AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·143

Atmospheric Corrosion inhibition of historical steel by FPTS

formulation based of triazole-thione
Ahmed Dermaj1, Driss Chebabe1, Hind Hammouch1, Mohamed Goursa1,
Najat Hajjaji1 and Abdellah Srhiri2
1
Laboratory of Electrochemistry, Corrosion and Environment, Faculty of sciences
2
SERVICHIM Sarl society corrosion inhibitors production, Morocco
Kenitra city 14000,
BP 133 MOROCCO
dermaj@gmail.com

Several techniques have been used to conserve archaeological metal objects: mechanical cleaning, elec-
trolytic treatment and even oil immersion. In this work, we have tested the inhibiting effect against corro-
sion of formulation, which is based on a synthetic compound (PTS). We have examined the inhibition effi-
ciency on corroded iron either in the presence and the absence of 3% NaCl solution. The results obtained
using different application methods (brush and immersion) after one month of exposure have shown that
the inhibiting effect was very important in the event of atmospheric corrosion. The surface analyses by
SEM/ EDX confirm these results.

Keyword: inhibitor, corrosion, archaeological iron, atmospheric corrosion

1. INTRODUCTION
The corrosion of a metal is often considered as an in-
convenience because it implies a change of the objects in
the course of time. The exhibition of an old object is ac-
companied by a change depending on the environmental
conditions, which can sometimes accelerate objects
degradation.
The knowledge of the corrosion system, its initiation
as well as its evolution, depends on the choice of the con-
servation techniques and different methods used to pro-
tect the objects against corrosive agents [1].
For protection against the corrosion, many ways are
accessible [2]: manufacture new metals resistant to corro-
sion, establish physical barrier to isolate the metal using
organic coatings as example, or apply an electrolyte using
corrosion inhibitors.
The use of the inhibitors is an adapted and convenient
method to protect metals in the most situations.
The state of conservation of an archaeological object
essentially depends on the nature of the alloy from which
it has been manufactured, as well as the environment ag-
gressiveness [3].
In this study, we are interested in protection of the fer-
rous objects. At first, we have studied the electro-chemi-
cal behaviour of iron in different environments (marine,
acidic, alkaline…) [4-7].
Then, we have tested the effect of a formulation in-
hibitor containing a synthetic compound (PTS), on the
corroded iron coupons in the presence and absence of 3
wt% NaCl solution.
The obtained results with two applied methods, brush
143
and immersion show that after one month, the inhibition
effect is very important. The EDX surface analysis con-
firms these results.
2. EXPERIMENTAL CONDITIONS
2.1 Material: corroded iron
All the coupons are iron based metal measuring 7cm
length, 5cm width and of 2mm thick. These coupons were
corroded artificially to simulate the behaviour of historical
and archaeological metal artefacts. Analytical work on the
samples was carried via atomic emission arc induced spec-
troscopy. Analyses were carried out on three different
spots on the metal surface. Each spot was analyzed in tripli-
cate and an average value in % for each element was ob-
tained. This composition weight %(wt%) is 0.157 wt % C,
0.201 wt % Si, 0.519 wt % Mn, 0.007 wt % P, 0.009 % S
>99 wt% Fe, total remaining elements < 0.2%.
2.2 SEM-EDX
The micrographic negatives have been taken out us-
ing SEM (HV 16 Kv), equipped by EDX analysis (ZAF
quantification standard less).
2.3 Inhibitor
The products used as organic corrosion inhibitors is as
follow: Formulation FPTS of 3-phenyl-1, 2,4-triazole-5-
thione (PTS), synthesized in our laboratory.
2.4 Studying methods: Atmospheric corrosion
Before beginning experiments, iron samples were
cleaned with a brush, and then degreased with ethanol.
AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·144
A. Dermaj et al.
The inhibitor formulation, was used either by immersion of
coupons into ethanol solution of FPTS for an hour, or by
brushing FPTS formulation directly on the iron surface.
3. RESULTS AND DISCUSSION
3.1 Iron samples
After the preparation of iron coupons, visual inspec-
tion was carried out, and the condition of iron samples
during this study was documented using digital pho-
tographs. Figure 1 represents the condition of coupon
before application of the inhibitor.
Face 1 Face 2
Figure 1 - Iron sample before FPTS application
In general, these coupons present two different zones:
— White zone, characterised by its brightness and ab-
sence of corrosion pits.
— Black zone corresponds to corrosion pits dispersed
in the whole surface indicating the development of
artificial corrosion.
After the mechanical cleaning of these metal coupons,
we have chosen a group of five samples A, B, C, D and E.
After the application of the inhibitor on these
coupons by immersion or brush in the presence and the
absence of 3% NaCl solution, they were exposed to am-
bient temperature 25oC and controlled relative humidity
between 63% to 68%) (Figure 2).
A: Inhibitor by immersion without 3% NaCl solution
B: Inhibitor by brush in the presence of 3% NaCl solution
C: Inhibitor by brush without 3% NaCl solution
D: Reference with 3% NaCl solution
E: Reference without 3% NaCl solution
A B C D E
Figure 2 - state of surface samples after 10 days of exposure
In spite of the bad quality of the photos, all coupons
don’t undergo any visual modifications except the refer-
144
ence with 3% NaCl solution treatment that showed a
corrosion accelerated on the whole surface which seems
to cover with corrosion products. The general view of
this case coupon is dark.
3.2 SEM and EDX analysis
The obtained results after a month of exposure to
the atmospheric corrosion, with and without inhibitor
are illustrated below.
3.3 Reference sample exposed to atmospheric corrosion:
To examine the effect of chloride solution on the
iron coupons behaviour, we have compared two cases:
coupons with 3% NaCl solution sprayed on the surface
and coupons without 3% NaCl.
3.3.1 Without 3% NaCl solution
The state of the reference sample in the absence of
3% NaCl solution is illustrated by the SEM photo shown
in Figure 3.
White site 100Ìm
(B)
Black site
(A)
Figure 3 - SEM photo of a reference sample
in the absence of 3% NaCl
This photo shows the existence of black and white
area. So as to understand the difference between the two
observed sites on samples areas, EDX analysis coupled
to SEM observations was carried out. The correspond-
ing spectrum is shown in Figure 4.
Black site (A)
White site (B)
Figure 4 - EDX spectra of a reference sample
in the absence of 3% NaCl after a month of exposure
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Atmospheric Corrosion inhibition of historical steel by FPTS formulation based on triazole-thione

