AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·115

Testing New Coating Systems for the Protection

of Metal Collections Exposed
in Uncontrolled Museum Environment
Amalia Siatou, Vasilike Argyropoulos, Dimitrios Charalambous,
Kyriaki Polikreti and Agathi Kaminari
Technological Educational Institute (TEI) of Athens
Department of Conservation of Antiquities and Works of Art
Ag. Spyridonos, 12210, Aigaleo, GREECE
Phone, fax: (+30) 2105385459
e-mail: bessie@teiath.gr

The paper describes an evaluation of the performance of environmental friendly coatings and coating
systems (i.e., with corrosion inhibitor additives), for the protection of museum copper and iron alloy ob-
jects. The protective ability of the six best performing coating systems was tested on corroded copper
and iron alloy coupons. Accelerated aging in a climatic chamber and visual examination, using optical
and SEM observation as well as colorimetry, were used to rate them. Varying results were found ac-
cording to each metal. In general Poligen® ES 91009 (aqueous wax emulsion-BASF), with or without
corrosion inhibitor (CI) additives protects better iron alloy coupons as opposed to Paraloid® B-72. The
improvement of Paraloid® B-72, a coating commonly used in conservation, by adding CI additives is al-
so discussed. However, the preliminary results for copper alloy coupons were similar for all coatings.

Keywords: Metal Protection, Coatings, Corrosion Inhibitor Additives, Uncontrolled Indoor Environment

