochemical
cells designed for in situ measurements (Letardi 2004,
Cano 2014, Ramírez Barat 2015). A ten-fold concentrated
artificial rain solution (Bernardi 2008, Agnoletti 2011)
was used as electrolyte; the composition is reported
in Table 1. Polarization resistance measurements were
obtained from -20 to +20 mV vs. open circuit potential
(OCP) at a scan rate of 0.167 mV/s. EIS spectra were
acquired in potentiostatic mode at OCP in the frequency
Figure 2. Typical coupons appearance after weathering: a) large samples range 100KHz-10mHz with10mV applied potential.
after 18 months; b) small samples at different exposure times
Table 1. Composition of synthetic rain used.
Characterisation techniques A solution at 1000x concentration was prepared in deionised water
and then diluted at 10x to be used as electrolyte in electrochemical
For each alloy, subsets of 3 large samples and 3 small measurements. Analytical grade salts were used
samples were monitored in situ for colour variation at Salt Concentration mg/L
regular intervals with a portable spectrophotometer CaSO4.2H20 1.443
Minolta d2600 [8 mm diameter measurement area, (NH4)2SO4 1.504
360-750nm, illuminant D65, 10° observer, UV 100%]. NH4Cl 1.915
Measurements were done using a positioning mask to NaNO3 1.513
repeat the measurement on the same points, in order CH3COONa 0.319

to minimise scatter of data due to small-scale lack of HNO3 65% Some drops of 50% solution diluted in water to
adjust pH to 5
homogeneity. The results are expressed according to the
CIE 1976 L*a*b* colour reference space: the variable L*
The small samples were analysed also with metallo-
represents lightness, while a* (red-green) and b* (yellow-
graphic techniques to fully characterise the natural
blue) are the chromatic coordinates.
urban-marine patina growth morphology on the different
A PHYNIX Surfix PRO FN Thickness Gauge was used to metal substrates. Metal samples were embedded in epoxy
measure the patina’s thickness at the end of the exposure resin and ground with SiC grinding paper up to 2000
time. The instrument was zeroed and calibrated with grit size followed by polishing with 3 and 1 μm diamond
12 μm and 51 μm thickness standard, using a freshly paste. For bare alloys characterisation, the weathering
polished unexposed sample as bare reference for each steel was etched with 2% nital solution and the copper
alloy. On each sample an average of 9 readings (5 mm alloys with ferric chloride in alcohol solution.
diameter measurement area) evenly distributed over the
Weathered sample surface was examined by scanning
whole area was acquired.
electron microscopy (SEM). The SEM micrographs
Patina composition was characterised on small samples were obtained using the secondary electrons detector
by XRD and FTIR measurements on the coupons surface, of a Hitachi S-4800 microscope, equipped with a cold-
without any sampling performed. FTIR spectra in Atten- cathode field emission electron gun.
4 ICOM-CC | METAL 2016 | NEW DELHI, INDIA SCULPTURE

Results and discussion

Copper and bronze show the characteristic casting micro-
structure (Figure 3). Copper has small and regular polyg-
onal phase-α grains about 25 μm in size; no cast shrinkage
porosity is observed. Both ternary and quaternary bronze
show as-cast microstructure with large irregular grains
of α-phase and solidification defects such as pores and
shrink cavities. Dark spots appear due to segregation of
tin surrounded by δ-phase. Small grey segregates can be
observed in QB alloy, probably lead, due to its limited
solubility in copper. WS is a hypoeutectoid steel with
very fine and equiaxial grains. Microstructure consists
of a ferrite matrix with small perlitic colonies.

Figure 4. CIELab color values as function of exposure time

Figure 3. Metallographic examination of CU (a), WS (b), TB (c) and QB (d)

Bronze coupons TB and QB are characterised by fairly

similar colour values (Figure 4); they show almost the
same colour variation upon weathering, with slightly
higher b* (tendency to yellow) for TB. Copper samples are
darker (lower L*) and more reddish (higher a* values). A
bigger colour variation than for the bronzes is measured
for CU in the first months of exposure, while after one
year the general trends of pure copper and its alloys are
quite similar. WS samples undergo a larger chromatic
variation, with the major colour changes in the first 3-6
months. For all alloys, the colour became more stable
after about 14 months of exposure.

