Materials Chemistry and Physics 141 (2013) 240e247

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Materials Chemistry and Physics

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The use of Euphorbia falcata extract as eco-friendly corrosion inhibitor

of carbon steel in hydrochloric acid solution
A. El Bribri a, M. Tabyaoui a, b, *, B. Tabyaoui a, H. El Attari c, F. Bentiss c
a
Laboratoire de Chimie Organique, Bioorganique et Environnement, Faculté des Sciences, Université Chouaib Doukkali, B.P. 20, M-24000 El Jadida, Morocco
b
Laboratoire des Matériaux, Nanoparticules et Environnement, Université Mohamed V Agdal, Faculté des Sciences, 4 Av. Ibn Battouta, B.P. 1014 RP,
M-10000 Rabat, Morocco
c
Laboratoire de Catalyse et de Corrosion des Matériaux (LCCM), Faculté des Sciences, Université Chouaib Doukkali, B.P. 20, M-24000 El Jadida, Morocco

h i g h l i g h t s g r a p h i c a l a b s t r a c t

EFE is a good eco-friendly inhibitor

for the corrosion of carbon steel in
1 M HCl.

EFE acts as mixed-type inhibitor in
1 M HCl medium.
Z / Ω cm

Weight loss, ac impedance and po-

larization methods are in reasonable
agreement.

The adsorption of EFE is well
described by the Langmuir adsorp-
tion isotherm. 0 25 0 500 750
Z / Ω cm

a r t i c l e i n f o a b s t r a c t

Article history: Euphorbia falcata L. extract (EFE) was investigated as eco-friendly corrosion inhibitor of carbon steel in
Received 30 March 2012 1 M HCl using gravimetric, ac impedance, polarization and scanning electron microscopy (SEM) tech-
Received in revised form niques. The experimental results show that EFE is good corrosion inhibitor and the protection efficiency
3 April 2013
is increased with the EEF concentration. The results obtained from weight loss and ac impedance studies
Accepted 9 May 2013
were in reasonable agreement. Impedance experimental data revealed a frequency distribution of the
capacitance, simulated as constant phase element. Polarization curves indicated that EFE is a mixed
Keywords:
inhibitor. The corrosion inhibition was assumed to occur via adsorption of EFE molecules on the metal
Organic compounds
Surfaces
surface. The adsorption of the E. falcata extract was well described by the Langmuir adsorption isotherm.
Corrosion test The calculated DGoads value showed that the corrosion inhibition of the carbon steel in 1 M HCl is mainly
Adsorption controlled by a physisorption process.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction Use of inhibitors is one of the most practical methods for protection
against corrosion especially in acid solutions to prevent metal
Acid solutions are generally used for the removal of undesirable dissolution and acid consumption [1]. The use of synthetic organic
scale and rust in several industrial processes. Hydrochloric and compounds containing oxygen, sulphur and nitrogen to reduce
sulphuric acids are widely used in the pickling processes of metals. corrosion attack on steel has been widely studied in some details
[2e6]. The strict environmental legislations and increasing
ecological awareness among scientists have led to the development
* Corresponding author. Laboratoire de Chimie Organique, Bioorganique et of “green” alternatives to mitigate corrosion. Recently, natural
Environnement, Faculté des Sciences, Université Chouaib Doukkali, B.P. 20, M-
compounds such as herb plants were employed as inhibitors in
24000 El Jadida, Morocco. Tel.: þ212 661 749 041; fax: þ212 523 342 187.
E-mail address: hamidtabyaoui@yahoo.fr (M. Tabyaoui). order to develop new cleaning chemicals for green environment

0254-0584/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matchemphys.2013.05.006
 A. El Bribri et al. / Materials Chemistry and Physics 141 (2013) 240e247 241

