Accepted Manuscript

Title: Corrosion inhibition of iron in acidic solution by a green

formulation derived from Nigella sativa L.

Author: M. Chellouli D. Chebabe A. Dermaj H. Erramli N.

Bettach N. Hajjaji M.P. Casaletto C. Cirrincione A. Privitera
A. Srhiri

PII: S0013-4686(16)30803-9
DOI: http://dx.doi.org/doi:10.1016/j.electacta.2016.04.015
Reference: EA 27050

To appear in: Electrochimica Acta

Received date: 30-9-2015

Revised date: 4-4-2016
Accepted date: 5-4-2016

Please cite this article as: M.Chellouli, D.Chebabe, A.Dermaj, H.Erramli, N.Bettach,
N.Hajjaji, M.P.Casaletto, C.Cirrincione, A.Privitera, A.Srhiri, Corrosion inhibition
of iron in acidic solution by a green formulation derived from Nigella sativa L.,
Electrochimica Acta http://dx.doi.org/10.1016/j.electacta.2016.04.015

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 Corrosion inhibition of iron in acidic solution by a green formulation
derived from Nigella Sativa L.

M. Chellouli a, D. Chebabe a, A. Dermaj a, H. Erramli a, N. Bettach a, N. Hajjaji a,

M.P. Casaletto b,*, C. Cirrincione b, A. Privitera b, A. Srhiri c

a
Laboratory of Material, Electrochemistry and Environment, University IbnTofail, Faculty of
Sciences, Kenitra, Morocco
b
Consiglio Nazionale delle Ricerche, Istituto per lo Studio dei Materiali Nanostrutturati, Via Ugo La
Malfa 153, Palermo, Italy
c
Servichim Sarl, 101 Rue Maamoura, n. 10 Kenitra, Morocco

*Corresponding author:

Dr. Maria Pia Casaletto, Consiglio Nazionale delle Ricerche, Istituto per lo Studio dei Materiali

Nanostrutturati, Via Ugo La Malfa 153, Palermo, Italy

Phone: +39 091 6809378

E-mail address: mariapia.casaletto@cnr.it

Abstract
In this work the corrosion inhibition of iron in acidic solution by a formulation based on the oil

extracted from the seeds of Nigella Sativa L. (labeled as FBN) was investigated by means of

potentiodynamic polarization, electrochemical impedance spectroscopy and weight loss

measurements. Results showed that the formulation acts as a good mixed type (cathodic/anodic)

inhibitor. The dissolution rate decreased with the increase of the FBN concentration and the

immersion time. An inhibition efficiency of 99% was reached for FBN concentration at 2500 ppm.

Surface analysis of the samples was performed by Scanning Electron Microscopy coupled with

chemical analysis (SEM-EDS) and X-ray Photoemission Spectroscopy (XPS). Results confirmed

1
a good protective action of the FBN film on the iron substrate in acidic solution. The FBN

formulation is a not toxic and environmentally safe product, as determined by acute toxicity tests,

and can be fruitfully used for a sustainable conservation of iron-based artifacts.

Keywords: Corrosion inhibitors; Historical iron artifacts; Potentiodynamic polarization; EIS;

Surface analysis.

1. Introduction
Corrosion of metallic artifacts is one of the important issues in the preservation and conservation

of ancient and historical artworks. Metals from Cultural Heritage may suffer from degradation

phenomena during the archaeological burial, from indoor atmospheric corrosion during exhibition

or storage in uncontrolled environment conditions and from outdoor atmospheric degradation in

the case of Monumental Heritage. Electrochemical techniques can be used in Conservation Science

both as analytical methods for the investigation of the constitutive materials and alteration products

of the artifacts and for the assessment of the performance of corrosion inhibitors, and as

restorative/conservative methods. Recently, potentiodynamic polarization and electrochemical

impedance spectroscopy (EIS) have been successfully used for the analysis of the anti-corrosive

efficiency of protective coatings and films applied to ancient metals [1]. Conservation materials

and processes should be used following standardized, reliable and reproducible procedures for

protecting the surface, stabilizing the artifact and avoiding any further degradation induced by

humidity, corrosive agents and polluted atmosphere. Archaeological metallic objects exhibited in

museums often underwent spontaneous degradation due to aggressive environment [2, 3].

Furthermore, environmental protection and preservation of the health of professionals working in

2
the Conservation of Cultural Heritage should be addressed for a sustainable scientific approach

[4]. The development of alternatives, safe, reliable, non toxic and long-lasting materials and of

tailored applications and validation methods for the conservation of metallic artworks are

nowadays a mandatory demand. Environmental-friendly approaches and safety solutions should

be used and new green and low toxic corrosion inhibitors should be found in order to replace the

hazardous materials commonly and extensively used in the daily practices of conservation.

Nowadays eco-friendly compounds, especially derived from plant extracts, draw the attention as

effective inhibitors of corrosion protection of metallic substrates in acidic solutions due to their

biodegradability, non-toxic nature, economical aspects (availabilty of raw material sources in large

scale and low cost extraction processes) [5].