The patina thickness of WS samples increased rapidly in

the first months (Figure 5), with a slower growth rate after
6 months which led to about 60 μm after 18months. On
CU, TB and QB samples, the patina seemed to develop
slower and patina thickness started increasing only after 6
months, with a slower growth rate after 1 year; on bronzes
the patina thickness after 18 months reached about 5 μm Figure 5. Patina thickness as function of exposure time; ( top) all the four
while on copper it was just about 3 μm. alloys considered; (bottom) detail for copper and copper alloys
COPPER ALLOYS AND WEATHERING STEEL USED IN OUTDOOR MONUMENTS: WEATHERING IN AN URBAN-MARINE ENVIRONMENT 5

ATR-FTIR measurements for CU samples (Figure 6a)

reveal the gradual formation of copper hydroxychlorides
Cu2Cl(OH)3 with characteristic vibrational bands in the
3450-3320 cm-1 and 990-820 cm-1 regions. Also, copper
phosphates (cornetite, libethenite, and pseudomalachite)
were observed at 637, 613 cm-1 after 1 month of exposure
but their presence decreased thereafter. On the contrary,
the presence of some copper hydroxysulfates, in particular
brochantite, was ascertained and slightly increased with
time (3589, 3567, 1121, 1113, 1101, 872, 782, 739, 642,
625, 600 cm-1). Traces of Nantokite (804, 787 and 703 cm-1)
could also be present along the exposure time. TB and QB
samples were characterized by a similar patina composi-
tion with the formation of copper hydroxychlorides and
copper phosphates (as for CU samples). Nantokite was
slightly visible on QB samples but not on TB samples
(maybe due to a concentration lower than the detection
limit of the FTIR spectrometer). Moreover, we observed
mixed basic lead carbonate/sulfate minerals leadhillite
and hydrocerusite (1392, 1097, 1046, 840, 684 cm-1) that
gradually disappeared in favour of the formation of copper
hydroxysulfates, such as brochantite. (Figures 6-b and
6-c). On WS samples, the presence of iron oxyhydrox-
ides, such as lepidocrocite (L) and possibly goethite (G)
and akaganeite (A), was observed (1148 (L), 1092 (A),
1021 (L), 903 (G), 891 (L), 806 (G), 788 (L/A), 744 (L)
and 690-670 (G/A) cm-1), as mentioned in the literature
(Raman et al 1991, Thickett 2004), (data not shown).

XRD spectra on CU, TB and QB are dominated by metal

peaks for 2θ greater than 41, while corrosion products
peaks ranges mainly at lower 2θ; all measurements
show the early formation of cuprite and its continued
growth during weathering. As already mentioned for
FTIR results, several Cu2Cl(OH)3 polymorphs (ataca-
mite, botallackite, clinoatacamite) can be identified; the Figure 6. ATR-FTIR spectra recorded after 1, 3, 6, 12 and 18 months of
monoclinic form(s) (Jambor 1996) can be recognised exposure on a) copper, b) ternary bronze and c) quaternary bronze
coupons. Upward arrows: peaks from copper hydroxychlorides;
from the first months, while atacamite is clearly visible
downward arrows: peaks from copper phosphates, and (b,c only) lead
from 6-12 months onward on CU, TB - QB; a small peak mixed carbonate-sulfate minerals
from nantokite is generally present. Copper sulfates are
much better identified on CU, where brochantite peaks dependent on exposure time. On WS coupons, which
are clearly visible at 18 months (Figure 7) along with are characterised by a thicker rust layer, peaks from the
posnjakite in the first months of exposure, while antlerite underlying metal disappeared after 1 month (Figure 8);
(A) may be recognised on TB and QB. Copper phosphates the rust layer is known to be composed of a large amount
cannot be clearly identified on CU, while libethenite may of X-ray amorphous substances (Yamashita 1998) which,
be identified on alloys along with cornetite on TB and along with a wide distribution of particle sizes, give rise to
pseudomalachite on QB at longer exposure times. On non-intense and well-defined Bragg peaks; lepidocrocite
QB lead carbonate hydrocerussite is clearly identified is clearly identified in all XRD spectra on WS coupons,
after 1 month exposure with intensity of peaks not very with traces of akaganeite; identification of goethite is not
6 ICOM-CC | METAL 2016 | NEW DELHI, INDIA SCULPTURE