1. INTRODUCTION
The conservation literature has documented well the
problems associated with coating failure, and the damage
that results to metal objects [1,2]. The best option would be
to avoid coating museum metal objects and to simply store
them in a controlled environment. However, a survey of
the environmental conditions of 23 Greek Museums found
that only one third of them have controlled environment in
terms of Relative Humidity (RH) and Temperature (T), in
storage and/or exhibition rooms [3, 4]. Thus, when metal
objects from a collection are treated, conservators believe
that the object’s best hope for survival is the use of a coat-
ing and/or corrosion inhibitor.
As part of the European research project funded by the
6th Framework (INCO), “PROMET”, the Metals Conser-
vation laboratory at the Technological Educational Insti-
tute (TEI) of Athens, is conducting research into the test-
ing of new coatings and/or coating systems for the long-
term protection of copper and iron alloy historical objects.
The coating systems are either new coatings, such as Poli-
gen® ES 91009, or traditionally used ones, such as Par-
aloid® B-72 to which corrosion inhibitors (CI) are added
for improving their protective ability.
2. BACKGROUND
Protective coatings form barrier films that prevent ei-
ther chemical compounds or corrosion current from com-
115
ing in contact with the metal substrate [5,6]. Whereas, CIs
are namely chemical compounds that when added to a so-
lution in contact with a metal; interact with the metal sur-
face reducing its corrosion rate [7]. However, apart from
adding CIs to a solution, they may be also added to the
coating itself to help improve its properties [7-8].
To protect metal objects, conservators usually use ma-
terials such as coatings made up of acrylic resins and/or
synthetic waxes [9]. Furthermore, CIs are applied to iron
and copper alloys as part of a stabilization treatment [10].
3. COATING SELECTION
Our market survey was focused on testing, commercial-
ly available non-toxic CI additives that would be added to
coatings already in use by conservators (i.e., waxes and/or
acrylic resins) and non-toxic, biodegradable, ready-to-use
inhibiting coatings. During our research, we also came
across a very promising product, the ready-to-use liquid
polyethylene wax with the trade name: Poligen® ES 91009
(BASF), the synergistic use of CI additives to this coating is
also discussed.
All new products tested derive from major coating and
corrosion inhibitor manufacturers namely: BASF (Poli-
gen® ES 91009) an international Chemical Company [11],
Cortec Co. (M370, M235, M435) a world leader in innova-
tive corrosion protection solutions [12], and DOW (Alka-
terge T) also an international Chemical Company [13].
AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·116
A. Siatou et al.
More than 35 coatings and coating systems developed
for metals industry were selected for further testing. Ease
of application, tackiness and aesthetic appearance were
the criteria tested on clean brass substrates to determine
the most appropriate coatings for our conservation re-
search. 12 coatings and combinations were rated “good or
excellent” and from this list 6 were selected as the most
promising ones (see Table 1) for further testing using ac-
celerated aging. Most of the new coatings tested are meant
for temporary protection of new metal structures in indus-
try and automotives; therefore their applicability and per-
formance on corroded surfaces needs to be determined.
Part of the results of the coating evaluation is present-
ed in this paper and some are still forthcoming. However,
our evaluation will lead to the selection of the 3 most ap-
propriate coatings for further testing on coupons under re-
al museum conditions for one year interval, and as well as
on real copper and iron alloy historical objects.
The products that are described in this paper consists
of Paraloid® B-72 (reference coating), the most common-
ly used coating by conservators [9]; a new ready-to-use liq-
uid wax, Poligen® ES 91009; and five coating systems, i.e.
Poligen® ES 91009 or Paraloid® B-72 with a CI additive.
4. THE SUBSTRATES
Metal coupons, with dimensions 50 x 75 x 0.8mm, simu-
lating the composition and corrosion of historic copper
and iron alloy objects, manufactured by the PROMET
partners, SVUOM Ltd. and Heritage Malta respectively,
were used as substrates for testing the different coating sys-
tems. Pure copper sheets with the same dimensions were
also used for comparative reasons. The chemical and min-
eralogical composition of the coupons is given in “Table
2”. The different substrates, with a total number of 94
coupons, are divided into the following categories:
— Group 1: Pure copper sheets (purchased by TEI)
— Group 2: Corroded bronze alloy prepared by SVUOM
— Group 3: Corroded iron alloy prepared by HM
5. EXPERIMENTAL PART
For comparative reasons, a common methodology for
preparing, testing and evaluating coatings was decided to
be followed by all partners within the consortium. After re-
peated discussion and a literature survey, the partners of
PROMET concluded that the methodology of preparation
of the object before coating application and the application
of the coating itself are considered common sense among
conservators. Furthermore, ISO and ASTM standards for
testing and evaluating coatings on metal substrates refer to
clean metal substrates and all preparation methodology
necessitates metal stripping before coating application [14,
15]. Additionally, ISO or ASTM standards describing the
accelerated aging of metal substrates covered with organic
coatings refer mostly to outdoor conditions.
This led the PROMET partners in creating our own
116
manuals applicable within the consortium, which deter-
mined a common methodology for the coupons prepara-
tion and the coating application and as well the perfor-
mance of accelerated corrosion tests. The methodology de-
scribed below summarizes these manuals.
5.1 Coupons Preparation
Since the coupons simulated real historical objects,
they must be treated according to common conservation
practices and by professional conservators.
The first step was to remove loose corrosion products
from the surface of the coupons without destroying the ar-
tificially created patina. Thus, cleaning to the bare metal
surface was avoided. Cleaning was undertaken by mechan-
ical means (i.e. rotating drills and scalpels). The iron alloy
coupons were cleaned by our Maltese partner (HM) and
the bronze alloy coupons by TEI. For Group 1, no cleaning
prior to degreasing was necessary. Removal of grease
caused by handling was carried out for all coupons using
acetone. After cleaning and degreasing, removal of any
possible moisture in the corrosion products in groups 2 & 3
was removed by placing the coupons in a furnace at 110 oC
for two hours. All coatings are meant for cold application
therefore the coupons were stored in a dry cabinet with sil-
ica gel until their temperature was stabilized in normal
conditions (20-25 oC & 50-55% RH) prior to coating.
5.2 Coating Preparation and Application
The preparation of the coatings is described in “Table
3”. All coatings were applied cold as a liquid. The CI addi-
tives were added to the liquid coating and were stirred until
dilution.
Application by immersion was selected for all coatings.
After discussion amongst the PROMET partners, this
method of application is the most appropriate for testing
the coatings themselves since it ensures a uniform and con-
tinuous film. Therefore, each coupon was immersed in the
coating for 5 minutes, and was left to dry in the fume hood
for 24 hours. During immersion, the coupons were placed
with an inclination of 20 degrees to the vertical in a beaker
and were totally covered by the coating. The beaker was
covered, with a glass dish, in order to minimize evapora-
tion of the solvent. All handling was performed with clean
talc free gloves and tongs. After immersion, the coupons
were placed horizontally in order to ensure even film for-
mation. To create aeration on the back side of the coupon,
each coupon was placed on two small ceramic bases (trian-
gular, 4x4x10mm, to minimize the contact point) and was
left to dry.
5.3 Accelerated Aging
Accelerated corrosion tests were carried out so as to
provide a quick preliminary evaluation according to the
corrosion environment in which real artefacts are exposed.
The coatings selected by TEI are intended for historical
objects cleaned according to conservation standards,
where the final object’s surface has thin layers of corrosion
AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·117

