Natural and artificial ageing of protective coatings for outdoor bronzes

protection

Sara GOIDANICH1, Chiara PETITI1, Barbara SALVADORI2, Andrea CAGNINI3,

Monica GALEOTTI3, Simone PORCINAI3, Antonello VICENZO1, Edoardo
GUERRINI4, Stefano TRASATTI4, Davide GULOTTA1
1
Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico
di Milano, Milan, Italy, sara.goidanich@polimi.it; chiara.petiti@polimi.it;
antonello.vicenzo@polimi.it; davide.gulotta@polimi.it
2
Institute for the Conservation and Valorization of Cultural Heritage, National Research
Council, Sesto Fiorentino, Italy, salvadori@icvbc.cnr.it
3
Opificio delle Pietre Dure, Florence, Italy, andrea.cagnini@beniculturali.it;
monica.galeotti@polimi.it; simone.porcinai@beniculturali.it
4
Department of Chemistry, Università degli Studi di Milano, Milan, Italy,
stefano.trasatti@unimi.it; edoardo.guerrini@unimi.it

Abstract
Any protective treatment for cultural heritage applications should fulfil specific requirements. Besides
being transparent and colourless, they should be chemically and physically resistant to the degradation
agents, possibly not toxic and removable without altering the underling patina and metallic substrate.
For a better efficacy, protective coatings can be applied in association with corrosion inhibitors. A
crucial issue in the evaluation of new products is related to their long-term performances. Typically, this
aspect is investigated through accelerated ageing tests. However, these procedures seldom fully
represent the complexity of real exposures. Thus, when possible despite the long time required, it is
advisable to perform also natural ageing.
This research was aimed to investigate and compare the long-term efficacy of traditional and innovative
coatings for outdoor bronze surfaces. Coatings were applied in single, double and triple layer and in
combination, through blend or pre-treatment, with corrosion inhibitors. The different treatments were
applied on both patinated and non-patinated bronze specimens. The characterisation of the different
treatments immediately after application was performed and reported on a previous work. [1]
A multi-analytical approach was adopted for the study of the long-term behaviour of the different tested
treatments, including colorimetric, SEM-EDX, FTIR, LPR and EIS measurements.
Natural and artificial ageing have been compared in order to investigate whether the artificial ageing
process could be considered representative of the real effect of outdoor exposure.

Keywords Natural and artificial ageing; outdoor bronzes; corrosion inhibitors; coatings; long-term
efficacy

Introduction
Bronze is one of the most common metallic materials employed in cultural heritage, and in
particular, a large number of bronze sculptures are exposed in outdoor environment. Therefore,
prevention and control of bronze corrosion is a crucial issue in conservation of metallic
artefacts, especially in aggressive environments as outdoor urban or marine ones. A commonly
adopted way to protect outdoor metallic artefacts is to apply protective systems constituted by
coatings that may also be coupled with corrosion inhibitors.
Waxes and acrylic resins-based coatings are diffusely employed, in association with
benzotriazole (BTA) as corrosion inhibitor. However, some criticalities of BTA have been
highlighted, mainly related to its toxicity [2–4] and its scarce stability and permanence on
treated surfaces [5–8], with risk for environment and for operators or visitors. There is, thus,
the need of studying innovative protective systems in combination with non toxic and “green”
inhibitors. The assessment of the long-term efficacy of new products for conservation is clearly

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a crucial issue because the different treatments cannot be tested on objects with artistic or
historical value since the risk to damage them would not be acceptable. For this reason,
protective treatments are typically tested on laboratory specimens. In this case, the surface
condition of the specimens before the application of coatings or inhibitors becomes crucial since
it may significantly influence the obtained results [9,10]. Patination techniques [9,11–13] and
accelerated ageing procedures [10,13–15] are therefore used to reproduce surface condition
similar to the ones of real objects. A first screening of products is normally based on the
characterisation and study of their properties just after application. Accelerated ageing tests are
then normally used to study the long-term performance of the best performing treatments.
Unfortunately natural ageing is extremely time-consuming and rarely can be applied.
The available standards for accelerated ageing procedures for industrial application [16–19] are
too aggressive to be representative of the conditions to which objects with an artistic or historic
value are exposed. In literature, different accelerate ageing procedures for the cultural heritage
field have been proposed, such as wet and dry techniques with synthetic rain [9,11,20–23] and
climatic chamber with UV exposure [24]. The last one, in particular, has been especially
proposed for the study of the degradation of organic coatings. Such kind of tests are the most
reliable tool available so far for the study and screening of new products and are therefore
frequently used to test and select the best performing treatments to be applied on the real
artefacts. However, the complexity of real exposure cannot be completely reproduced in the
laboratory under accelerating test conditions. It is therefore of great importance to compare the
results of accelerated and natural ageing.
The aim of this work was the long-term evaluation of a series of protective treatments, that were
characterised on a previous study [1], and the comparison of natural ageing in urban conditions
with two different accelerated ageing procedures in solar box and by exposure to artificial rain,
respectively. The natural ageing consisted in two-year exposure in the city of Milan. Both
artificially patinated and not patinated specimens were used for this study.

