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Conservation problems and a new method of protection:

The case of bronzes at the Archaeological Museum of Rabat, Morocco
Najat Hajjaji1, Fatima Zohra El Harrif2, Choumicha Kaouane3, Abdellah Srhiri4,
Hisasi Taknouti5 and Kamal Rahmouni5,
1
Laboratory of Electrochemistry, Corrosion and Environment, Faculty of Science
2
National Institute of Science of Archaeology and Patrimony, Morocco
3
Direction of Patrimony, No 17, Morocco
4
SERVICHIM SARL society of corrosion inhibitors production, Morocco
5
LISE - UPR 15, CNRS, Paris VI-France
Faculty of sciences BP 133
Kenitra city, MOROCCO
Phone: (00212)61109025
Fax: (00212)37379682
e-mail: n_hajjaji@yahoo.fr

The paper outlines the general conservation problems and needs for the archaeological bronzes at the museum
in Rabat Morocco. It also describes the preventive conservation measures that were taken in order to improve
the environmental conditions of the bronzes on display in the exhibition room of the museum. However, the
main aim of this study was to test a new corrosion inhibitor able to protect archaeological bronzes against corro-
sion. The authors have synthesized an organic product named 3-phenyl 1,2,4- triazole-5 thione noted PTS. This
compound acts as good corrosion inhibitor to protect bronze in neutral chloride medium. So as to facilitate its
use in application to bronze artefacts, a special formulation known as FPTS was prepared. The inhibiting effect
of FPTS was studied using transient electrochemical technique and surface analysis. The results indicate that
FPTS has good inhibiting effect and this inhibitor formulation acts on both anodic and cathodic processes.

Keywords: archaeological bronze, museum, preventive conservation, corrosion inhibitors

1. INTRODUCTION The PROMET project is very important in this effort

Since the end of the 19th century, the excavations car-
ried out in Morocco have produced a large number of ar-
chaeological objects made of copper alloys such as bronze.
The most spectacular and important bronze objects are ex-
hibited at the Archaeological Museum of Rabat.
Most of these objects have been discovered in Volubilis,
a prosperous Roman city between 1st century BC and 3rd
Century AD, but many objects were also found in Banasa,
Thamusida, Sala, Lixus or Tamuda, and represent one of
the most important and famous collections of Roman
bronzes from North Africa and the Mediterranean basin [1].
The museum collection is representative of different
periods of the ancient history of Morocco and expresses
the first influence evidences of the Mediterranean civi-
lization in Mauritania Tingitana, which corresponds to the
Roman period in Morocco. Some of the objects are on
display to the general public, but many are stored away in
the museum in uncontrolled conditions, which favours
active corrosion for the bronze objects.
To deal with the problems of preserving this impor-
tant collection, scientific, analyses, conservation treat-
ment were carried out in Morocco and abroad to find a
best solution to preserve them.
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to preserve this museum collection by helping our effort
to preserve such a metal collection, and to strengthen our
international cooperation with leading scientists in this
field to determine the best practice for our country. Ten
bronze artefacts were selected to test new corrosion in-
hibitors after initial testing using bronze coupons. The re-
sults of this investigation will allow for new knowledge as
to the best way to protect such artefacts.
2. THE EXHIBITION CONDITIONS
The bronze collection encounter great problems re-
lated to the conditions of their exhibition at the museum,
which are divided into two factors: natural and human
ones. As far as the natural factors are concerned, uncon-
trolled environment (temperature, light and relative hu-
midity), insects and dust are the leading threats. Less
qualified technical staff and a lack of resources is also
contributing to the continued corrosion of these collec-
tions. In 2003, the renovation of the museum’s buildings
helped to improve the environmental conditions.
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Conservation problems and a new method of protection: Bronzes at the Archaeological Museum of Rabat

