Beruflich Dokumente
Kultur Dokumente
Most archaeological objects made of iron or copper are exposed to corrosive agents, such as pollutants, fluctu-
ating humidity, etc, and are slowly lost in Museums. In our laboratory, we have tested formulation (OTH) on
an uncorroded surface of iron and bronze Cu-8Sn, in 3% sodium chloride solution. The inhibiting effect of this
formulation was investigated by electrochemical measurements. The obtained results indicate that this formu-
lation acts as good corrosion inhibitor. In the present work, the formulation (OTH) was tested as an atmos-
pheric corrosion inhibitor on corroded surface of iron and bronze coupons. The artificially aged coupons have
a similar composition to archaeological and historical objects. The state of coupons surfaces was carried out by
visual observations, and recorded by digital photographs, examination with a Scanning Electron Microscope
(SEM) coupled to Energy Dispersive Spectrometry (EDS). Electrochemical measurements were carried out
in the case of bronze coupons. From all experiments, (OTH) is a good inhibitor of historical iron and bronze
against atmospheric corrosion and also in 3% NaCl corrosive medium.
Keywords: Opuntia ficus indica, atmospheric corrosion, steel, bronze, artefacts, corrosion inhibitor
H. Hammouch et al.
Elm Cu Zn Sn Pb
At% 85 5 5 5
New Corrosion Inhibitor Containing Opuntia ficus indica Seed Extract For Bronze and Iron-based Artefacts
From this Figure, one clearly distinguishes two main 3.1.1. b In the presence of inhibitor
zones, the white zone which may correspond to the part of Figure 6 shows the SEM photo of the steel coupon with
coupon where the metal surface is not corroded, even if the presence of OTH inhibitor. The inhibition test was car-
new and very small pitting are developing due to the at- ried out with the immersion of coupon in the formulation
mospheric exposure. The black zone may correspond solution. With the presence of OTH, one observes from
the coupon general view that corrosion does not appear on
sample area. The pitting corrosion is less developed com-
pared to the reference sample after one month of exposure
(a) time to atmospheric corrosion.
The EDS analysis given in Figure 7, corresponds to
spectra obtained by analysing black and white zones of iron
coupon treated with inhibitor formulation. These spectra
reveal the presence of oxygen, nitrogen, carbon and potas-
sium in the white zone, compared to the reference sample.
The presence of these elements were absent in the blank
essay. This gives evidence to the presence of inhibitor on
(b) the coupon surface.
(b)
Table 3 - Elements composition corresponding to the two Figure 7 - EDS spectra obtained on black (b) and white (a)
zones shown in figure 4, and issued from EDS spectra zones of iron surface with OTH inhibitor treatment
151
AP°YPO¶OY§OY TELOS 30-01-08 11:03 ™ÂÏ›‰·152
H. Hammouch et al.
In black zone: the EDS analysis reveals the presence of A: Photography of artificially aged steel coupon before
sulphur and potassium compared to the reference where exposure to atmospheric corrosion:
these elements were absent Table 4 (b). This may mean that Steel coupon artificially corroded presents corrosion pits
S and K and N elements come from inhibitor present on distributed on surface, with some intact zones.
steel surface. The corrosion inhibition may be also charac- B.C: Photography of steel coupons after 10 days of expo-
terised by a decrease of oxygen percentage from 50 to 44%. sure to atmospheric corrosion,
After 10 days there is not a visual change on the coupons
surface either for reference sample (B) and he treated one
(C). Metallic coupons must be exposed for a longer period.
D.E: Photography of steel coupons after 3 months of ex-
posure to atmospheric corrosion:
After 3 months, the corrosion is well developed in
many pits of the reference sample without corrosion in-
Table 4 - values of element percentage determined by EDS hibitor essentially in the sides of the coupon (D).
analysis on white (a) and black (b) zone of steel surface The coupon treated with the inhibitor (E) kept its ini-
protected with OTH applied by immersion tial aspect and its brightness.