Materials and methods

Specimens and protective systems

The bronze specimens (size 5 cm x 5 cm x 0.5 cm or 5 cm x 2.5 cm x 0.5 cm) were cast ingots
of a quaternary bronze alloy with the composition reported in Table 1, detected with EDS
analysis [1]. A set of specimens was artificially patinated with a procedure described on a
previous work [1], allowing to simulate the natural patina of outdoor bronzes [25-26], mainly
constituted by atacamite [Cu2Cl(OH)3] and antlerite [Cu3SO4(OH)4].

Table 1 - Composition of bronze alloy

Cu  Sn  Pb  Zn  Other elements (Ni, Fe…) 
88.3%  5.7%  1.6%  3.9%  <1% 

The main characteristics of the different products are noted here while a more detailed
description and the methodology of application is reported in [1]. The coatings were selected
among commercial products either commonly used by conservators or developed for other
applications and considered suitable for bronze conservation. The tested coatings, their
labelling, their combinations with corrosion inhibitors, the surface condition of specimens and
the ageing procedures are summarized in Table 2. The commercial tested products are: Reswax
WH is a mixture of microcrystalline and polyethylene waxes; Soter wax is a BTA-containing
natural crystalline wax (Bresciani, Milan, Italy); Fluoline HY is a fluorinated elastomer (CTS,
Florence, Italy); Silres BS 290 is a polysiloxane (Wacker Chemie AG); Incral 44 is a BTA-
containing (0.3 %) toluene solution of ethyl acrylate/methyl methacrylate copolymer (CTS,

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Florence, Italy). In addition, an innovative end-capped poly(lactic acid)s with a BTA moiety
(PF) [27] was tested. For comparative purposes, a solution containing polylactic acid PLA and
BTA (PM) was used. The BTA content was the same as in the commercial product Incral 44.
Benzotriazole (BTA) was selected as reference inhibitor to be compared with the less toxic
inhibitors 2-mercaptobenzoxazole (ME), sodium oleate (OL) and tolyltriazole (TT).

In Table 2 the combination of the protective treatment and the ageing procedure adopted are
also reported.

Table 2 - Coatings and corrosion inhibitors employed and their combination

Protective coating Pre-treatment with corrosion inhibitors

Sodium oleate
Benzotriazole

benzoxazole
No inhibitor

2-mercapto-

Tolytriazole
Labeling

(BTA)

(ME)
(OL)

(TT)
Product Description

-- -- NT ● ○ □ X         
Reswax WH Wax WR ● ○ □ X  ● ○ □  ● ○ □  ● ○ □  ● ○ □ 
Soter Wax WS ● ○ □ X  ● ○ □       
Fluoline HY Fluoropolymer FL ● ○ □ X  ● ○ □  ● ○ □  ● ○ □   
BTA containing
BTA-PLA PF ● ○ □ X         
Polylactic acid
Blend BTA- Polylactic acid
PM ● ○ □ X         
PLA blended with BTA
Silres BS 290 Polysiloxane SI ● ○ □  ● ○ □       
Incral 44 + Double-layered
DL ● ○ □ X  ● ○ □       
Soter protective coating
Soter + Incral Triple-layered
TL ● ○ □ X         
44 + Soter protective coating
○ = Not patinated, naturally aged
● = Patinated, naturally aged
□ = Not patinated, Solar box ageing
X = Patinated, Artificial rain ageing

Ageing procedures
Three different types of ageing procedures were employed.
Natural ageing. The natural ageing procedure consisted in exposing the specimens at 45° from
the horizontal, facing south in Milan, Italy, for two years
Artificial rain. This is an accelerated ageing procedure during which one set of specimens was
exposed to thermo-hygrometric variations in an Angelantoni Challenge 500 climatic chamber,
where temperature and relative humidity changed according to 50 cycles #1 followed by 60
cycles #2, as reported in Table 3. Since no effect was observed either on coated and uncoated
specimens, after a total of 110 cycles an additional wet/dry procedure was applied to simulate
a cyclic exposure to stagnant rain [20]. The ageing technique consisted of wetting and drying
cycles where the specimens were periodically dipped in artificial rain (Table 4): 240-minute
immersion, 60-minute drying. Each cycle was performed at room temperature and RH = 40-60.
The pH was kept at values between 4 and 5 acidifying with HNO3. This interval was chosen
taking into account the typical values of pH in european urban atmosphere [28]. A total of 60
cycles wet/dry was performed.

