Testing of a new wax coating Poligen ES 91009® and corrosion

inhibitor additives used for improving coatings for historic iron alloys
Vasilike Argyropoulosa*, Dimitrios Charalambousa, Agathi Kaminaria, Athanasios
Karabotsosa, Kyriaki Polikretia, Amalia Siatoua, Emilio Canob, David M. Bastidasb, Iris
Cayuela, José-Maria Bastidas b, Christian Degrignyc, Daniel Vellac, James Crawfordc
and Stavroula Golfomitsouc.

a
T.E.I of Athens, Dept. of Conservation of Antiquities & Works of
Art, Ag. Spyridonos, Aigaleo 12210, Greece
b
Consejo Superior Investigaciones Cientiicas (CSIC), Centro
Nacional de Investigaciones Metalurgicas (CENIM), Avenida
Gregorio del Amo, 8 Madrid 28040, Spain
c
Heritage Malta (HM), Conservation Division- Diagnostic Science
Laboratory, Old Royal Naval Hospital, Bighi CSP 12 Kalkara,
Malta
* Corresponding author: bessie@teiath.gr

Abstract
Research into commercially available Poligen ES 91009® wax coating and corrosion inhibitor (CI) additives for
improving protection coatings are tested using a systematic methodology on iron coupons. The testing involves
accelerated aging of coated and uncoated coupons in a climatic chamber, electrochemical measurements using
(polarization resistance (Rp) and electrochemical impedance spectroscopy (EIS)) in different electrolyte solutions,
along with long-term aging of coupons at the Criminology Museum in Greece and the Palace Armoury collection
in Malta. Both museums were selected for their uncontrolled environmental conditions and housing of historical
iron collections. The electrochemical measurements found Poligen® to be a superior coating when compared to
15% (w/v) Paraloid® B-72 in acetone, but the addition of CI additives did not improve their protective properties.
The accelerated aging of the coupons conirmed the electrochemical measurements, but for the long-term testing,
after 3 to 7 months of exposure in the museums it is still too soon to rate the coatings.

Keywords: coatings, corrosion inhibitor additives, accelerated aging, electrochemical measurements, long-term aging, uncon-
trolled museum environments

Introduction Test products

A survey of 50 institutions from the Mediterranean basin
showed that the most popular coating used by conservator-
restorers (C-Rs) to protect historical and archaeological iron
and copper alloy museum objects are Paraloid® B-72 alone or
combined with a synthetic wax (Argyropoulos et al. forthcom-
ing). However, studies have shown that Paraloid® B-72 with
wax is ineffective and even damaging for historic iron objects
in museums with uncontrolled environments (Argyropou-
los et al. 2005). Under the auspices of the 6th Framework Pro-
gramme European Commission (EC) project PROMET (www.
promet.org.gr), research was undertaken in testing a commer-
cially available new wax coating, Poligen ES 91009® (hereafter
referred to as Poligen®) and corrosion inhibitor (CI) additives
for improving current and new coatings. The results of this
ongoing research are presented with speciic reference to the
electrochemical studies of coated iron coupons after acceler-
ated aging and also with long-term testing at the Criminology
Museum in Greece and the Palace Armoury collection in Malta.
A selection of non-toxic corrosion inhibitor (CI) additives,
coatings, and ready-to-use coating systems produced by Dow
Chemical Company, Cortec Co., BASF and Bio-chemie & Bio-
technologie GmbH. was made after conducting a market sur-
vey. After initial testing, 12 highly rated products that met con-
servation standards (i.e., irreversibility, aesthetic appearance,
etc.) were selected for further testing.
These products included the ready-to-use liquid (ethylene in
water) wax named Poligen® (BASF). Also, many CI additives
applied either in Paraloid® B-72 or Poligen® were tested, such
as bis-oxazoline (Alkaterge-T®) by Dow Chemical Company;
and calcium sulfonate (M109), a blend of triazoles (M435), and
ammonium salt of tricarboxylic acid (M370) by Cortec Co.. Most
of these CI additives are well known in the literature for protect-
ing industrial objects (Morrison 2005; ANGUS 2000), but they
have never been used on museum objects. Furthermore, they
are safe and easy to use, and for Poligen® no solvent is required,
instead it is applied as a liquid and dries within 24 hours.