In this context in the last decade a consolidated collaboration between CNR (Italy) and CNRST

(Morocco) was carried out for investigating both chemically synthesized and naturally-derived

products as corrosion inhibitors [6-12]. The main application of corrosion inhibitors in

conservation is in the form of coatings or “dry-films”, chemically bonded to the surface of the

metal. Since the archaeological and historical artefacts are unique and cannot be sacrificed for

scientific reasons, reference materials are required to evaluate the anticorrosive properties of

innovative compounds toward corrosion. For this purposes modern reference copper, silver and

iron-based alloys were intentionally produced with a chemical composition and microstructure

similar to that of ancient alloys and were used as substrates for coatings production [13-16]. A

detailed investigation of new environmentally friendly and/or naturally produced corrosion

inhibitors for copper-based artifacts was carried out in order to find possible alternatives to the use

of benzotriazole, which is toxic and suspect carcinogenic. The assessment of the inhibiting

properties was realized by means of electrochemical and surface analytical techniques. In order to

3
focus primarily on safety and health concerns, natural plant extracts were tested as corrosion

barrier and/or inhibitors due to their ease of use, low cost and safety properties for both humans

and the environment [7-11]. A formulation based on the oil extracted by the seeds of Nigella Sativa

L. was investigated for bronze and iron corrosion in a marine environment (3% NaCl solution) [9,

12]. Recently, the application of plants extracts as corrosion inhibitor of low carbon steel in acidic

solution has been addressed in the literature [17-19]. Abdel-Gaber et co-authors reported the

positive effect of extracts of Nigella Sativa L. (Black cumin), Chamomile (Chamaemelum mixtum

L.), Halfabar (Cymbopogon proximus) and kidney bean (Phaseolus vulgaris L.) on the corrosion

inhibition of steel in H2SO4 solution [19]. The Nigella Sativa L. is a member of the botanical family

of Ranuncolacee and its seeds derive from a ripe fruit that grows abundantly in the Mediterranean

basin, Eastern Europe, Middle East and Western Asia. Commonly used in food and cooking

preparations, it has also a role as effective alternative medicine. Seeds are rich in several

constituents as primary or secondary metabolites, the content of which varies according to

geographical and climatic conditions. In the present work the properties of the Nigella Sativa L.

formulation as iron corrosion inhibitor were tested in an acidic solution simulating acid rain of an

industrial atmosphere in an urban area. Films of this formulation on iron-based substrates, with a

chemical composition and structure similar to historic artifacts, were produced by immersion at

room temperature and then submitted to corrosion. Experiments were performed as a function of

the concentration and of the immersion time. The inhibition was evaluated by means of weight

loss measurement, potentiodynamic polarization and electrochemical impedance spectroscopy.

The surface chemical and physical characterization was performed by X-ray Photoemission

Spectroscopy (XPS) and Scanning Electron Microscopy coupled with chemical analysis (SEM-

EDS).

4
The novelty of this work relies on the application of the Nigella Sativa L. formulation as a non-

toxic and environmentally friendly corrosion inhibitor for iron in an acidic medium for the

conservation of metallic artefacts in museums, outdoor low carbon steel artifacts and also objects

from industrial archaeology.

2. Experimental

2.1. Materials and chemicals

A reference low carbon steel alloy with the typical Widmanstätten microstructure observed in

many historical iron-based artifacts was used in this work. The iron-based coupons was produced

in the framework of the European PROMET project [13] with the following chemical composition:

0.52 wt % Mn; 0.20 wt % Si; 0.16 wt % C; 0.009 wt % S; 0.007 wt % P and Fe > 99 wt % as given

by the manufacturer (SVÚOM Company Ltd., Prague, Czech Republic).

Corrosion of the iron-based alloy was performed in an aqueous solution simulating acid rain of an

industrial atmosphere in an urban area near the seaside with high degree of pollution [20]. The

solution was prepared with the following composition: 0.2 g/l Na2SO4, 0.2 g/l NaHCO3 and 0.2

g/l NaCl acidified by sulfuric acid at pH = 3.6. All chemical reagents were of analytical grade and

the experiments were carried out at 293K temperature.

A formulation based on the oil extracted by the seeds of Nigella Sativa L., labeled as FBN, was

synthesized, purified and characterized in the laboratories of the University Ibn Tofail in Kenitra

(Morocco) and tested as corrosion inhibitor. The Nigella Sativa L. seeds were collected during the

flowering and seedling periods from the North region of Morocco and identified by the Botanic

Laboratory of the Department of Biology, Faculty of Sciences, University Ibn Tofail, Kenitra,

(Morocco). The seeds were dried at 323K for 48h and then mechanically powdered by grinding.

5
Oil extraction was performed by cyclohexane in a Soxhlet apparatus for 8h. The organic solvent

was removed by using a rotary evaporator at 313K and then the oil was filtered and stored at 277K.

The chemical composition of the oil was determined by gas-chromatography by dosage of methyl

esters after the trans-esterification of the oil [12,19]. The oil resulted essentially based on fatty

acids: linoleic acid (56%), oleic acid (23%), palmitic acid (12%) and stearic acid (3%) were found

as major constituents. In this study weight loss and electrochemical measures were carried out by

using a concentration of the FBN formulation in a range from 250 to 2500 ppm by weight.