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 Table 3 - Thermo-hygrometric cycles employed in climatic chamber.
T (°C) RH (%) Time (min)
0 85 60
10 85 60
20 65 60
40 45 60

50 cycles
60 30 60
#1

40 45 60
20 65 60
10 85 60
0 85 60
0 80 90
60 cycles

30 80 90
#2

60 30 90
T: Temperature; RH: Relative humidity, Heating rate: 1 °C/min.

Table 4 - Composition of the synthetic rain used for Wet/Dry cycles.

Salt Concentration (mg/l) Concentration (mol/l)
CaSO42H2O 14.4 8.410-5
(NH4)2SO4 15.0 1.110-4
(NH4)2Cl 19.1 3.510-4
NaNO3 15.1 1.810-4
CH3COONa 3.2 3.910-5

Solar box accelerated ageing. A third set of specimens was subjected to accelerated,
photochemical ageing up to 965 h using a Solar Box CO.FO.ME.GRA model 3000e equipped
with a Xenon-arc lamp and an outdoor type UV filter with cut-off <290 nm to eliminate
radiation not present in the external sunlight. According to the ISO 1134/2004 protocol [29],
irradiance was kept at 500 W/m2 and black standard temperature (BST) at 65±2 ◦C.

Electrochemical techniques
The evaluation of the protective performance of the coatings was carried out by means of
electrochemical measurements. Polarisation Resistance (Rp) was obtained by Linear
Polarization Resistance (LPR) and Electrochemical Impedance Spectroscopy (EIS).
Measurements were performed using a contact probe similar to the one developed by Letardi
and co-authors [30–33] for in situ measurements and a portable potenziostat Ivium
Technologies CompactStat. The probe consists in concentric AISI 316 stainless steel counter
and reference electrodes embedded in a PTFE housing. Oligo-mineral water was used as
electrolyte. The contact between the probe and the working electrode is made through a cloth
soaked with the electrolyte. Linear polarization measurements were performed by scanning the
working electrode potential ±0.01 V about the open circuit potential (i.e., corrosion potential,
Ecorr) at a scan rate of 0.6 V/h. Electrochemical impedance spectroscopy (EIS) measurements
were performed at the open circuit potential using a 10 mV excitation signal, in the frequency
range from 100 kHz to 10 mHz. Ivium® software was employed for both LPR and EIS data
acquisitions and elaboration.

4
Rp was determined from EIS measurements as the difference of the absolute impedance, |Z|, at
the lowest and highest frequencies [34]. For technical reasons, only some preliminary
measurements could be performed just after ageing. All samples were therefore kept for several
months in the laboratory before performing a complete electrochemical characterisation after
ageing. At least three measurements were performed per each specimen. The reported values
are the average between all the Rp obtained per each samples by LPR and EIS.

Results and discussion

Bronze surfaces, when exposed to the atmosphere, are expected to form a patina of corrosion
layers that may provide protection against corrosion. Both patinated and not patinated
specimens were subjected to natural ageing for 2 years in Milan. An additional set of not
patinated specimens was subjected to photochemical aging in solar box while another set of
patinated specimens was exposed to artificial aging (climatic chamber followed by wet/dry
cycles). The urban exposure in Milan led to the formation of a quite thick black patina on both
patinated and not patinated untreated samples (Fig. 1). The greenish patina originally present
on the patinated specimen is not any more visible. The artificial patina was apparently partially
removed or transformed by the artificial rain that also favoured the growth of new corrosion
products, even though in lower amount, if compared to the urban exposure. As expected, the
solar box led to the formation of a very thin patina of corrosion products on the surface. This
ageing procedure, indeed, is mainly aimed at evaluating the stability of organic coatings when
exposed to solar light, rather than to induce corrosion.
In order to evaluate the level of protection provided by the patina formed under the different
ageing procedures, LPR and EIS measurements were performed. The reported Rp values,
inversely correlated to corrosion rate, are the average of the LPR and EIS measurements. The
Rp values, after ageing and several months of storage in the laboratory, were in general higher
than the preliminary ones measured just after ageing, suggesting that the storage in the
laboratory had favoured the formation of a more protective patina.
As it can be observed in Fig. 1, the natural exposure to the urban environment of Milan,
followed by the storage period in the laboratory, led to a significant reduction of corrosion rate
suggesting that a stable, compact and protective patina was formed. Before exposure, the
patinated sample presented slightly higher Rp values compared to the not patinated ones, while
after natural ageing the situation is reversed, suggesting that the presence of the artificial patina
did not favour the formation of a more protective patina.
Apparently the weathering in artificial rain did not allow the formation of protective corrosion
layers, since the Rp values are quite close to the ones obtained before exposure. This may be
due to the low pH of the artificial rain [20,21] that led to the consumption of most of the original
patina.