obvious for any of the samples; however, magnetite and/ The mixed composition of cuprite with copper hydrox-
or maghemite (Yamashita 1998) may be present. ychlorides (atacamite, clinoatacamite) and hydrox-
ysulfates (brochantite, antlerite) on copper alloys
Although the main compounds identified by ATR-FTIR
coupons and the mixed iron oxyhydroxides, including
and back-reflection XRD are the same, some differences
akaganeite, on WS coupons after 18 months exposure
may be seen, such as the identification of lead carbonate
corresponds to the main components of the patina
on QB samples for different exposure times. We suggest
generally reported for outdoor monuments (Selwyn
this can be linked to the different penetration depth of
2004, Aramendia 2011), when chloride pollution is
ATR-FTIR (0.3-3 μm) compared to XRD (2-120 μm)
present. The large coupons weathered for 18 months
with respect to the patina growth. This issue is of rele-
would thus be useful to test treatment performance on
vance for in situ characterisation of monuments. Further
complex patina layers.
investigations are in progress.

Figure 9. (a) Low frequency Impedance module and (b) Polarisation

Resistance Rp as function of exposure time

Preliminary values of |Z|10mHz and Rp obtained (Figure 9)

show a similar behaviour, especially for copper alloys.
Some discrepancies are clearly visible, mainly for WS.
As is well known, especially in the case of bare metals, a
lower frequency may be required for |Z| to approximately
equal the Polarisation Resistance. A deeper analysis of
electrochemical measurements is in progress for better
Figure 7. XRD spectra on CU, TB, QB after 18 months exposure Copper
oxide cuprite: black arrows; copper chlorides: clinoatacamite (CA), exploitation of the results. Nonetheless, we can gener-
atacamite (AT), nantokite (NT), botallakite (BT); copper sulfates: ally observe a higher corrosion rate for WS than copper
brochantite (BR), antlerite (AN), posnjakite (PN); copper phosphates: alloys in the marine environment selected. As expected,
libethenite (LT), cornetite (CN), pseudomalachite (PM); lead carbonate:
data also show a lowering trend of corrosion rate with
hydrocerussite (HC)
increased weathering time, which is more marked for
copper alloys than for WS and in the first 9-12 months.
For longer weathering time, copper alloys are charac-
terised by |Z|10mHz of the order of 100KΩcm2 as the one
measured on outdoor bronze monuments (Sansonetti
2015, Letardi 2016).

SEM (Figure 10) on the surface of CU samples show a

thin layer of fine grained corrosion products at 1 month
which can be associated to the early formation of cuprite.
After 6 months, this layer grows in an irregular pattern.
At 18 months, the corrosion products layer seems thicker
Figure 8. XRD spectra on WS at different weathering time without clearly defined crystals. TB and QB show similar
COPPER ALLOYS AND WEATHERING STEEL USED IN OUTDOOR MONUMENTS: WEATHERING IN AN URBAN-MARINE ENVIRONMENT 7

–– the non-destructive characterisation of patina thick-

ness and composition without scraping from surfaces
along with laboratory measurements on metallo-
graphic sections can provide relevant information for
in-situ diagnostic measurements.

Through the completion of planned measurements, the

overall analysis of experimental data and an informed
dialogue between conservators and scientists, we can
glimpse an improvement in metal conservation-res-
toration methodologies based on clear scientific and
ethical criteria.