The examination of this Figure indicates that analysis

at the black site shows an important quantity of oxygen,
and less weight percentage of iron. Other chemical ele-
ments were detected as shown in Tables 1A and 1B.

Table 1 A - EDX analysis of black site (A)

Table 1B - EDX analysis of white site (B)

Figure 6 - EDX spectra of reference sample in presence

of 3% NaCl after one month of exposure

In the event of white site, the peak attributed to oxygen
is nonexistent. The corresponding analyses show the pres-
ence of iron peaks with high intensity.
The white zone which is resistant to corrosion contains
the basic metal elements.
The black zone contains in addition to the basic ele-
ments, a great percentage of the oxygen and the carbon
which may indicates corrosion at the level of this zone.
3.3.2 In the presence of 3% NaCl solution
Our visual assessment shows a big difference with the
sample without sodium chloride. The metal coupon is
completely corroded as shown in Figure 5.
The Table 3 shows the % of three elements present in
corrosion products.
Table 3 - EDX analysis of a reference sample
in the presence of 3% NaCl
We note the following:
— The existence of only one zone in the whole area
formed by a layer of the corrosion products.
— Appearance of rust layer which is fissuring and cover-
ing all sample surfaces.
— A presence of higher wt% of oxygen and Cl- in the cor-
rosion products layer. This may lead to propose a for-
mation of oxychloride iron as corrosion product, cover-
ing the sample area.
— So the effect of the chloride ions is marked well.