10 METAL 07

Museum test locations
Criminology Museum
The problems with the collection of 200 bladed-weapons from
the 19th and 20th centuries housed at the Criminology Museum
have been discussed elsewhere (Argyropoulos et al. 2005). The
museum is a 76m2 room located on the irst loor of the Dept.
of Forensic Medicine and Toxicology, University of Athens,
serving both as an exhibition and as a storage room. Apart from
the bladed-weapons and guns, the museum also houses sensi-
tive material such as wet human tissue specimens, including
12 decapitated heads of infamous criminals. For this reason,
the windows of the museum are covered, to block out natural
light, and a heating/cooling system is not used. The environ-
mental conditions, relative humidity (RH) and temperature
(T) are monitored on a continuous basis, using a Tinytag® plus
data-logger, and the results are shown in igure 1. The SO2, NO2,
NO, and O3 were measured using automatic analyzer during a
one-week period in February 2007 and are given in table 1. The
RH and T for summer and winter seasons are 41.7±6.9% and
28.6±2.7 °C, and 59.2±10.4% and 17.3±3.4 °C respectively. This
uncontrolled museum environment requires that after conser-
vation of the iron blades, a coating be used to preserve them in
their display cases.
Palace Armoury
The problems with the collection of 1500 armour pieces from
the 16th and 17th centuries housed at the Grand Master’s Palace
in Valletta, Malta have also been well documented (Vella et al.
2004). In 1975, the collection was transferred to the ground
loor level of the Palace, in a location that typically from old
Table 1: SO2, NO2, NO, and O3 measurements carried out
by the Environmental Research Laboratory at N.C.S.R.
Demokritos using automatic analyzers during the period of
16/2/2007-23/2/2007 at the Criminology Museum. Meas-
urements were recorded every 15 minutes during the week
but only week summary results are presented in table 1.
Analyzers were located near coupon rack in museum
16/2/2007-23/2/2007
ΝΟ ppb ΝΟ2 ppb SΟ2 ppb Ο3 ppb
Max 110 43.4 1.97 14.8
Min 0.42 6.32 0.51 1.89
Avg 24.2 20.1 0.81 5.76
StDev 21.2 8.06 0.28 3.33
Figure 1: RH and T measurements
at the Criminology Museum in
Athens between July 2006 to
March 2007
buildings suffers from rising damp. The room conditions are
uncontrolled in terms of RH and T and Malta being a small
island has the presence of chlorides (due to the close proximity
of the Mediterranean sea). Some of the armour pieces are on
display in the open, and some are attached to the walls. Dust
particles, primarily airborne from the surroundings, are obvi-
ously present and contaminate these objects. The environ-
mental conditions are monitored for RH and T on a continuous
basis using HOBO® data-loggers, and are shown in igure 2,
where the means and standard deviations for the period of May-
November 2006 for T and RH are 25.20 +/- 2.12 °C and 63.13%
+/- 6.61% respectively. The SO2, NO2, and O3 are collected by
passive sampling using Gradko diffusion tubes for 3 to 4 weeks
are given in table 2 over a period July 2006 – February 2007 sit-
uated just next to the rack with the coupons.
Over the years, several protective systems, such as polyure-
thane varnish, wax, and various trade named anti-corrosion oils
were tried to protect the armour. Unfortunately, all were found
to be ineffective and in some cases when failure occurred, ili-
form corrosion propagated.
Test methodology
The protocol for testing and examining these products was
speciically designed for indoor museum conditions and is
described in detail elsewhere in these proceedings (Degrigny
et al. 2007). Essentially the protocol involves accelerated test-
ing of coatings, with or without CI additives, on corroded iron
alloy coupons, along with long-term aging of a selection of the
above coatings on similar coupons and on real artefacts.
Furthermore, electrochemical testing (polarisation resistance
(Rp) and electrochemical impedance spectroscopy (EIS)) was
undertaken for Poligen®, and Paraloid® B-72, with and/or
without CI additives and Renaissance® wax as well, in two
different electrolytes, 0.1 M NaCl and 0.35 %(w/v) (NH4)2SO4
+0.05%(w/v) NaCl in H2O on non-corroded steel coupons,
as well as the coupons that underwent accelerated aging. The
details of the experimental set up for the electrochemical mea-
surements are described elsewhere (Cano et al. forthcoming).
Application and preparation of the coating systems are also
described in detail elsewhere (Siatou et al. forthcoming). How-
ever, it is important to note that for accelerated aging of corrod-
ed iron coupons, protection systems were applied by immer-
sion as opposed to long-term aging of the iron coupons where
coatings were applied using a ine nylon-bristle brush, with a
criss-cross ilm. Immersion application for the accelerated aging
was decided in order to ensure a uniform and continuous ilm.
Vol. 5. Protection of metal artefacts 11
 Figure 2: RH and T measurements
at the Palace Armoury collection
in Malta between May-November
2006
Relative humidity