5
  
 
 
 

Fig. 1 – Effect of the different ageing procedures on not patinated (A solar box; B natural
ageing) and patinated (C natural ageing; D artificial rain) not treated specimens

As it can be observed in Fig. 2, the formation of corrosion products was significantly reduced
by all protective treatments during the two years of exposure in Milan. However, the protection
was not complete since all samples darkened due to the formation of corrosion products.
It is important to verify how much of the initial protection remains and if the products showing
the best performances after application [1] are still the ones providing the highest protection
against corrosion.

Fig. 2 – Picture of all the aged samples: not patinated aged in solar box and by natural
ageing: patinated aged with artificial rain and by natural ageing
The previously obtained results [1] are recalled in Fig. 3 and can be summarised saying that all
the artificially patinated samples presented higher Rp than not patinated ones, suggesting that,
before ageing, this patina provided an additional protection. In general, all the inhibitors led to
a decrease of corrosion rate even though the inhibition efficiencies were not very high. The
efficacy of the different coatings can be summarised as follows:
SI> TL>>DL>PM>PF>WS>>WR≈FL≈NT
The SI coating and the ME inhibitors were discarded since they caused an inacceptable colour
alteration of the specimens.

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 Fig. 3 – Polarisation Resistance of not patinated and patinated specimens before ageing
After natural ageing, the efficacy of all protective treatments is dramatically reduced, while the
not treated samples have formed a protective patina that at the time of the Rp measurements
appears to provide a better protection against corrosion than most of the coatings.

Fig. 4 - -Polarisation Resistance after natural ageing of not patinated and patinated
specimens
In some cases, not patinated samples present higher Rp than the patinated ones; in other cases
the situation is reversed.
The SI coating, that was the best performing one before ageing, is now providing moderate
additional protection only on patinated specimens, while the not patinated ones present Rp
values lower than the not treated samples.
In the case of not patinated specimens, the only two treatments that provide some residual
protection compared to the not treated sample are the DL_BTA and the TL, confirming that the
protection of a not patinated surface is challenging. In the case of patinated samples also PM,
that performs better than PF, presents some residual efficacy, suggesting that apparently the
BTA performs better when blended.
The BTA pre-treatment just slightly improved the performance of the coatings. The alternative
less toxic inhibitors perform or similarly to BTA or even better. Unfortunately, the one that
presents the highest efficacy is ME, that was discarded for the high colour variation. Based on
the obtained results, the most promising alternative inhibitor seems to be OL.

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 Fig. 5 – Comparison of natural and solar box ageing on not patinated specimens
The solar box ageing resulted significantly more aggressive than the 2 years exposure for WR.
Among the waxes WS, which contains BTA, resists better to solar box exposure. In general all
the products that were applied after a BTA pre-treatment resist better than the ones without it,
confirming the capacity of BTA to stabilise protective coatings against UV-Visible
deterioration [35,36]. Apparently ME, OL and TT do not present the same capacity. SI, DL and
TL seem to resist better to solar box ageing than to natural exposure in urban environment.
For the weathering with artificial rain, only specimens without pre-treatment with inhibitors
were tested. As it can be observed in Fig. 6, in some cases (NT, WR, FL and PF) the artificial
rain was significantly more aggressive than the natural ageing, while it resulted slightly less
aggressive in the case of WS-containing coatings: WS, DL and TL. The higher deterioration
under artificial rain weathering may be ascribed to a higher rain aggressivity compared to the
natural exposure, that apparently affects more some products than the other ones. The lack of
solar exposure should be always considered when evaluating an artificial rain exposure.

Fig. 6 - Comparison of natural and artificial rain weathering on patinated specimens

Conclusions

The results of the different natural and accelerated ageing procedures confirm the importance
of ageing procedure for the selection of protective treatments, since in some cases the best
performing treatment in terms of corrosion protection before and after ageing may not be the
same.
Accelerated tests provide valuable information about the long-term behaviour of the treatments.
However, solar box or weathering with artificial rain alone cannot substitute natural ageing that
remains a fundamental and time consuming final step for the study of protective treatments.

8
Further tests are required to verify if a combination of the two may provide a better accelerated
simulation of a real exposure. Among the tested inhibitors, sodium oleate (OL) looks to be a
promising candidate to substitute BTA since it is definitely less toxic and it performs similarly
or slightly better. Further investigation are required with different surface conditions in order
to confirm it.

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