3.4 Application of the inhibitor (FPTS) by brush method

50Ìm 3.4.1 SEM observations and EDX analysis in the absence

Figure 5 - SEM photo of a reference sample
in the presence of 3% NaCl
The corrosion products layer is heterogeneous and fis-
sured. The observed heterogeneity may be attributed to
oxide and chloride corrosion products formed on the
coupon, which was confirmed by EDX analysis showing
oxygen, chloride and iron peaks in Figure 6.
145
of 3% NaCl
The results obtained with FPTS on iron coupons in the
absence of 3%NaCl are given in Figures 7 and 8.
The microscopic observations in Figure 7 show the
presence of white zones corresponding to a basic iron met-
al uncorroded, and also the presence of corrosion pits rich
on iron oxides. More information about the presence of in-
hibitor film on the surface are carried out by EDX analyses
as given in Figure.8.
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A. Dermaj et al.
B 100Ìm A 20Ìm
Figure 7 - SEM photo of iron coupon coated by FPTS
in absence of 3%NaCl after one month of exposure.
Black site (A)
White site (B)
Figure 8 - EDX spectra of iron coupon protected by FPTS
in the absence of 3%NaCl after one month of exposure
There are differences on elemental composition be-
tween the distinguished zones. The white zone composi-
tion is represented in Table 4.
Table 4 - EDX analysis of white site for iron
coupon protected by FTPS in the absence of 3%NaCl
Compared to a reference composition of the white site,
we note the apparition of new elements when the FPTS is
present on the coupon surface like S, C, and K and which
come only from inhibitor formulation. EDX analysis of
black zone is represented on Table .5
146
Table 5 - EDX analysis of black site for iron coupon
Protected with FPTS in the absence of 3%NaCl
From Table 5, the presence of C, S and K attributed to
the inhibitor film, and also it appears that the oxygen per-
centage in this zone compared to the reference one, de-
creases from 50% to 27%, which may be due to the pro-
tecting character of the FPTS formulation.
3.4.2 SEM observations and EDX analysis in the pres-
ence of 3% NaCl
SEM observations of iron coupon presented in Figure
9 show the existence of two zones which correspond to the
EDX spectra represented in Figure 10. The EDX analysis
permits to note only one zone. This leads us to conclude
that the inhibitor forms thick corrosion products on the
metal area as shown in Figures 9 and 10.
200Ìm 500Ìm
Figure 9 - SEM photo of iron coupon with FPTS
in presence of 3%NaCl after one month of exposure
A remarkable difference is seen in samples surface be-
tween photographs obtained in the presence and the ab-
sence of inhibitor with of 3 % NaCl as a corrosive solution.
This difference may be explained by a decrease of chloride
from 5% to 0.12% as shown in Table 6, and oxygen from
57.64% to 22% when the inhibitor was added, also the
presence of Nitrogen, Carbon and Sulphur was noted .
Figure 10 - EDX spectra of iron coupon contains FPTS in
presence of 3%NaCl solution after one month of exposure
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Atmospheric Corrosion inhibition of historical steel by FPTS formulation based on triazole-thione
Table 6 - EDX analysis of iron coupon with FPTS
in the presence of 3%NaCl
3.5 Inhibitor applying by immersion
The inhibitor FPTS was also tested by immersion of the
iron coupon in solution of 20ml of ethanol containing 15
mg of inhibitor in the absence of 3% NaCl during 1 hour.
The choice of percentage of the inhibitor is based on
the concentration effect of PTS(3-phenyl-1, 2,4-triazole-5-
thione) [10].
The visual observation shows a remarkable difference
of the surface state compared to the reference. The pro-
tected iron coupon presents a good resistance to atmos-
pheric corrosion; corresponding SEM photo reported in
Figure 11.
100Ìm
Figure 11 - SEM photo of iron coupon with FPTS in the
absence of 3% NaCl solution after one month of exhibition
EDX spectra and elemental composition are reported
in Figure 12 and Table 7 respectively
Figure 12 - EDX analysis of metal coupon (A) contains
FPTS in the absence of 3% NaCl solution
after one month of exposure
147
Table 7 - EDX analysis of iron coupon with FPTS applied
by immersion
The obtained results show the existence of sulphur, ni-
trogen and an increase of carbon percentage due to the in-
hibitor presence on the surface coupon.
Comparison with reference system in the presence and
the absence of 3% NaCl indicates a decrease of oxygen
percentage, justifying the inhibiting effect of the FPTS ap-
plied by immersion method.
After three months of exposure, the state of iron sur-
faces is represented in Figure 13:
A C
B
D E
Figure 13 - The state of surface iron coupon
(A, B, C, D and E) after three months of exposure
A: reference without inhibitor and 3%NaCl solution
B: inhibitor by immersion without 3% NaCl solution
C: inhibitor by brush without 3% NaCl solution
D: reference without inhibitor but with 3% NaCl solution
E: inhibitor by brush in the presence of 3%NaCl solution
A general observation of the iron surface after 3
months shows the presence of pits on the whole surface for
the reference coupon. For coupon treated by immersion of
FPTS manifests a development of corrosion in the level of
pits.
— The system brush is more resistant against atmospheric
corrosion (not evolution of the corrosion both in the
level of pits and white site) In the presence of 3% NaCl
solution, all coupon surfaces were severely corroded.
— For the system brush with NaCl, the development of
active corrosion on the black site of iron coupon was
seen.
4. CONCLUSION
This study has been realized by visual inspection, spectro-
scopic methods (SEM and EDX) techniques to study ar-
AP°YPO¶OY§OY TELOS 30-01-08 11:03 ™ÂÏ›‰·148
A. Dermaj et al.
chaeological iron. From all these techniques we have
proved the inhibiting effect of FPTS against atmospheric
corrosion. The effect of FPTS leads to strong reduction of
oxygen percentage and ions chloride.
ACKNOWLEDGEMENTS
This work was realized in the framework of “PROMET”
project. The authors gratefully acknowledge the financial
support. Also they would thank CNRST Morocco for its
collaboration (PICS).
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