Testing new coating systems for the protection of metal collections exposed in uncontrolled museum environment

products, and exposed to an uncontrolled indoor museum 6.1 Colour Measurements

environment. Thus, it was decided to use mild corrosion
conditions by applying humid-dry cycles without any addi-
tional contaminants, such as sulphur or chlorides.
Again, according to the manuals created by the PRO-
MET partners, coated and uncoated coupons were placed
in a climatic chamber while control coupons of each cate-
gory where stored under stable conditions (in terms of RH
and T) for comparative reasons.
During accelerated aging, the coupons were placed,
per group, on racks made of Plexiglas with an inclination
20 -30 degrees to the vertical. The racks were then placed
in a Vöetsch Industrietechnik/ VC 4034 climatic chamber
and underwent 30 cycles of varying humidity according to
the following regime:
a) 16h at 350C and 90%RH (high humidity conditions)
b) 8h at 230C and 55%RH (normal conditions)
The duration of each cycle was 24 hours. However, the
total duration of accelerated aging took two months, since
the chamber was only operative on working days. When
the chamber was not in operation, i.e. weekends or holi-
days, the coupons were stored under normal conditions
(20-25 0C and 50-60%RH).
Colorimetry was performed by a Dr. Lange/ MICRO
COLOR II (LMC 6) colorimeter [18, 19]. Light reflected
from the material (380-780nm, D65) is collected in an inte-
gration sphere, normalized to the source light of the re-
flectance, and calibrated with the measurement of a pure
white standard (100% reflection) and a black box (zero re-
flection) over the entire wavelength spectrum of visible
light.
From the colour spaces that are commonly in use in lit-
erature L*a*b* and its derivative L*C*H* were used by
TEI. It can be visualized as a cylindrical coordinate system
in which the axis of the cylinder is the luminosity variable
L*, ranging from 0% to 100%, and the radii are the chro-
maticity variables a*- green (negative) to red (positive) -
and b* -blue (negative) to yellow (positive) “fig.1”. The
L*C*H* variables are given by the formulas (2), (3), (4).
+ b* (yellow)
(a*,b*) or
b*
C* (C*,∏*)
∏*

5.4 Monitoring a*
- a * (green) + a* (red)
Regular visits to monitor the performance of the coat-
ings during aging were carried out by visual examination
and photographs of the coupons condition under a stere- - b* (blue)
omicroscope. Special tables were used to record the condi-
tions of the coupons by stating the colour alteration, the
appearance of metal corrosion and the coating defects per Figure 1 - a*b* and C*H* systems
coupon, per cycle.
The monitoring took place during the time interval
where the coupons were exposed to laboratory conditions
(b). During monitoring they were removed from the cli-
matic chamber for a short period of time. All handling was
performed with talc free gloves.