Temperature

Table 2: Pollutant gas levels inside the exhibit hall of the the Criminology Museum, a rack made of Plexiglas according
Palace Armoury collection as measured by passive diffu- to ISO/DIS 11844-2 (2003) was placed vertically on top of a
sion tubes. Tubes are located next to the coupon rack. The wooden display case next to the wall in the area where sensitive
analysis was carried out by Gradko Co organic materials are displayed. At the Palace Armoury, the rack
had an inclination of 30° to the vertical to allow accumulation
Exposure Period Pollutant gases in ppb of particles and was located on a wall adjacent to the armour
O3 NO2 SO2 exhibits in the Armour Hall. At the Criminology Museum,
07/11/06 - 30/11/06 3.12 10.82 0.06 5 groups of coupons (10 coupons for each group) were placed
on the rack: 15% (w/v) Paraloid® B-72 in acetone (Group TC1),
30/11/06– 29/12/06 3.77 10.55 0.10
Poligen® (Group C1), Poligen® with M370 (Group C2), Poli-
29/12/06 – 07/02/07 5.70 10.24 0.21
gen® with M435 (Group C3) and unprotected coupons (Group
07/02/07 – 27/02/07 9.08 6.99 0.35 NC). At the Palace Armoury, 5 groups of coupons were also
placed, but only Groups TC1, C1, and NC were common to the
However, for the long-term aging, a brush application had to be Criminology Museum. Coatings were applied with a brush
used to simulate the manner in which C-Rs usually apply such in criss-cross fashion. Exposure testing of the coupons com-
coatings. menced on July 28 and November 7, 2006 at the Criminology
Exposure racks were installed at the Criminology Museum and Museum and Palace Armoury respectively.
the Palace Armoury, with 45 iron coupons in each location. At The results for the long-term aging of the iron coupons after 3

Figure 3: Average thickness measu-

rement of coated and uncoated
reference and accelerated aged
iron coupons using an Elcometer
300 thickness gauge with probe for
magnetic materials based on elec-
Thickness, µm