2.1 Exhibition Room
Between 1952 and 2003, the bronze collection was ex-
hibited in an oval room in a surface area of 162m2. This
room has 24 windows situated in the roof and permanent-
ly closed to avoid the entrance of the natural light Howev-
er, some of them can remain opened for a long time, es-
pecially when broken and aerosol salts from the Atlantic
Ocean can easily contaminate the room especially by the
wind and the salty fog. This room was accessible by a
large door leading directly to the outside. The museum is
located in a narrow street and only approximately 200m
from a main avenue, which exposes the collections to the
pollution created by the heavy traffic. Such conditions
will also be enhanced by the climate of Rabat, the hydro-
gen sulphide and the sulphur dioxide as well as the carbon
dioxide, which is producing carbonic acid.
Salt efflorescence traces were located in the roof of
this room, which is a sign of water infiltration. Further-
more, the walls were covered by low density wooden pan-
els, which absorb the humidity during winters and release
it in the summers.
The exhibition room of the bronze collection was dis-
played in a long showcase along the wall and totally
opened at the top. The objects were organized according
to the themes and laid out on wooden panels. The statues
were put on marble or rock plinth without any more pro-
tection, and could be easily touched by the visitors. The
lighting was issued from fluorescent tubes and the natural
light from the door and the 24 windows.
Apart from the curator, the technical and scientific
staff do not have sufficient training in conservation to
deal with the preservation of such large collections.
a. Lighting: two luxmeters were placed in the open show-
case. One of them is located near the door and another in-
side the room. On average 250 lux was recorded during the
year with a large peak of 900 lux in July and August between
6 and 8a.m. in the morning coinciding with the morning sun-
shine. Whereas, those placed near the door recorded on av-
erage more than 350 lux with a peak in October equivalent
to 500 lux recorded between 8 and 10a.m. in the morning.
b. Climate: sensors were placed at the entry and the bottom
of the room to control the thermo-hygrometric variations
recorded in the room. The overall results have still not been
given to the museum. However, initial results show that the
RH recorded during three days in November oscillated be-
tween 73% and 92% and the temperature between 18 and
21oC with a marked increase between 12 a.m. and 5 p.m.
2.3 New data
During July and August 2006, new measurements
were carried out by the Moroccan members of the
PROMET project inside the showroom. The results (Fig-
ures 1, 2 and 3) do not reveal big fluctuations in the tem-
perature nor in the RH during three days: the 3rd and 15th
July and the 3rd August. However, the RH is always
greater than 60%, and in the presence of salt aerosols
greatly increases the corrosion rate of metals.

2.2 New exhibition conditions

During the summer 2003, the museum was completely
renovated. The large glass case in the wall was replaced
by several mobile showcases with filtered and incorporat-
ed lighting. Such conditions largely decreased the pene-
tration of the insects, dust and airborne pollutants. As far
as the water-tightness of the new display cases no water
Figure 1 - Variations of temperature in Bronze room
infiltration is possible.
at different time of the day
Lighting was also improved by installing a new electri-
cal network to avoid natural light by closing completely
the 24 windows of the room and the door leading to the
outside. The showroom became accessible by another
large room for the exhibition of the marble collection.
Between 2000 and 2001, the International Centre for
the Study of the Preservation and Restoration of Cultural
Property (ICCROM) organized a course of conservation-
restoration of the cultural heritage collections of the mu-
seums called “Rabat Course” with the aim to strengthen
the experience of scholars from the Maghreb countries.
Thus the metal collections (bronze and iron) benefited
from several studies related to the conditions of their ex-
hibition and storage rooms. Our paper provides a sum-
mary of these studies [2]: Figure 2 - variations of RH in Bronze room at different
hours of the day
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N. Hajjaji et al.

3.2 Inhibitor
The product tested is an organic corrosion inhibitor,
PTS, which was synthesized in our laboratory and tested
as a formulation noted FPTS [3].

3.3 Corrosive medium

The bronze coupons were exposed to atmospheric
corrosion. The electrochemical test was carried out in 3%
NaCl solution, prepared with distilled water and the
reagent grade chemical products.