[7]. Plant extracts are incredibly rich sources of naturally synthe- Science, El Jadida (Morocco). The dried plant material is stored in
sized chemical compounds (e.g. amino and organic acids, glucosi- the laboratory at room temperature before extraction. The plant
nolates, alkaloids, polyphenols, tannins) and most are known to extract is prepared by refluxing aerial parts of E. falcata, in absolute
have inhibitive action. Moreover, they can be extracted by simple methanol for 4 h, then filtered, and the solvent is evaporated in
procedures with low cost. The uses of the natural products as vacuo to give the E. falcata extract (EFE). The phytochemical study
corrosion inhibitors for different metals have been reported by of E. falcata extract was previously described [35]. As given in Fig. 1,
several authors [8e20]. Most of the natural products are nontoxic, four diterpenes were isolated by E. Sulyok et al. from the E. falcata
biodegradable and readily available and renewable sources of ma- extract by a combination of different chromatographic methods
terials. Various parts of the plants, leaves [21], fruits [22], seeds [35]. The structure elucidation was already conducted, by E. Sulyok
[23,24], and flowers [25,26] were extracted and used as corrosion et al., using the spectroscopic analysis, including 1D and 2D NMR
inhibitors. The reviews of the literature on several plant extracts as (1He1H COSY, HSQC and HMBC) and HRESIMS experiments. The
corrosion inhibition of mild steel in HCl solution were recently stereochemistry was studied by means of NOESY measurements
published by Singh et al. [27]. They showed that all the reported [35]. The concentration range of EFE used in the corrosion tests was
plant extracts were found to inhibit the corrosion of mild steel in 0.6e3.0 g L1.
acid media. Indeed, the extract Andrographis paniculata has a better The material used in this study is a carbon steel (Euronorm:
inhibition performance (98%) than the other leaves extract. C35E carbon steel and US specification: SAE 1035) with a chemical
Strychnos nuxvomica showed better inhibition (98%) than the other composition (in wt%) of 0.370% C, 0.230% Si, 0.680% Mn, 0.016% S,
seed extracts. Moringa oleifera extract is reflected as a good corro- 0.077% Cr, 0.011% Ti, 0.059% Ni, 0.009% Co, 0.160% Cu and the
sion inhibitor of mild steel in 1 M HCl with 98% inhibition efficiency remainder iron (Fe). The steel samples were pre-treated prior to the
among the studied fruits extract. Bacopa monnieri extract showed experiments by grinding with emery paper SiC (120, 600 and
its maximum inhibition performance to be 95% at 600 ppm among 1200); rinsed with distilled water, degreased in acetone in an ul-
the investigated stem extracts. Corrosion inhibition effect of Justicia trasonic bath immersion for 5 min, washed again with bidistilled
gendarussa extract on mild steel in 1 M HCl medium was also water and then dried at room temperature before use. The acid
studied by Satapathy et al. [28] and inhibition efficiency up to 93% solutions (1 M HCl) were prepared by dilution of an analytical re-
was achieved with 150 mg L1 of extract. Aqueous extracts of Cordia agent grade 37% HCl with doubly distilled water.
latifolia and Curcumin were investigated as corrosion inhibitors for The gravimetric measurements were carried out at the definite
mild steel in industrial cooling systems by Minhaj et al. [29]. The time interval of 6 h at room temperature (30  1  C) using an
extracts showed maximum inhibition efficiency of 97.7% and 60%, analytical balance (precision  0.1 mg). The steel specimens used
respectively. Also, the inhibitive effects of aqueous extracts of have a rectangular form (length ¼ 5 cm, width ¼ 2 cm,
Eucalyptus (leaves), Hibiscus (flower), and Agaricus on the corrosion thickness ¼ 0.3 cm). Gravimetric experiments were carried out in a
of mild steel for cooling-water systems, using tap water, have been double glass cell equipped with a thermostated cooling condenser
investigated by means of weight loss and polarization methods containing 250 ml of non-de-aerated test solution. After immersion
[29]. All the plant extracts were found to inhibit corrosion of mild period, the steel specimens were withdrawn, carefully rinsed with
steel following and their inhibitive efficiencies were in the order: bidistilled water, ultrasonic cleaning in acetone, dried at room tem-
Agaricus (85%), Hibiscus (79%), and Eucalyptus (74%). perature and then weighed. Duplicate experiments were performed
Plants in the spurge family (Euphorbiaceae) are well known for in each case and the mean value of the weight loss is calculated.
the chemical diversity of their isoprenoid (sesqui-, di- and tri- Ac impedance tests were performed in a polymethyl methac-
terpenes) constituents. The genus Euphorbia is the largest in this rylate (PMMA) cell with a capacity of 1000 ml at 30  1  C, using a
family, comprising more than 2000 species, and diterpenoids are thermostat. A saturated calomel electrode (SCE) was used as the
amongst their characteristic compounds. Moreover, Euphorbia reference; while a platinum leaf was used as a counter electrode. All
diterpenes possess a number of interesting biological activities, potentials are reported vs. SCE. The working electrode was pre-
such as skin irritant and tumour-promoting activities (due to their pared from a square sheet of carbon steel such that the area
protein kinase C-activating effects), and also antiproliferative, exposed to solution was 7.55 cm2. The impedance spectra were
antiviral and multidrug resistance-reversing activities [30e33]. The
Euphorbia falcata extract was previously tested for the first time, by
El Bribri et al., as corrosion inhibitor on carbon steel in 1 M HCl
using only the gravimetric method [34]. The effect of temperature
on the corrosion rate was also investigated. Both kinetic and stan-
dard thermodynamic parameters were calculated and discussed in
detail. In a continuation of this programme, the present paper re-
ports the detailed study of the inhibition effect of E. falcata extract
(EFE) on the corrosion behaviour of carbon steel in normal hydro-
chloridric solution (1 M HCl) at 30  C using gravimetric, ac
impedance and polarization methods. Treated and untreated
metallic surface are examined using scanning electron microscopy
(SEM). The corrosion inhibition mechanism is discussed based on
the adsorption properties of EFE on carbon steel after acid
immersion.