tromagnetic induction

12 METAL 07
 and 7 months for the Palace Armoury collection and the Crimi-
nology Museum are discussed in this paper along with the elec-
trochemical measurements undertaken for the corroded iron
coupons that underwent accelerated testing.
Results and discussion
The results of the scientiic examination of the iron alloy cou-
pons that underwent accelerated aging with the products
described above are discussed in detail elsewhere by Siatou et
al. (forthcoming). In summary, the scientiic examination after
accelerated aging in a climatic chamber of all the iron coupons
coated with Paraloid® B-72 with and without CI additives
failed by iliform corrosion as opposed to the Poligen® with or
without CI additives, which showed no signs of failure. How-
ever using scientiic examination, it was impossible to rate the
coupons coated with Poligen® with or without CI additives.
For this reason, it was necessary to carry out electrochemical
measurements on these coupons according to the Groups NC,
TC1, TC2 - Renaissance® wax, C1, C2, C3, C4 - 15 % (w/v) Par-
aloid® B-72 in acetone with Alkaterge-T®, and C5 - 15% (w/v)
Paraloid® B-72 acetone with M109. The measured thickness
of each coating is given in igure 3, and shows varying differ-
ences between those with Paraloid® B-72 as opposed to Poli-
gen® with or without CI additives. Also, from the standard
deviations shown in the igure 3, the coatings are not uniform
in thickness across the coupon, as was assumed to be the case
when using the immersion method of application.
Figure 4 gives the results of the polarization resistance mea-
surements in electrolyte 0.1 M NaCl for the artiicially corroded
and accelerated aged coupons in comparison to the measure-
ments taken using the non-corroded steel (labelled and referred
to as reference), where in the latter case, coatings were applied
with a brush. Good agreement was found when comparing the
Rp results for the coated accelerated aged coupons to those of
the reference coupons.
Rp, Ω cm2
(*) The values of Rp for these samples are higher than the highest resistance
measurable with the experimental setup used
For the accelerated aged coupons, the least protection was found
for the Renaissance wax® (TC2) as opposed to the best protec-
tion for Poligen® coating without CI additives (C1). In fact, the
addition of CI additives to the Poligen® reduced the protective
effect of the coating (C2 and C3). For accelerated aged coupons
covered with Paraloid® B-72, the protective effect was less than
Poligen® alone, and the CI additives did not improve the protec-
tive properties of the coating on the accelerated aged coupons.
When comparing the results for the coated accelerated aged
coupons with the coated reference coupons there is no uniform
tendency in the differences between the two sets: NC and TC2
show similar values, coatings based with Paraloid® B-72 (TC1,
C4, and C5), the accelerated testing show a slight increase in
values of resistance as opposed to the reference coupons. How-
ever, for Poligen®-based coatings (C1, C2, and C3) the reference
coupons show better resistance than the accelerated aged cou-
pons. It is unknown if the difference in the measured thickness
of the coatings (as attributable to the application technique:
immersion for accelerated aged coupons or brushing for the
reference coupons) plays a role in the results. Furthermore, the
greater measured thickness on the accelerated aged coupons as
opposed to the reference coupons may be attributable to the
presence of corrosion products.
Results led to the selection of TC1, C1, C2, C3, and NC coated
coupons for long-term aging of coated coupons at the Crimi-
nology Museum. The methodology requires that coupons
are removed from the rack after 3, 6, 9, and 12 months and are
examined scientiically, as well as with relectance FTIR analy-
sis and EIS measurements.
Visual examination using a stereomicroscope for the iron cou-
pons of all groups after 3 months of exposure showed no signs
of corrosion/coating failure at the Criminology Museum, and
for groups TC1 (Paraloid® B-72) and C1 (Poligen®) at the Pal-
ace Armoury. However, the group of uncoated coupons did
develop new corrosion products at both museums. Scanning
Figure 4: Polarization resistance of
coated and uncoated reference and
accelerated aged iron coupons in
0.1 M NaCl solution
Vol. 5. Protection of metal artefacts 13
 a/ b/

Figures 5: Iron coupon before (a) and after (b) 7 months of long-term aging at the Criminology museum without any coating

electron microscopy (SEM) at 8 keV conirmed that there was but, in the latter case, after 7 months, evidence of coating failure
no damage to either coating tested at the Palace Armoury, but begins to appear. However, more time must lapse before we can
only the evidence of dust particles. make a clear judgement on the effectiveness of these coatings.
After 7 months of exposure at the Criminology Museum, chang-
es to the coupons were observed. At least 3 of the 6 NC (uncoat- Materials list
ed) coupons showed signiicant signs of corrosion in limited • Poligen ES 91009
areas (see igure 5). For the groups TC1, C1, C2, and C3 some cou- BASF Aktiengesellschaft
pons have begun to show evidence of newly formed corrosion Carl-Bosch-Str. 38
visible only through the stereomicroscope, making it dificult to 67056, Ludwigshafen, Germany
rate them at this point in time. Results for the Palace Armoury at https://worldaccount.basf.com
this time period for comparative purposes are not yet available. • Corrosion Inhibitor Additives
Cortec Co.: 4119 White Bear Parkway
Conclusion St. Paul, MN 55110 U.S.A
Results show that the Poligen ES 91009® alone is a better pro- European Representative: Ivan Rogan Nova Ves 57
tective coating than Paraloid® B-72 or Renaissance® wax for 10000 Zagreb
iron coupons based on the electrochemical results and/or the Croatia
scientiic examination of the accelerated aged coupons. Initial http://www.cortecros.hr/
results indicate that the CI additives do not seem to improve • Dow chemical Company:
the protective effect of any coating when the iron coupons have Prins Boudewijnlaan 41
corrosion products. Thus, it may be that these commercially 2650 Edegem
available CI additives are only effective on clean metal surfaces. Belgium
To date, the long-term aging of coupons after 3 months of expo-
sure show no differences between the coupons coated with
Paraloid® B72 and Poligen® at the two museum locations,
Palace Armoury in Malta and Criminology Museum in Greece,

14 METAL 07
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Vol. 5. Protection of metal artefacts 15