3.4 Techniques
The electrochemical tests was carried out using a
Figure 3 - variations of the temperature in bronze EG&G apparatus 6310 with a classical three electrode
room and reserve at different days cell. A platinum grid was used as counter electrode,
Ag/AgCl as a reference electrode, and bronze coupon as
3. NEW ORIENTATION TO PROTECT THE AR- a working electrode. The analysed frequency range was
CHAEOLOGICAL BRONZES 100 KHz to 1 mHz, 5 points per decade and 5mv as ampli-
tude of the sinusoidal signal used.
The PROMET project aims at establishing a common The SEM EDX analysis was carried out using HV 16
vision for the problems of museums and a practical ap- KV with ZAF quantification.
proach for resolving conservation problems and looking
for better and efficient method to protect and preserve 4. RESULTS AND DISCUSSION
their metal artefacts.
We have chosen a “phalere” from the ten bronzes se- 4.1 SEM/EDX observations of phalera fragment
lected in PROMET project for further analysis and to test A small thin section of the phalera was taken and is
the new corrosion inhibitor using some electrochemical shown in Figure 5.
and spectroscopic techniques. First the phalere’s compo-
sition and patina layer were determined using scientific
analysis. Then, a new organic compound, 3-phenyl 1,2,4-
triazole 5-thione (PTS) as corrosion inhibitor was tested
on bronze coupons before applying this new protection
method to this archaeological object. The bronze
coupons were prepared by author’s partner in PROMET
project.

3.1 The “phalera”

The photo illustrates in Figure 4 the original form of
this bronze. The patina layer formed is a green to grey
colour.
Figure 5 - SEM photograph of Phalere cross section

The SEM observations revealed various zones on the

sample area as shown in Figures 5 and 6.

Figure 4 - General view of phalere

This phalere measuring: L= 8,2cm and l= 5,9cm was

manufactured locally during the Roman period. Figure 6 - Cross-section of Phalere
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Conservation problems and a new method of protection: Bronzes at the Archaeological Museum of Rabat
The patina layer in grey colour at the surface was few
tens of micrometers. This patina layer analysis permits to
class it in type II as described in previous work [1]. EDX
analysis was also carried out on the cross section to deter-
mine the metal’s chemical composition. The correspond-
ing results are summarised in Table 1.
Table 1 shows that oxygen is the major constituent of
patina layer, and Si, Cu, Zn, Sn, Pb, Cl and P were also
detected.
The results at the substrate show that the bronze is
quaternary Cu-Pb-Sn-Zn alloy.
Table 1 - Bronze composition of phalere
External part of patina is rich in exogenous elements
like O, P, C, Mg, K and poor in principal constituents of
substrate like Cu, Sn, Pb, and Zn. The first elements
come from soil during patina formation.
It is interesting to note that the P is present only in the
superficial layer, and this element may come from human
manipulations.
We can also note that the Cu/Sn ratio is higher in the
corrosion layer rather than the metal substrate. This may
interpreted by selective dissolution of copper named as
decuprification in accord with previous paper [4].
4.2 Electrochemical measurments with bronze coupons
Electrochemical measurements were carried out with
the PROMET bronze coupon, which have roughly a same
composition as the archaeological artefacts.
The electrochemical impedance spectra were collect-
ed at the open-circuit potential. The diagrams obtained
without inhibitor are illustrated in Figure 7. The shape of
these diagrams is not modified by immersion time, and
one capacitive loop followed by an initiation at low fre-
quencies of a beginning of second time constant as shown
in this figure.
Figure 7 - Effect of immersion time of bronze coupon
in 3% NaCl solution
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The values of R (resistance) and C (capacitance) as-
sociated to high frequencies semi circle, are given in
Table 2. The associated characteristic frequency Fc corre-
sponds to the apex of the capacitive loop.
Table 2 - Fc, C and R values issued from Figure 7
I’immersion Frequency Capacitance Resistance
period (h) (Hz) (ÌF) (kø)
2h 1 106 1.50
24h 0.398 110 3.61
48h 0.251 123 5.18
72h 0.158 269 3.75
The resistance value associated to this high frequency
loop, and obtained by intersection of obtained semi circle
with real axis. The obtained value increases with an in-
crease of immersion time. Simultaneously, the capaci-
tance is raised. This may correspond to a roughening and
the accumulation of corrosion products at the surface,
which can result from the hydrolysis of patina layer or the
formation of corrosion products. The patina layer may re-
sult in a volume increase. The application of surface
analysis techniques indicate that the electrical properties
of patina layer are modified.
The impedance diagrams in presence of inhibitor are
presented in Figure 8, which shows that an increase of im-
mersion time modifies the behaviour of the bronze
coupon.
The polarisation resistance increases dramatically when
the immersion time increases from 2 to 144 hours. This re-
sistance increase is accompanied by an apparition of two
time constants. The second one seems to have a higher val-
ue than 8 kohms. The inhibiting effect may be reinforced
with immersion time and in comparison with blank test, a
frequency shift was noted to higher values in presence of in-
hibitor. It passes for example from 1Hz to 250 Hz after 2
hours of immersion time. The low frequency loop is very
marked by the presence of the inhibitor and at high immer-
sion time values. The associated resistance values seem to
diverge to the infinite [2]. The polarisation resistance is like-
ly very high with inhibitor addition compared to blank es-
say. The values of dielectric parameters for the two capaci-
tive loops are displayed in Table 3.
Figure 8 - Effect of immersion time of bronze coupon
in 3% NaCl solution + 0.07% of inhibitor FPTS
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N. Hajjaji et al.