The effect of inhibitor is also marked by the absence of a 3.2 Bronze samples
new corrosion pits on the level of white sites, which keeps its As for the steel coupons, the bronze coupons were pre-
metal brightness compared to the state of coupons before pared by PROMET partner [9]. The patina layer was
experiments, and its capacity to limit the development of pit- formed artificially under special conditions by this partner.
ting corrosion when compared to the reference sample. Our study was to apply the OTH corrosion inhibitor for
Visual inspection of the artificially aged steel coupons analysing its behaviour for bronze in laboratory atmos-
surface shows clearly that application of OTH by immersion pheric conditions as described for steel coupons.
method for 1 hour in ethanol/ OTH formulation protects the Bronze samples with a composition analogous to that
metal surface against further atmospheric corrosion. of archaeological and historical metal objects were artifi-
The observations propose an establishment of inhibitor cially aged in a climatic chamber with moist air containing
thin film, which may protect the metal surface against at- sulphur dioxide. The patina formed on the surface was in-
mospheric corrosion. vestigated by SEM / EDS in the presence and absence of
OTH formulation applied by immersion.
3.1.2 Digital photographs The electrochemical reactivity of patina will be deter-
The condition of coupons surfaces were recorded by mined by EIS experiments.
digital photographs shown in Figure 8, in order to show the 3.2 1 SEM/ EDS analysis
protective effect of the inhibitor on samples treated by im- This technique has also been applied to compare the
mersion compared to the references ones exposed to at- bronze coupons varying condition after exposure with and
mospheric corrosion after 3 months without corrosion inhibitor.
Photographs below represent the coupons surface be- 3.2.1. a. Reference sample
fore exposure, after 10 days and after 3 months of exposure Figure 9 shows a bronze reference state of coupon cov-
to atmospheric corrosion in our laboratory. ered with patina layer. The examination of this Figure
shows a heterogeneous surface with green and brown sites.
The patina layer is discontinuous, which affects the corro-
sion resistance of this metal.
New Corrosion Inhibitor Containing Opuntia ficus indica Seed Extract For Bronze and Iron-based Artefacts
H. Hammouch et al.
4. CONCLUSION
Figure 14 - Impedance spectra of bronze sample protect- The obtained results using digital and SEM surface ob-
ed by (0.02%) of inhibitor in 3% (w/v) sodium chloride at servations, coupled with EDS spectra lead us to propose
different immersion times that OTH natural inhibitor formulation applied by immer-
sion method on the artificially aged steel surface, acts as a
good atmospheric corrosion inhibitor. The corrosion inhi-
bition efficiency is clearly marked after 3 months of expo-
sure. This inhibiting effect may correspond to an establish-
ment of inhibitor film on metal surface.
For bronze coupons, surface analysis and visual inspec-
tion, confirm the presence of inhibitor on the surface, this
was justified by electrochemical impedance, which in pres-
Figure.15 - Electrical equivalent circuit used to simulate ence of inhibitor shows a semicircle in high frequencies
EIS data for the bronze corrosion in 3%NaCl range.
with inhibitor The inhibiting film is reinforced according to the im-
mersion time certainly by corrosion products.
As can be seen in Figure 14, in the presence of inhibitor
on the metal surface, one notes that the impedance ACKNOWLEDGEMENTS
changes in shape and size. There are two semicircles de-
tected for all immersion times of bronze sample with in- This work was realized in the framework of “PROMET”
hibitor. The shape and size of impedance spectra in the project. The authors gratefully acknowledge the financial
presence of OTH inhibitor tends to stabilize after 144h of support. Also they would like to thank CNR Morocco for its
immersion. In high frequency (HF) range, the characteris- support (PICS).
tic frequency fc, at the maximum of the imaginary part is
631Hz. However, it is only about 0.63Hz for the low fre- REFERENCES
quency semicircle (LF).
In the presence of inhibitor, the first semicircle located [1] Bonnard, N., Brondeau, M.T., Lafon, D., Miraval, S.,
at high frequencies range may be associated to the in- Protois, J.-C., Schneider, O.: “Fiche toxiculogique du
hibitor film. The second semicircle may be attributed to Chromate de zinc”, Fiche Technique No 256, Institut
the charge transfer at the interface patina/3% NaCl. National de Recherche et de sécurité, Edition (2005).