2. Experimental details

E. falcata L. extract (EFE) was prepared according to a previously

described experimental procedure [34]. The aerial part of E. falcata
was collected in June 2008 in the region of El Jadida (Morocco). A Fig. 1. Chemical structures of the four diterpenes, isolated from the Euphorbia falcata
specimen has been deposited at the Herbarium of the Faculty of plant.
242 A. El Bribri et al. / Materials Chemistry and Physics 141 (2013) 240e247

recorded 6 h after the exposure of the working electrode to the where Wb and Wa are the specimen weight before and after im-
solution (no deaeration, no stirring). Ac impedance measurements mersion in the tested solution, w0 and wi are the values of corrosion
were performed using a potentiostat Solartron SI 1287 and a weight losses of carbon steel in uninhibited and inhibited solutions,
Solartron 1255B frequency response analyzer and ZPlot 2.80 soft- respectively, A the area of the carbon steel specimen (cm2) and t is
ware was used to run the tests and to collect the experimental data. the exposure time (h).
The response of the electrochemical system to ac excitation with a The values of percentage inhibition efficiency, hWL (%), and
frequency ranging from 105 Hz to 102 Hz and peak to peak corrosion rate (CR) obtained from weight loss method at different
amplitude of 10 mV was measured with data density of 10 points concentrations of EFE are summarized in Table 1. It is very clear that
per decade. All EIS diagrams were recorded at the open-circuit the EFE inhibits the corrosion of carbon steel in 1 M HCl solution, at
potential, i.e., at the corrosion potential Ecorr. The duration of one all concentrations used in this study, while the corrosion rate (CR)
EIS experiment was about 10 min. The impedance data were ana- decreases continuously with increasing additive concentration at
lysed and fitted with the simulation ZView 2.80, equivalent circuit 30  C; the maximum hWL (%) of 93.2% is achieved at 3.0 g L1. This
software. behaviour is in good agreement with the findings of our work in the
Linear polarisation resistance (LPR) and potentiodynamic case of mild steel, recently described [34]. The EFE extract can be
polarisation measurements were performed in a conventional considered as an excellent inhibitor for carbon steel in acid medium
three-electrode cylindrical Pyrex glass cell. The temperature is compared to the other plant extracts, previously described [27].
thermostatically controlled. Pure carbon steel specimen was used In order to obtain a better understanding of the corrosion pro-
as the working electrode, a platinum electrode as the counter tection mechanism of EFE against the corrosion of carbon steel in
electrode and a saturated calomel electrode (SCE) as the reference normal hydrochloric medium, a detailed study on this inhibitor was
electrode. The working electrode (WE) in the form of disc cut from carried out using ac impedance technique.
steel has a geometric area of 1 cm2 and is embedded in polytetra-
fluoroethylene (PTFE). A fine Luggin capillary was placed close to 3.1.2. Ac impedance study
the working electrode to minimize IR drop. All test solutions were Fig. 2aed shows the impedance spectra of carbon steel obtained
de-aerated in the cell by using pure nitrogen for 10 min prior to the at open-circuit potential after an exposure period of 6 h in 1 M HCl
experiment. During each experiment, the test solution was mixed solution in the absence and presence of different concentrations of