2.2. Gravimetric studies

As well known, the electrochemistry of corroding metals involves two or more half-cell reactions.

In the case of iron corrosion under our experimental conditions (aerated acidic solution at pH=3.6),

oxygen reduction represents the cathodic semi-reaction.So the half-cell reactions can be expressed

by the following equations:

Fe Fe2++ 2e- (1)

O2 +4H++4e- 2H2O (2)

The quantity of solid iron lost by corrosion can be determined either by measuring the weight loss

(or thickness lost) of the metallic iron specimen [21] or by measuring the concentration of

dissolved Fe2+ ions that are produced in solution.

Gravimetric method measuring the weight loss or thickness lost of the metallic iron specimen and

inductively coupled plasma atomic emission spectroscopy (ICP-AES) were used in this study for

the evaluation of the corrosion rate of iron specimens.

Iron-based samples with dimension of 2cm x 1cm x 0.2cm were used for weight loss

measurements. Prior to all measurements, the exposed area was mechanically abraded by 400, 600,

800, 1000 and 1200 grades emery papers. Specimens were washed thoroughly with distilled water,
6
degreased and dried with acetone. Gravimetric measurements were carried out in a double walled

glass cell equipped with a thermostated cooling condenser. The weight loss W(mg) was

determined by weighing the cleaned samples before and after 24h of immersion at 293K in the

corrosive solution in the absence and in presence of different concentrations of FBN. The

gravimetric test was performed by using an analytical balance with a precision of 0.1 mg. Weight

loss allowed calculation of the mean corrosion rate in mg cm-2 h-1.

The corrosion rate (ν), and the inhibition efficiency (IE%) were calculated by the following

equations:

𝑊
𝜈= (3)
𝑆𝑥𝑡

Where W is the weight loss in mg; S is the surface of the specimen in cm2 and t is the immersion

time in s.

ν0−ν
𝐼𝐸% = x 100 (4)
ν0

Where ν0 and ν are the corrosion rate of iron specimens in the absence and presence of the FBN

formulation, respectively.

Results obtained by this method should be considered with moderation because, in general, it is

difficult to strip the corroded surface. So they have only a qualitative relevance.

The FBN inhibition efficiency was also calculated independently by using the ICP-AES technique

for iron elemental determination as trace element in solution. A Perkin Elmer Optima DV4300

inductively coupled argon plasma emission spectrometer was used. The concentration of the

dissolved Fe2+ ions in the acid rain solution was determined both in the absence and in presence

of different concentrations of FBN at 293K.

7
As in the case of the weight loss measurement, this method presents a shortcoming, because it

measures only the metal ions in solution without measuring the ions remained in the corrosion

products. In order to determine the main kinetic parameters connected to corrosion,

electrochemical techniques such as potentiodynamic polarization and electrochemical impedance

spectroscopy were used.

2.3. Electrochemical measurements

Prior to each measurement, the specimens were polished with different grades of emery papers as

above, degreased with acetone and rinsed in distilled water before insertion into the test solution.

The cylindrical rods, mounted into glass tubes of appropriate diameter using epoxy resin, offered

an active flat disc shaped surface of 1cm2 geometric area to contact the electrolyte. Experiments

were conducted in a conventional three electrode cell assembly operated in a Faraday cage to

minimize ambient electrical noises: the iron surface was the working electrode; a rectangular

platinum foil was used as counter electrode and the saturated calomel electrode was the reference

electrode. Before polarization and impedance experiments, the working electrode was immersed

in the test solution for 30 min to establish a steady state open circuit potential (OCP). After

measuring the OCP, the electrochemical measurements were performed by using a Bio-Logic SP-

200 electrochemical apparatus interfaced with a computer.

The cathodic and anodic polarization curves were performed using a scan rate equal to 1 mVs-1.

The automatic ohmic drop compensation (ZIR) was performed by using Bio-logic SP-200

instrument. The electrochemical parameters values (Icor , Ecor, βc et βa) were determinated using the

EC-LAB V 10.36 software.

The inhibition efficiency (IE %) was calculated from potentiodynamic polarization curves using

the following equation:

8
 Icorr,0 −Icorr
IE % = x 100 (5)
Icorr,0

where Icorr,o and Icorr are the corrosion current density in the absence and presence of the inhibitor.

Electrochemical impedance studies were carried out by using signals of 10 mV amplitude in the

frequency spectrum range from 100 kHz to 0.01Hz at the stable open circuit potential (OCP). The

registration of EIS spectra started after 30 min of immersion time. Impedance data were analyzed by

the EC-LAB software [22].

The inhibition efficiency at different concentrations of FBN was evaluated by the following equation:

IE % = Rp - R°p x 100 (6)

Rp

Where Rop and Rp are the polarization resistances for the uninhibited and inhibited solutions,

respectively [23].