6. EVALUATION Whereas, L* is again the luminosity, C* is the total

chroma “magnitude” and H* the chroma “hue”.
For the examination of the artificially aged coatings, a
systematic evaluation procedure was carried out using vi- To ensure that colorimetry measurements before and
sual, macro- and microscopic examination. At the primary after ageing are carried out on the same area, a hard paper
stages of the work, ISO and/or ASTM standards were con- mask was made. The mask has an opening, which fits exact-
sidered for evaluation purposes, but they were found to re- ly the colorimeter probe. The mask has the same dimen-
fer only to major defects and macroscopic observations sions as those of the coupon “Fig. 2.
[16, 17]. However, in the case of museum metal objects, we
are interested even for microscopic changes in the coating
or the metal substrate and the use of these standards were
not applicable.
The examination of the coupons was concentrated in
the central part of the coupon. One centimetre of the
perimeter of each coupon was excluded from the evalua-
tion procedure, since the edge effects are not representa-
tive of the coatings performance and can lead to false re- Figure 2 - Corroded coupon (left). Mask (center). The
sults [20]. mask on the coupon and the probe fitted to the hole in
the mask (right).
117
AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·118
A. Siatou et al.
6.2 Photographic Recording
Photographs of the coupons before and after coating
and after accelerated corrosion, offer a macroscopic data
record. For comparative reasons, the same photographing
conditions were ensured for each series of photographs.
Here again, a protocol created by PROMET partners was
used.
TEI’s photographic conditions include artificial light-
ing in a dark room. A digital camera was adjusted on a copy
stand and four 50W lamps (Philips photoscenic) were
placed opposite to each other, with an inclination of ap-
proximately 45o to vertical, facing the coupons. A grey
cardboard was used as a background and in the case of
high gloss coupons rice paper was placed in front of the
lamps to avoid reflections. The coupons were pho-
tographed in sets, according to the type of the applied coat-
ing system.
6.3 Examination using SEM
A JEOL JSM-5310 Scanning Electron Microscope was
used to examine the coating appearance on a microscopic
scale. The voltage was adjusted to 3kV and the pressure in
the chamber down to 10-4 Pa. The voltage was kept in such
a low level in order to avoid high temperatures that would
damage the coatings [20]. The aim was to observe the coat-
ing micro-morphology due to aging; and thus the coupons
were not covered by carbon. Due to the low voltage value,
the focusing was limited in a rather small depth of field, i.e.
examination only on the outer surface layers of the coat-
ings. Thus, it was impossible to see the metal corrosion lay-
er under the coating layer.
7. RESULTS AND DISCUSSION
7.1 Coating Application
In general, the visual examination of the coupons
showed a uniform film formation in all cases. The only ex-
ception was the application of Poligen® ES 91009 (with or
without CI additives) on group 2. More specifically discol-
oration, cracking and exfoliation of the film occurred wher-
ever there were remaining loose green corrosion products
“Fig.3”. However, the problem did not occur with copper
alloy coupons with brown corrosion products. The problem
was solved by re-cleaning to the point were no loose corro-
sion products remained on the coupons’ surface and then
recoating.
Figure 3 - Bronze coupon coated with Poligen ES 91009.
Discoloration, cracking and exfoliation of the coating in
the presence of green corrosion products. Steroscopic pho-
tographs left to right magnification x0,75, x3, x6
118
The colour measurements taken before and after the
coating application showed decrease in luminosity for all
coatings. Surfaces with high surface roughness largely dif-
fuse, i.e., reflect more “white” light and show larger lumi-
nosity [21]. The application of the coating decreases sur-
face roughness and luminosity decreases. As for the total