with a magnetic stirrer and the gas bubbling was maintained. EFE at 30  C, respectively. Inspection of the data reveals that the
Solartron Instruments SI 1287 potentiostat monitored by a personal impedance diagram obtained with 1 M HCl (Fig. 2a) shows only one
computer via a GPIB Interface and CorrWarr2.80 software were capacitive loop at high frequency (HF) values with one capacitive
used to run the tests and to collect the experimental data. Before time constant in the Bode-phase plot (Fig. 2b).
each Tafel experiment, the carbon steel electrode was pre-polarised The same trend (one capacitive loop) was also noticed for car-
at 800 mVSCE for 10 min and thereafter the WE was allowed to bon steel immersed in 1 M HCl containing different concentrations
corrode freely and its open-circuit potential (OCP) was recorded as of EFE (Fig. 2c and d). The shape of the capacitive loops suggests
a function of time up to 1 h, the time necessary to reach a quasi- that the charge transfer controls the corrosion of carbon steel at
stationary value for the open-circuit potential. This steady-state Ecorr [37]. On the other hand, the diameter of the depressed semi-
OCP corresponds to the corrosion potential (Ecorr) of the WE. For circle increases gradually with the increase of the EFE concentra-
LPR measurements, the WE was polarised only in the range tion and consequently the inhibition efficiency increases. When
20 mV vs. Ecorr at a scan rate of 0.125 mV s1. After studying the Nyquist plot contains a “depressed semicircle with the centre under
open-circuit potential and LPR tests, the potentiodynamic Tafel the real axis” (Fig. 2a and c), such behaviour is characteristic for
measurements were scanned from cathodic to the anodic direction, solid electrodes and often referred to as frequency dispersion
E ¼ Ecorr  200 mV, with a scan rate of 0.5 mV s1. The Tafel and LRP which has been attributed to the surface heterogeneity due to
data were analysed and fitted using the polarisation CorrView 2.80 surface roughness, impurities or dislocations [38], fractal structures
software (Scribner Associates, Inc.). [39], distribution of activity centres, inhibitors adsorption and for-
Micrographs of the carbon steel surface before and after the mation of porous layers [40].
immersion in 1 M HCl with and without corrosion inhibitor, coated The transfer function can be represented by a resistance R1
by a film of 50 nm of gold by sputtering, were taken using Scanning parallel to a capacitor C and in series to them an additional resis-
Electron Microscopy (JEOL-5300). The energy of the acceleration tance R2:
beam employed was 6 kV.
1
ZðuÞ ¼ R1 þ (3)
3. Results and discussion 1=R2 þ iuC
It can be assumed, on the basis of the statements above, that the
3.1. Corrosion inhibition evaluation
transfer function, defined by Eq. (2), is represented by the equiva-
lent circuit shown in Fig. 3a. This transfer function is applicable for
3.1.1. Gravimetric tests
homogeneous systems with one time constant when the centre of
The effect of addition of different concentrations of EFE on the
corrosion of carbon steel in 1 M HCl solution was studied by weight
loss measurements at 30  C after 6 h of immersion period. For every Table 1
concentration, the mean value of the corrosion rate CR Corrosion parameters obtained from weight loss measurements for carbon steel in
(mg cm2 h1) was determined and the inhibitor efficiency, hWL (%), 1 M HCl containing various concentrations of EFE at 30  C.