Acknowledgements
This work was partially supported by the European Union
Seventh Framework Programme (FP7/2007-2013) under
Figure 10. SEM microphotographs at 1000x magnification on the surface
grant agreement n° 262584 JERICO-TNA (end user
of 1, 6 and 18 months exposure (from left to right) of CU, TB, QB and WS agreement n° 13/1210589/BF, 2013-2015), CREMEL
(top to bottom) samples project (HAR2011-22402) and the pre-doctoral FPI
grant BES-2012-052716 funded by the Spanish Ministry
features, with thin irregular crusts of corrosion prod-
of Science and Innovation.
ucts visible from the first month. These crusts thicken
and form coarser aggregates with time. Thin cracks are
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Yamashita, M., H. Nagano, T. Misawa and H.E. Townsend. Emilio Cano is Tenured Scientist at the Centro Nacional
1998. Structure of Protective Rust Layers Formed on de Investigaciones Metalúrgicas (CENIM)-CSIC in
Weathering Steels by Long-term Exposure in the Indus- Madrid, Spain. He obtained his PhD in Fine Arts from
trial Atmospheres of Japan and North America. ISIJ the Complutense University of Madrid in 2001. His
International 38: 285-290. fields of expertise include corrosion and protection of
metallic cultural heritage, indoor corrosion, electro-
Authors chemical techniques applied to conservation science, XPS
and corrosion inhibitors. He has published more than
Paola Letardi has a degree in Physics and worked in the
100 research papers in international scientific journals
field of Material Science and Surface Spectroscopy, with
and presented communications to about 60 scientific
particular interest in the development of methodologies
conferences, both in corrosion science and conservation
and instrumentation. She has been active in national and
science. He is Assistant Coordinator of the ICOM-CC
international projects on diagnostics and monitoring for
Metals Working Group.
the Conservation of Cultural Heritage. Her research is
focused on the study of corrosion of metals in the marine Edith Joseph is a project leader at the University of
environment and on specific applications of electrochem- Neuchâtel and the University of Applied Sciences ARC
ical and spectroscopic techniques in the field of artifacts Conservation-restoration (Neuchâtel, CH). In 2009, she
of historical interest. obtained a PhD degree in chemistry from the University
of Bologna (Italy). Her main research activities are the
Blanca Ramírez-Barat has a degree in Chemistry
application of spectroscopic techniques for the char-
and in Fine Arts, both from the Complutense Univer-
acterization of artistic and archaeological objects. The
sity of Madrid, and an MSc in Materials Science and
characterization of heterogeneous matrixes and the
Engineering from Carlos III University. After several
interaction between organic substances and inorganic
years in R&D management, she has joined the research
compounds, in particular microorganism-metals, are
group “Corrosion and protection of metal in cultural
some of her research interests. She is author of more than
heritage” at the CENIM-CSIC. She is currently working
40 papers published in international journals and books,
in the development of an electrochemical cell for in-situ
related to analytical chemistry and conservation science.
diagnose of metallic cultural heritage.
Monica Albini received an MSc degree in Science
applied to Cultural Heritage from the University of
Rome “Sapienza” (Italy) in 2010. After collaborations
with Italian institutions and museums in the field of
archaeometry and diagnostic of metallic artefacts, she
has joined the Laboratory of Microbiology of the Univer-
sity of Neuchâtel (Switzerland) as PhD student. Her
research is currently focused on biotechnology applied
to the development of new conservation treatments for
copper-based alloys.
Pierluigi Traverso graduated in Industrial Chemistry
from the University of Genoa (Italy) in 1989. Since
2001, he was a researcher at CNR-ISMAR. His research
is focused on the study of corrosion and protection of
metals in various natural and anthropogenic aggres-
sive environments. He gained experience in research
and service analysis with industrial partners that have
promoted the development of technologically advanced
products. His expertise in experimental measurements
is related to electrochemistry, microscopy, analytical
chemistry and different spectroscopy.