chroma changes there is a general trend: Most off the sam-
ples turn more yellow-red after coating application.
7.2 Coating Performance after Accelerated Aging
Comparison of the colour measurements before and af-
ter accelerated aging for iron coupons show that luminosity
remains the same, as opposed to the copper coupons where
there is large increase in luminosity for all coatings. Clean
copper had an increase of luminosity for Poligen® ES 91009
but decrease for Paraloid® B-72. Regarding chroma change,
corroded iron and copper alloy coupons appear less red/yel-
low (more green/blue) whereas clean copper coupons show
colour changes that do not follow a specific pattern.
SEM examination found the same surface appearance
regardless the substrate for Poligen® ES 91009 as shown in
Fig.4c. The films formed are membrane like, tightly ad-
hered to the substrate and follow the underlying uneven
surface of the coupons. On the contrary, Paraloid® B-72
forms a compact film on both copper and iron. However,
numerous cracks are visible on the surface of iron alloy
coupons whereas in the case of the copper, alloy spots are
visible as seen in “Fig. 4a,b”. Crack lengths vary from a few
microns to 2 mm. It was not possible to see them under the
stereoscope but only under the SEM.
Figure 4 - SEM photos of the examined coatings:a) Par-
aloid® B-72 on bronze alloy, b) Paraloid® B-72 on iron al-
loy, c) Poligen® ES91009
On iron alloy coupons coated with Poligen® ES 91009
(with or without CI additives); the comparison between the
control coupons and the accelerated ones showed no visual
alteration that would imply coating failure or metal corrosion.
However, coating failure in the form of filiform corro-
sion was the main characteristic of all aged iron coupons
covered by Paraloid® B-72 with or without CI additives as
shown in Fig.5. Examination of the samples under the
SEM shows that the threads on the iron coupons are under
the protective coating “Fig.4b”. This means that the metal
surface just below the coating is corroding away. The coat-
ing detaches from the substrate and is pushed up by the
corrosion products. In this way the filament grows [22].
The source of initiation for filiform corrosion is usually
a defect or mechanical scratch in the coating [23]. In our
case, the filaments always start from an already existing
corrosion spot and follow the linear scratches created by
AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·119
Testing new coating systems for the protection of metal collections exposed in uncontrolled museum environment
the coupon mechanical treatment (polishing) grinding
lines “Fig.5c”.
Figure 5 - Coating appearance on corroded iron coupons
under a stereomicroscope, formation of filliform corrosion
on coupons coated with Paraloid® B72, (magnification
x0,75) a)Left, coupon coated with Poligen® ES
91009;b)Center, coupon coated with Paraloid® B72;c)
Right, detail of (b) (magnification x4).
Additionally in the case of copper alloy coupons the
comparison between the control coupons and the acceler-
ated ones showed no visual alteration that would imply
coating failure or metal corrosion, in all coatings applied.
8. CONCLUSIONS
The results of the evaluation are summarized in Table 3.
From the examination, it appears that the addition of the CI
additive to either Paraloid® B72 or Poligen® ES 91009 does
not offer additional protection to the either copper or iron
coupons. Regarding the protection systems applied to iron al-
loy coupons, the Poligen® ES 91009 coating with or without
CI have better results than Paraloid® B72 with our without
CI additives. Regarding the examination of copper alloy
coupons with or without coatings no additional protection
was observed for coated coupons. However, the application of
Poligen® ES 91009 for copper alloys must be performed with
extra care since exfoliation was found to occur in some cases.
ACKNOWLEDGMENTS
The authors would like to thank the Greek Center of Met-
al Research (∂§∫∂ª∂) -252 Pireos st., 177 78 Attiki,
Greece- for performing the accelerated corrosion tests in
their climatic chamber.
REFERENCES
[1] Argyropoulos, V., Giannoulaki, M, Sakki, Z., Karydas,