was calculated using Eqs. (1) and (2), respectively [36]: Inhibitor Concentration (g L1) CR (mg cm2 h1) hWL (%)
Blank 2.50
Wb  Wa
e e
CR ¼ (1) EFE 0.6 0.44 82.4
At 1.2 0.30 88.0
  1.8 0.24 90.4
w 2.1 0.22 91.2
hWL ð%Þ ¼ 1  i  100 (2) 3.0 0.17 93.2
w0
 A. El Bribri et al. / Materials Chemistry and Physics 141 (2013) 240e247 243

Fig. 2. Nyquist and Bode diagrams for carbon steel in 1 M HCl without and with EFE after 6 h of immersion period at 30  C.

the semicircle lies on the abscissa. Indeed, the structural model of Fig. 3b shows the electrical equivalent circuit employed to
Fig. 3a is inadequate in our case and representative example given analyse the impedance plots, where the capacitor in Eq. (2) is
in Fig. 4a and b corroborates the frequency dispersion behaviour. It replaced by a CPE. The resistance R1 reflects the charge transfer
is evident that it cannot describe the observed depression of the resistance Rct, CPE has the meaning of a frequency distributed
capacitive semicircle and it is necessary to replace the capacitor by double-layer capacitance and R2 is the resistance of the solution Rs.
some element, which has frequency dispersion like the constant The same equivalent circuit is often found to describe the corro-
phase element (CPE). This element is a generalised tool, which can sion inhibition with organic compounds [44e46]. Excellent fit
reflect exponential distribution of the parameters of the electro- with this model was obtained for all experimental data. Simula-
chemical reaction related to energetic barrier at charge and mass tion of Nyquist and Bode plots with above model shows excellent
transfer, as well as impedance behaviour caused by fractal surface agreement with experimental data (Fig. 4c and d, representative
structure. Therefore, CPE instead of a capacitive element is used to example). It is clear that the measured impedance plots (Nyquist
get a more accurate fit of experimental data set. The impedance and Bode) are in accordance with those calculated by the used
function of a CPE is defined by the mathematical expression given equivalent circuit model. The electrochemical parameters,
below [41,42]: including Rs, Rct, A and n, obtained from fitting the recorded EIS
data are listed in Table 2. In this table are also given the calculated
ZCPE ¼ A1 ðiuÞn (4) “double-layer capacitance” values, Cdl, derived from the CPE pa-
rameters and the relaxation time constant (s) (a measure for the
where A is a proportionality coefficient, u is the angular frequency time required for return to the equilibrium state) according to
(in rad s1) and i2 ¼ 1 is the imaginary number. n d an exponent [47]:
related to the phase shift and can be used as a measure of the
 1=n
surface inhomogeneity [43]. For whole numbers of n ¼ 1, 0, 1 CPE
Cdl ¼ AR1n
ct (5)
is reduced to the classical lumped elements capacitor (C), resistance
(R) and inductance (L). The value of n ¼ 0.5 corresponds to Warburg
impedance (W). s ¼ Cdl Rct (6)
Inspection of the results in Table 2 indicates that the Rct value
increased in the presence of EFE, in the whole studied concentra-
tion interval, reaching a maximum value of 566.6 U cm2 at 3 g L1.
Also, the value of the proportional factor A of CPE decreases in a
regular manner with inhibitor concentration. The change of Rct and
A values can be related to the gradual replacement of water mol-
Fig. 3. Electrical equivalent circuit used for modelling the interface carbon steel/1 M ecules and other ions originally adsorbed on the surface by EFE
HCl solution without and with EFE. molecules and consequently to a decrease in the number of active
244 A. El Bribri et al. / Materials Chemistry and Physics 141 (2013) 240e247