154
AP°YPO¶OY§OY TELOS 30-01-08 11:03 ™ÂÏ›‰·155
New Corrosion Inhibitor Containing Opuntia ficus indica Seed Extract For Bronze and Iron-based Artefacts
[2] Wu, X., Chou, N., Lupher, D., and Davis, L.C.: ”Ben- [10] Yalçin, C. and Tekin, A.: “Monitoring of seed compo-
zotriazoles: Toxicity and Degradation”, In: Proceed- sition of prickly pear (Opuntia ficus indica ) fruits dur-
ings of the 1998 Conference on Hazardous Waste Re- ing maturation period”, Journal of the Science of
search, pp. 374-382 (1998). Food and Agriculture 83, 8 (2003) 846-849.
[3] Dermaj, A., Chebabe, D., Hajjaji, N., Joiret, S., Rah- [11] Sawaya, W.N.: “Chemical characterization of prickly
mouni, K., Srhiri, A., Takenouti, H., Vivier, V: pear seed oil, Opuntia ficus indica” J.Food Sci.47, p.
“Etude de la corrosion du bronze Cu-8%Sn)et de l’ef- 2060 (1982).
fet inhibiteur du 3-phenyl1,2,4-triazol5-thione” In: [12] Sanchez, M.A. and Cattaneo, P.: “Opuntia ficus indica
Gabrielli, C. (ed.) Acte du 17ème Forum sur les Im- (L) Mill.”, An. Asoc. Quim. Argent 75(5) :531-549
pédances Electrochimiques, Paris 257-268 (2005). (1987).
[4] Dafali, A., Hammouti, B., Aouniti, A., Mokhlis, R., [13] Srhiri, A., Derbali, Y. and Picaud, T.: “Effect of or-
Kertti, S., Elkacem, K.: “2-Mercapto-1-Methylimida- thoaminothiophenol on nickel,in 3% sodium chloride
zole as corrosion inhibitor of copper in aerated 3% Na- solution”. Journal of Corrosion Science 50, pp. 788-
Cl solution”, Ann.Chim.Sci.Mat, 25, pp. 437-446 (2000). 796 (1995).
[5] Bierwagen, G., Shedlosky, T.J., and Stanek, K.: “De- [14] Trachli, B., “Etude sur la corrosion du cuivre et sa
veloping and testing a new generation of protective protection par des méthodes non polluantes”, Co-
coatings for outdoor bronze sculpture” Progress in tutelle Doctoral Dissertation, P&M Curie University
Organic Coatings 48, pp. 289-296 (2003). (France), Ibn Tofail University, Morocco, 2001.
[6] Hammouch, H., Bennaghmouch, L., Srhiri, A., and [15] Rahmouni, K.: “Corrosion et protection des bronzes
Hajjaji, N.: “Inhibition of iron corrosion using Opuntia recouverts de patine: Etude électrochimique et spec-
extract”, FAO CactusNet Newsletter August (2005). troscopique de la surface d’objets archéologiques et
[7] El-Etre, A.Y., Abdallah, M. and E.El-Tantawy, Z.: synthèse d’une patine équivalente sur un bronze du
“Corrosion inhibition of some metals using Lawsonia commerce”, co-tutelle thesis, Ibn Tofail and Paris VI
extract”, Corrosion science 47 (2) pp 385-395 (2005). universities (2005).
[8] Heritage Malta team, ”Design and production of ref- [16] Dermaj, A., Hajjaji, N., Joiret, S., Rahmouni, K.,
erence materials” WP3 / TASK 3.2 / D3-4, Internal Srhiri, A. Takenouti, H., Vivier, V.: “Electrochemical
Report. and spectroscopic evidences of corrosion inhibition of
[9] SVUOM PROMET team, Artificial ageing, cleaning bronze by a triazole derivative”, Electrochimica Acta
and handling of bronze coupons WP3, Internal Re- 52, pp. 4654–4662 (2007).
port ( 2005).
155