2.4. Surface characterization by SEM-EDS and XPS

The morphology and the chemical composition of the surface of a 2500 ppm FBN film on iron

substrates were investigated both before and after the corrosion in the acidic medium.

The surface morphology was investigated by Scanning Electron Microscopy (SEM) coupled with

Energy Dispersive Spectroscopy (EDS) using a Leica Stereoscan 440 electron microscope and a

Princeton Gamma-Tech energy dispersive spectrometer with an accelerating voltage of 20 kV.

SEM images were recorded after immersion of the samples for 24h in acid rain medium both in

the absence and in the presence of 2500 ppm FBN.

9
The surface chemical composition of the pure iron substrates and the FBN films was investigated

by X-ray Photoelectron Spectroscopy (XPS) both before and after the corrosive attack by the acidic

solution. Before experiments, the iron surface was polished by emery papers (from 600 to 2400),

then rinsed with distilled water, sonicated in ethanol and then dried in air overnight. Film of the

formulation of Nigella Sativa L. were produced by immersion of the iron substrate in a 2500 ppm

FBN ethanolic solution for 1h. Samples were submitted to corrosion by immersion in the acidic

solution for 1h, then rinsed with distilled water and dried in air overnight. All experiments were

performed at room temperature.

Photoemission spectra were collected by a VG Microtech ESCA 3000 Multilab spectrometer,

equipped with a standard Al Kα excitation source (hν=1486.6eV), a multi-channeltrons detection

system and an ultrahigh vacuum (UHV) chamber with a base pressure lower than 1 x 10-6 Pa during

data collection. The hemispherical analyzer operated in the CAE mode at a constant pass energy

of 20eV. The binding energy (BE) scale was calibrated by measuring C 1s peak (BE = 285.1 eV)

from the adventitious carbon. The accuracy of the energy measure is ±0.1 eV. Photoemission data

were collected and processed by using the VGX900 software. Data analysis was performed by a

nonlinear least square curve-fitting procedure with a properly weighted sum of Lorentzian and

Gaussian component curves, after background subtraction according to Sherwood [24]. Surface

relative atomic concentrations were calculated by a standard quantification routine including

Wagner’s energy dependence of attenuation length [25] and a standard set of VG Escalab

sensitivity factors. The uncertainty on the atomic quantitative analysis is about ± 10 %.

3. Results and discussion

3.1. Gravimetric methods

10
The weight-loss of iron specimens was investigated in the absence and presence of different

concentrations of FBN in acid rain solution after 24 h of immersion time at 293K. The values of

corrosion rate (ν) and the inhibition efficiency (IE %) are reported in Table 1.

The corrosion rate (ν) decreased with an increase of FBN concentration in the solution due to the

interaction of the inhibitor molecules with the iron surface. The best corrosion inhibition efficiency

value was reached for 2500 ppm of FBN concentration as shown in Table 1.

The ICP-AES technique was also used to determine the concentrations of dissolved Fe2+ ions in

the acid rain solution after 24h in the absence and presence of different concentrations of FBN.

Results of the concentration of Fe2+ ions expressed in mg/l are reported in Table 2, along with the

calculated inhibition efficiency.

The concentration of dissolved Fe2+ ions in solution decreased as the FBN inhibitor concentration

increased. The inhibition efficiency increased with the FBN concentration up to a maximum value

for a concentration of 2500 ppm of FBN.

As shown in Table 1 and Table 2 a good corrosion inhibition efficiency was obtained by a

relatively low FBN concentration. The obtained inhibiting effect may be attributed to the formation

of a protective film on the iron surface.

Electrochemical techniques were used for a detailed investigation of the corrosion of iron in the

acidic medium, both in the absence and in the presence of FBN.

3.2. Potentiodynamic polarization

11
3.2.1. Open circuit potential

As early emphasized, special attention was accorded to the stability of the open circuit potential

OCP, before each polarization measurement. Moreover, the measure of the variation with time of

the OCP of the working electrode is important for the definition of the domain of corrosion, partial

and complete inhibition and the determination of the inhibitor-threshold concentrations.

In the present study, the variation of Ecor with time was determined in acidic solution in the absence

and presence of different concentrations of FBN at 293 K. Results are reported in Fig. 1.

Fig. 1. Variation of the open-circuit potential of iron in acidic rain solution

at different FBN concentrations.

As shown in Fig. 1, the corrosion potential (Ecor) of the iron electrode in the pure acid rain solution

tends towards more negative value first, giving rise to a short step. This behavior was already

reported by West [26] and could represent the breakdown of pre-immersion, air formed oxide film

on the surface [27]. This step is followed by the growth of an oxide film until a steady state

potential is established [28].

3.2.2. Potentiodynamic curves

In order to highlight the behavior of FBN as cathodic, anodic or mixed type inhibitor and its effect

on the kinetics of the electrochemical reaction, polarization measurements were carried out in the

absence and presence of different concentrations of FBN at 293K. The cathodic and anodic

polarization curves of the iron substrate in acidic solution in the absence and in the presence of

different concentrations of FBN are reported in Fig. 2. All of these curves were obtained after 30

12
min immersion of the electrode in the electrolytic solution at open circuit potential (Eoc) and after

performing the automatic ohmic drop compensation (ZIR). Then the cathodic and anodic

polarization curves were plotted separately in Fig. 2a and Fig. 2b, respectively.