A. G., Zarkadas, C., Pouli, P., Melessanaki, K., Gak-
oumaki, A., Anglos, D., 2005, “Problems in stabilizing
historic iron-bladed weapons displayed in an uncon-
trolled environment in the Criminal Museum of Athens,
Greece”, accepted for publication in the upcoming
preprints of ICOM-CC Triennial Meeting in the Hague.
[2] Sease, C., Selwyn, L. S., Zubiate, S., Bowers, D. F. and
Atkins, D. R. 1997, “Problems with coated silver:
whiskers formation and possible filiform corrosion”, in:
Studies in Conservation, Volume 42, No.1 pp.1-11.
119
[3] Personal communication with Conservator-Restorer
Professionals, working as fulltime or part-time staff, in 9
different Greek museums.
[4] A student survey, provided by Maria Papadimitriou
(specialist in preventive conservation), conducted dur-
ing the course “Environment of Museums and Sites” at
TEI of Athens (2005), where the students were asked to
visit 14 different museums across Greece and register
the environmental conditions in these museums.
[5] Plenderleith, H., Werner, A. 1971, “The Conservation of
Atniquities and Works of Art”, 2nd Edition, 1989, Eng-
land, Oxford University Press.
[6] Munger, C., 1984, “Corrosion Prevention by Protective
Coatings”, U.S.A., NACE publication.
[7] Sastri, V. S., 1998, “Corrosion Inhibitors –principles and
applications”, England Wiley publications
[8] Brooman, E., 2002, “Modifying Organic Coatings to
Provide Corrosion Resistance- Part I: Background
and General Principles”, In: Metal Finishing, January
2002 pp. 48-53.
[9] Argyropoulos, V., Giannoulaki, M., Michalakakos, G.,
Siatou, A., 2007, “A survey of the types of corrosion in-
hibitors and protective coatings used for the conserva-
tion of metal objects from museum collections in the
Mediterranean basin”, this volume.
[10] Cronyn, J., 1990, “The elements of Archaeological Con-
servation”, 2001 edition, New York, Routledge Int.
[11] http://www.basf.com, 2006
[12] http://www.cortecvci.com, 2006
[13] http://www.dow.com, 2006
[14] ASTM G 1-03,Standard practice for preparing, clean-
ing and evaluating corrosion test specimens.
[15] ISO 4618-1/2/3: 1998, Paints and varnishes – Terms and
definitions for coatings materials:Part 3: Surface prepa-
ration and methods of application.
[16] ISO 4628-6: 1982, Paints and varnishes – Evaluation of
degradation of paint coatings –Designation of intensity,
quantity and size of common types of defect – Part 6:
Rating of degree of chalking by tape method
[17] ASTM D 661-93, Standard test method for evaluating
the degree of cracking of exterior paints.
[18] MICRO COLOR II Colorimeter - Dr Lange, Operat-
ing Instructions, BDA 295 Ed. 2.
[19] DIN 5033 Farbmessung.
[20] Personal communication with Annick Texier from Lab-
oratoire de Recherche des monuments historiques 29,
rue de Paris,F - 77420 - Champs-sur-Marne, France
[21] Berns, R.S., de la Rie, E.R., 2002, “The relative impor-
tance of surface roughness and refractive index in the effects
of varnishes on the appearance of paintings”, Preprints of
the 13th triennial meeting of the ICOM Committee for
Conservation, Rio de Janeiro, Vol.1, pp. 211-216.
[22] Bautista, A., 1996, “Filiform corrosion in polymer-coat-
ed metals”, Progress in Organic Coatings 28, pp. 49-58.
[23] Grundmeier, G., Schmidt, W. & Stratmann, M., 2000,
“Corrosion protection by organic coatings: electrochem-
ical mechanism and novel methods of investigation”
Electrochimica Acta 45, pp.2515–2533.
AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·120

A. Siatou et al.

List of manufacturers and distributors

Poligen® ES 91009 Dow, chemical Company - Greek Representative: N.

BASF chemical company, Greek representative: Dr. D.A. Kralis S.A., Deligiorgi 55-59, 10437 Athnes Greece
DELIS AG, Paleologou Pemizelou 5,10556, Athens.
https://worldaccount.basf.com Lab equipment
Tech-line SA “Chemicals-quality control”, Achileos 2, 10
Paraloid® B-72 437, Athens, Greece
Exaireton, Poulopoulou 18, Athens, Greece
Plexiglas manufacturer
Corrosion Inhibitor Additives
Koutsourelakis Vardis, Midias 47, 17122, Athens,
Cortec Co., European Representative: Ivan Rogan, Nova
Ves 57 10000 Zagreb, Croatia, http://www.cortecros.hr/ Greece

120