Table 3 - Values of parameters associated to impedance were developed in the Laboratory of Electrochemistry, Cor-
spectra presented in Figure 8 rosion and Environment in the Faculty of Sciences in Kenitra
(Morocco). The inhibiting performance was tested on bronze
Time RHF RBF CHF CBF FHF FBF coupons. The FPTS shows good inhibition efficiency, and it
(h) (kΩ) (kΩ) (ÌF) (ÌF) (kHz) (Hz) will be very interesting to test it on real artefacts for protec-
2 0.088 0.661 0.450 240 3.98 1.00 tion especially in a marine environment. Currently, the effect
24 0.104 1.67 0.380 378 3.98 0.251 of the corrosion inhibitor on the phalera fragment is being
48 0.161 2.73 0.240 584 3.98 0.100 tested, and this inhibitor will be tested other bronze artefacts
72 0.677 3.89 0.230 648 1.00 0.063 selected from our collection from the Rabat museum.
120 1.85 »8 0.216 - 0.398 -
144 2.95 »8 0.210 - 0.251 - ACKNOWLEDGEMENTS

For the surface area of 1cm2
The summary of this table suggests that the low fre-
quency loop has the same physical origin to the loop ob-
served in absence of inhibitor. The values of RHF associ-
ated to high frequencies semi circle are lower than those
obtained. Thus, the attribution of this loop to charge
transfer leads to an increase of the rate of corrosion. This
would be contradictory with previous analyses confirming
inhibiting effect of FPTS to protect bronze. The high fre-
quency loop may be therefore associated with a thin in-
hibitor film formed on bronze surface.
In accordance with this interpretation, the low fre-
quency tail observed after long immersion may be attrib-
uted to the Faradic process being held on the level of the
sites where the film is missing.
The estimated values of polarisation resistance are
higher than those obtained for blank tests the inhibitor
acts as a barrier to protect the substrate bronze. Simulta-
neously, the FPTS may be linked with the patina layer de-
posited on bronze coupon and reinforce its stability [4].
5. CONCLUSIONS
No one doubts the importance of archaeological bronze
objects at the Rabat museum in terms of their great historical
and cultural value. However, for preserving and safeguarding
this rich and diversified inheritance, new corrosion inhibitors
This work was realized in the framework of “PRO-
MET” project and the authors gratefully acknowledge the
financial support. We also would thank the Direction of
Patrimony for giving agreement for this study, and the LISE
Laboratory (Paris VI-France) for its collaboration through
CNRS – CNRST project PICS no3388.
REFERENCES
[1] Boube-Piccot, Ch.: ‘‘Les bronzes antiques du Maroc”,
I la statuaire, Etude et Travaux d’Archéologie Maro-
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[2] Serarfi, S., Annane, S.: ‘‘La conservation des objets
de bronze en exposition”, Mémoire de fin d’études
pour l’obtention du diplôme d’étude supérieure spé-
cialisées en conservation-restauration, «Cours de
Rabat», (2000-2001).
[3] Dermaj, A., Chebabe, D., Hajjaji, N., Joiret, S., Rah-
mouni, K., Srhiri, A., Takenouti, H., Vivier,V.: ‘‘Étude
de la corrosion de bronze Cu-8%Sn et l’effet inhibi-
teur de 3-phenyl-1.2.4- triazole-5-thione”. Acte du
17ème Forum d’impédance, électrochimique, édité
par C. Gabrielli, Paris 257-268(2005).
[4] Rahmouni, K.: ‘‘Corrosion et protection des bronzes
recouverts de patine: étude électrochimique spectro-
scopique de la surface d’objets archéologique et syn-
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