As shown in Fig. 2, the addition of the FBN formulation produced a positive shift of Ecor as the

concentration of the inhibitor increased. Furthermore, the presence of the inhibitor affected both

the anodic behavior and the cathodic behavior.

Fig. 2. Potentiodynamic polarization curves of iron in acidic solution at different FBN

concentrations in the cathodic (a) and anodic (b) domain, respectively, after ohmic drop
compensation (ZIR).

As shown in Fig. 2a, in the cathodic domain the low value of the corrosion potential in the absence

of inhibitor (Ecor = -0.524 V/SCE), indicated the active state of corrosion. The shape of the cathodic

curves showed a plateau attributed to the oxygen diffusion process, indicating that mass transport

is an important factor which must be considerated in the cathodic process [29]. Addition of FBN

to the corrosive medium is accompanied by a displacement of Ecor towards a positive potential

direction. The disappearance of the diffusion plateau, obtained in the case of the blank, and the

appearance of a wide domain of linearity, with the decreasing of the cathodic current densities,

indicates that the inhibitor changes the cathodic behaviour.

In the anodic domain reported in Fig. 2b, the values of the anodic current density without inhibitor

increased promptly at the vicinity of Ecor and tended to stabilize toward a value of 11.9 mA/cm2,

which is too high to correspond to the passivation of metal [18].

In the presence of the inhibitor, the anodic polarization curves showed a decrease of the current

density values with the increase of the FBN concentration. At low FBN concentration the anodic

effect of inhibitor is limited to the vicinity of corrosion potential. At high anode overvoltage,

13
anodic current densities increased rapidly and approached the value obtained with the pure acidic

solution (blank).

Starting from the concentration of 1000 ppm of FBN, the appearance of a current plateau in a wide

potential range was observed. The corresponding current value is in the order of 2.33 μA.cm-2.

This indicates that the metal surface is protected by the inhibitor. Starting from this concentration

of FBN, the obtained current density value at potential -0.2 V/SCE is very low compared to the

blank at the same potential. This low current density value obtained in presence of FBN may be

attributed to a passivity of iron resulting from the formation of an inhibitor film on the surface

which is kept up to 0.2V/SCE.The kinetic parameters of the corrosion of the iron electrode were

determined by the EC- lab software. Results are summarized in Table 3.

As shown in Table 3, the value of Icorr decreased as a function of the addition of inhibitor, starting

from 72.59 up to a value of 0.51μA.cm-2 at 2500 ppm of FBN. The inhibition efficiency increased

with increasing FBN concentrations. The inhibition efficiency around 99% indicates a good

protective effect of the FBN inhibitor against iron corrosion in acidic solution at the considered

pH.

Results allowed us to conclude that the FBN is a mixed inhibitor which acts by decreasing the

current density and displacing the corrosion potential in the anodic direction. This behavior

becomes marked when the concentration of FBN increases. This good inhibiting effect of FBN

may be related to its adsorption on the electrode surface with the consequent formation of a barrier

film.

3.3 Electrochemical Impedance Spectroscopy

14
Electrochemical Impedance Spectroscopy (EIS) provides information about the kinetics of the

electrode processes and the surface properties of the investigated systems. Mechanistic

information can be obtained from the shape of the impedance diagram [30]. Data analysis can be

performed by the adequate choice of structural models of the interface [31, 32] and results are

widely used for the investigation of the corrosion inhibition processes [33, 34]. EIS measurements

were performed as a function of the inhibitor concentration and as a function of the immersion

time.

The complex plane impedance plot of the iron electrode in the pure acidic solution at 293K (blank

sample) is reported in Fig. 3.

Fig. 3. Nyquist plot of the iron electrode in acidic solution at 293K.

As shown in Fig. 3, in absence of the inhibitor, the impedance diagram showed the appearance of

two capacitive loops (RHF, CHF) and (RLF, CLF) with the beginning of the inductive loop at low

frequencies [35]. Due to the role of mass transport and the difficulty to distinguish the charge

transfer, we considered the polarization resistance Rp for evaluation of the corrosion rate and the

inhibition efficiency.

The complex plane impedance plots recorded for iron in acidic solution as a function of different

FBN concentrations at 293K are shown in Fig. 4. The addition of FBN at various concentrations

also displayed a capacitive behavior of the iron in the acidic solution.

Fig. 4. Nyquist plots recorded for iron in acidic solution

as a function of FBN concentration at 293K.

15
Examination of the Nyquist plots in Fig. 4 shows a change in the shape of the loops, with the

increase of the size of the loops in the HF range. The shape of these diagrams suggests that in the

presence of FBN the inhibiting effect may be attributed to a change of interfacial behaviour.

The polarization resistance Rp, determined from the extrapolation of the impedance spectra

towards the low frequency limit, increased with the inhibitor concentration. The initial Rp value of

about 0.39 kΩ.cm2 in the acidic solution without FBN, increased up to 2.15, 2.56, 73.91, 126.37

and 206.27 kΩ.cm2 for FBN concentrations of 250, 500, 1000, 2000, 2500 ppm, respectively.

However, these diagrams cannot be explained by using only a single RC circuit, thus a second RC

circuit was added in the model. The use of such an electrical equivalent circuit is in agreement

with previous results [36]. Those RC couples can be ascribed to the following contributions: the

high frequency contribution (Cf -Rf) can be ascribed to the dielectric character due to the formation

of thin film on the iron surface in presence of the inhibitor. The low frequency contribution can be

attributed to the double layer capacitance (Cdl) at the electrolyte/iron interface at the bottom of the

pores coupled with the charge transfer resistance (Rt) [37]. The equivalent electric circuits shown

in Fig. 5 were determined by the program EC-LAB for the EIS data fitting. The equivalent circuit

given in Fig.5a shows the presence of an inductive element L in the impedance spectrum in the

absence of inhibitor. The equivalent circuit model used in the fitting of the impedance data of iron

consists of the double layer capacitance (Cdl) in parallel to the charge transfer resistance (Rct). In

series with Rct there is a second time constant expressed by capacity C in parallel to one resistance,

which is in series with L. Cdl in our model represents an ideal capacitor.

16
 Fig. 5. Scheme of the equivalent circuit used to fit EIS data for iron in acidic solution
a) in the absence and b) in the presence of the corrosion inhibitor.

Electrochemical parameters associated with the EIS diagrams of Fig. 4 are shown in Table 4.

Results reported in Table 4 showed that the values of Rc increased with an increase in FBN

concentration and the Cd values slowly decreased according to the decrease of the surface

heterogeneity due to the inhibiting effect. The adsorption of FBN on the electrode surface caused

a displacement of water molecules and other ions originally adsorbed on the surface. In the high

frequency, the low capacity value (Cf < 10 μF/cm2) and the decrease of this capacity with the

increase in FBN concentration may be attributed to the formation of a protective layer on the

electrode surface [38], since higher FBN concentrations adsorbed on the electrode surface lead to

a decrease of surface heterogeneity and Cf value.

As shown in Table 4, the inhibition efficiency increased with the increase of the inhibitor

concentration up to the value of 99% at 2500 ppm of FBN.

Electrochemical impedance spectroscopy is a useful technique for long-lasting time tests because

it does not significantly disturb the system and it is possible to follow its evolution overtime [39].

The evolution of the impedance spectra in acidic solution containing 2500 ppm FBN measured at

open circuit potential and recorded for different immersion times is reported in Fig. 6.

Fig. 6. EIS spectra of the iron electrode in acidic solution

containing 2500 ppm of FBN at 293K as a function of the immersion time.

17
As shown in Fig. 6, the capacitive loops kept the same shape although a significant influence on

the size of the impedance spectra with increasing of immersion time was found. The polarization

resistance increased dramatically when the immersion time increased from 2h to 72h. The low

frequency loop is very marked by the presence of the inhibitor and at high immersion time values

studied. The associated resistance values seem to diverge towards very high values (about 1 MΩ).

These results show that the inhibitor acts as good barrier protecting iron substrate.

3.4. SEM-EDS analysis

Surface analysis was carried out by SEM-EDS technique in order to evaluate the surface

morphology of the iron substrate in acidic solution.

The SEM micrographs and the corresponding EDS spectra of the iron substrate after 24h of

immersion time in acidic solution in the absence and in the presence of 2500 ppm FBN are shown

in Fig. 7 (a) and (b), respectively.

Fig. 7. SEM images and EDS spectra of iron in acidic solution after 24h immersion
in the absence (a) and in the presence (b) of 2500 ppm FBN.

In absence of FBN, the SEM micrograph revealed a severe attack by the acidic solution on the

metal surface. The EDS spectrum reported in Fig. 7a showed the characteristic peaks of the

specimen and a marked presence of oxygen atoms, along with sulphur atoms. A totally different

situation was detected in the presence of 2500 ppm of FBN inhibitor. As shown in Fig. 7b, no

corrosion products were observed on the surface due to the formation of the inhibitor film, as

confirmed by the EDS data revealing a very low content of oxygen species and no traces of sulphur.

18
These results confirmed that the high inhibition efficiency values obtained in the chemical and the

electrochemical measurements can be attributed to a good protective FBN film formation on the

surface of the iron substrate.

3.5. XPS analysis

The surface chemical composition of the iron substrate and FBN film samples, both before and

after corrosion in the acidic solution, is reported in Table 5. Relative quantitative results are

expressed as atomic percentage (at. %).

The presence of the FBN film on the surface of the Fe substrate is evidenced in sample B by the

higher concentration of carbon and the increase of the oxygen content from the organic

composition of the oil with respect to sample A. Furthermore, also the appearance of N 1s and K

2p photoelectron signals derived from the formulation is detected by XPS analysis. The

concentration of iron on the surface of sample B correspondingly decreases with respect to sample

A as a consequence of the film formation.

After the corrosion treatment of the Fe substrate (sample A*), a significant increase in the oxygen

concentration was detected with respect to that on the surface of sample A. The appearance of the

S 2p photoelectron signal located at BE = 168.8 eV can be assigned to the presence of sulphates

species on the surface of sample A* as a result of the corrosive attack by the acidic solution [40].

The iron concentration decreased as a consequence of the formation of the corrosion products

(oxides and sulphates) on the surface of sample A*.

After the corrosion treatment of the FBN film, no traces of sulphur species were found on the

surface of the sample B*. The surface concentration of oxygen species increased as a consequence

19
of the corrosive attack with respect to sample B, but the variation is lower than that detected on

sample A*. A lower concentration of carbon detected on the surface of sample B* with respect to

sample B indicated a partially degradation of the organic film upon corrosion, as evidenced also

by the higher concentration of iron found on the surface of sample B* due to a no more

homogenous coverage of the surface by the FBN film.

The analysis of XPS spectra by a nonlinear least-square curve fitting procedure allows the

identification of elemental species in different oxidation states and chemical environments on the

surface. Results of the curve fitting of O 1s and Fe 2p3/2 photoelectron signals in the investigated

corroded samples are reported in Fig. 8 and Fig. 9, respectively.

Fig. 8. XPS curve fitting of O 1s spectra in the A* and B*samples.

The O 1s photoelectron peak detected on the surface of the Fe substrate after the corrosion attack

(sample A*) can be deconvoluted by three different components. The first component is located

at BE= 529.7 eV and is assigned to the presence of O2-ions due to iron oxides on the surface (FeO,

Fe2O3). A second component at BE = 531.2 eV is attributed to the presence of hydroxyl groups

(OH-) and FeOOH species. The third component of the peak is located at BE = 532.2 eV and it

can be assigned to surface oxygen species as in sulphates compounds, i.e. Fe2(SO4)3 [40].

The curve-fitting of the O 1s photoelectron peak on the surface of the FBN film submitted to

corrosion (sample B*) was performed by using only the first two components assigned to the

presence of iron oxides and hydroxides species on the surface. No evidence of sulphates species

20
was found on the surface of sample B*, as determined by the absence of the O 1s peak component

located at the higher binding energy side.

A different surface distribution of oxygen species was determined on the surface of A* and B*

samples by the curve fitting of O 1s photoelectron peak, as shown in Table 6. Oxygen species are

expressed as peak area percentage (total photoelectron signal area = 100 %). A higher

concentration of hydroxides and FeOOH species was detected on the surface of the corroded FBN

film (sample B*), together with less amount of oxides species and the absence of sulphates species,

with respect of corroded Fe substrate (sample A*).

Very similar Fe 2p spectra were recorded by XPS on the surface of the investigated samples after

the corrosion by the acidic solution. The curve fitting of Fe 2p3/2 spectra are shown in Fig. 9.

Fig. 9. XPS curve fitting of Fe 2p3/2 spectra in the A* and B*samples.

Results of the curve fitting of the Fe 2p3/2 spectra revealed the presence of Fe2+ and Fe3+ ions on

the surface of the corroded A* and B* samples. The component located at BE = 709.9 eV is

assigned to the presence of iron oxides on the surface (FeO; Fe2O3) and the component at BE=

711.3 eV can be attributed to iron hydroxides species as in FeO(OH) and to Fe3O4 [40]. The highest

binding energy peak around BE = 713.0 eV originates from the peak asymmetry observed in the

Fe oxide band envelope (FeO/Fe2O3) [41]. The only relevant difference in the Fe 2p spectra of the

investigated samples concerns the shoulder detected at the lowest binding energy side of the iron

21
photoelectron signal of sample A*, pointed by an arrow in Fig. 9. Only on the surface of the

corroded Fe substrate (sample A*) the XPS curve fitting revealed the presence of a component at

BE = 706.8 eV that can be assigned to Fe0 metallic iron species on that surface [40]. The

concentration of metallic iron corresponding to a 1.6 % peak area percentage is quite low, thus

indicating a hard corrosive attack by the acidic solution on the pure metallic surface with the

formation of several corrosion products in the form of oxides, hydroxides and sulphates of divalent

and trivalent Fe ions. The absence of this peak component in the Fe 2p3/2 spectrum of sample B*

suggests a good protection by the FBN formulation on the iron substrate, acting as a barrier film

against acidic corrosion.

4. Conclusions
In this work weight loss and electrochemical (OCP, polarization and impedance spectroscopy

measurements) methods were used to investigate the properties of a green formulation based on

the oil extracted by Nigella Sativa L seeds to act as a corrosion inhibitor of iron in acid rain

solution. The potentiodynamic results showed that the FBN act as mixed type inhibitor and the

inhibition efficiency increases with increasing FBN concentration. The best efficiency value of

99% is obtained for a concentration of 2500 ppm FBN. The electrochemical impedance

measurements confirmed the results obtained by the potentiodynamic curves. The good protective

effect of FBN is attributed to the formation of the inhibitor film on the iron surface. The capacity

and resistance values corresponding to the inhibitor film suggest that this film may be relatively

thin and compact. The protective effect is reinforced by increasing the immersion time leading to

a change of the mechanism of reactions taking place at the electrode surface. Results of the surface

analysis performed by SEM/EDX and XPS confirmed the formation of the FBN film on the iron

22
surface and its protective effect as barrier film against the corrosion by the acidic solution. These

first promising results seem to be useful for the application of the FBN formulation to the

conservation of iron artifacts in outdoor environments.

Acknowledgements

This work was financially supported in the framework of a bilateral cooperation agreement by the

Moroccan National Center of Scientific and Technological Research (CNRST) and the Italian

National Council of Research (CNR) about the research project on new green and low toxic

inhibitors for the conservation of metallic archaeological artefacts. The collaboration of the

Servichim Company is also gratefully acknowledged.

23
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27
FIGURES

Fig. 1. Variation of the open-circuit potential (OCP) of iron in acidic solution

at different FBN concentrations at 293K.

28
 a)

b)

Fig. 2. Potentiodynamic polarization curves of iron in acidic solution at different FBN

concentrations in the cathodic (a) and anodic (b) domain, respectively, after ohmic drop
compensation (ZIR).

29
Fig. 3. Nyquist plot of the iron electrode in acidic solution at 293K.

Fig. 4. Nyquist plots recorded for iron in acidic solution

as a function of FBN concentration at 293K.

30
 a)

b)

Fig. 5. Scheme of the equivalent circuit used to fit EIS data for iron in acidic solution
a) in the absence and b) in the presence of the corrosion inhibitor.

31
Fig. 6. EIS spectra of the iron electrode in acidic solution containing 2500 ppm of FBN
at 293K as a function of the immersion time.

32
a)

b)

Fig. 7. SEM images and EDX spectra of iron in acidic solution after 24h immersion
in the absence (a) and in the presence (b) of 2500 ppm FBN.

33
Fig. 8. XPS curve fitting of O 1s spectra in the A* and B*samples.

34
Fig. 9. XPS curve fitting of Fe 2p3/2 spectra in the A* and B*samples.

35
TABLES

Table 1. Effect of the FBN concentration on corrosion of iron in acidic solution

as determined by weight loss measurements.

FBN Concentration Corrosion rate IE

(ppm) (mg.cm-2h-1) (%)

Blank 2.24 -
250 0.76 66.1
500 0.55 75.5
1000 0.19 91.5
2000 0.11 95.1
2500 0.05 97.7

36
Table 2. Effect of the FBN concentration on corrosion of iron in acidic solution
as determined by ICP-AES.

FBN Concentration Dissolved Fe IE

(ppm) (mg/l) (%)

Blank 1.816 -
250 0.525 71.1

500 0.187 89.7

1000 0.073 96.0

2000 0.045 97.5

2500 0.031 98.3

37
Table 3. Kinetic parameters determined from polarization curves

FBN Concentration Ecorr - βc βa Icorr IE

(ppm) (V/SCE) (mVdec-1) (mVdec-1) (μA.cm-2) (%)
Blank -0.52 324 104 72.59 ---
250 -0.37 268 42 2.58 96.4

500 -0.35 247 60 1.86 97.4

1000 -0.28 203 147 0.67 99.0
2000 -0.31 199 168 0.57 99.2
2500 -0.33 214 156 0.51 99.3

38
 Table 4. Electrochemical data derived from EIS spectra for iron in acidic solution
at different FBN concentration at 293K.

Acidic Re RHF CHF RBF CBF

2 2 2 2 2
Solution (kΩ cm ) (kΩ.cm ) (μF/cm ) (kΩ cm ) (F/cm )

Blank 0.26 0.17 67 0.22 644

FBN Concentration Re Rf Cf Rct Cdl IE

(ppm) 2 2 2 2 2 (%)
(kΩ cm ) (kΩ.cm ) (μF/cm ) (kΩ cm ) (F/cm )

250 0.27 0.05 9.28 2.10 196 81.9

500 0.28 0.07 8.57 2.49 181 84.8

1000 0.28 19.21 2.02 54.70 68 99.5

2000 0.28 21.45 2.00 104.92 61 99.7

2500 0.26 29.11 1.65 177.16 48 99.8

39
 Table 5. XPS surface chemical composition of the investigated samples.
Elemental concentration is expressed as atomic percentage (atom. %).

DESCRIPTION SAMPLE C 1s O 1s Fe 2p S 2p N 1s K 2p

Fe substrate A 34.3 29.6 36.0

Fe substrate after corrosion A* 14.1 53.6 30.5 1.8

FBN Film B 44.2 36.4 16.7 1.7 1.0

FBN Film after corrosion B* 35.2 42.4 22.4 -

40
Table 6. XPS surface distribution of oxygen species in A* and B* samples
determined by the curve fitting of O 1s photoelectron signals.

O 1s peak 529.7 531.2 532.2

BE (eV) (eV) (eV)

Sample A* 37.8 40.0 22.2

Sample B* 29.0 71.0

41