Fig. 4. EIS Nyquist and Bode diagrams for carbon steel/1 M HCl þ 1.2 g L1 of EFE interface: ($$$) experimental; (d) fitted data using structural models in Fig. 3.

sites necessary for the corrosion reaction [44]. This can be where d is the thickness of the protective layer, ε is the dielectric
confirmed by the fact that the n factor values present an increasing constant of the protective layer and ε0 is the permittivity of free
trend with EFE concentration (Table 2). This behaviour can be space (8.854  1014 F cm1).
explained by reduction of surface inhomogeneity due to the The inhibition efficiency hZ (%) is calculated by Rct using Eq. (8),
adsorption of the inhibitor on the most active adsorption sites [9]. where R0ct and Rct are the charge transfer resistance values without
On the other hand, the calculated value of time constant s obtained and with inhibitor [49], respectively:
in the case of uninhibited solution was found to be 0.0056 s. The
addition of EFE results in an increase in s value at 1.8 g L1 1=R0ct  1=Rct
(s ¼ 0.0230 s) and s shows a slight decrease at 2.1 g L1 hZ ð%Þ ¼  100 (8)
1=R0ct
(s ¼ 0.0213 s). Upon increasing the concentration of EFE, the time of
adsorption process becomes much higher (s ¼ 0.0240 s for 3 g L1) It is obvious from the obtained results that the EFE inhibits the
which means slow adsorption process [46]. The simultaneous corrosion of carbon steel in1 M HCl solution at all concentrations
decrease of double-layer capacitance, Cdl, with increase of the EFE used in this study and the hZ (%) was seen to increase continuously
concentration indicates larger coverage degrees of adsorption. with increasing additive concentration at 30  C (Table 2). Indeed,
Generally, the decrease in Cdl is explained by a decrease in local the protection efficiency increases with increase of the EFE con-
dielectric constant and/or an increase in the thickness of a pro- centration, the maximum hZ (%) of 93.0% was achieved at 3 g L1.
tective layer at electrode surface, enhancing therefore the corrosion
resistance of the studied steel [45]. This trend is in accordance with 3.1.3. Polarization study
Helmholtz model, given by the following equation [48]: Polarisation curves of the carbon steel electrode in 1 M HCl
without and with addition of various concentrations of EFE are
εε0 shown in Fig. 5. Electrochemical kinetic parameters (corrosion
Cdl ¼ (7)
d potential (Ecorr), corrosion current density (jcorr) and cathodic Tafel

Table 2
Impedance parameters and inhibition efficiency values for carbon steel after 6 h immersion period in 1 M HCl containing different concentrations of EFE at 30  C.

Conc. (g L1) Rs (U cm2) Rct (U cm2) 104 A (U1 sn cm2) n Cdl (mF cm2) s (s) hZ (%)
1 M HCl 5.68  0.04 39.6  0.3 2.64  0.11 0.881  0.006 142.51 0.0056 e
0.6 5.21  0.02 249.1  1.2 1.14  0.02 0.864  0.002 65.36 0.0163 84.1
1.2 7.45  0.01 426.5  0.7 0.82  0.03 0.867  0.001 49.17 0.0210 90.7
1.8 9.31  0.04 480.3  1.7 0.79  0.01 0.873  0.001 48.99 0.0230 91.7
2.1 5.95  0.02 496.8  2.1 0.67  0.01 0.882  0.001 42.70 0.0213 92.0
3.0 7.09  0.03 566.6  2.6 0.65  0.01 0.886  0.001 42.34 0.0240 93.0
 A. El Bribri et al. / Materials Chemistry and Physics 141 (2013) 240e247 245

potential higher than 300 mVSCE, the presence of EFE did not
change the current-vs.-potential characteristics (Fig. 5). This po-
tential can be defined as the desorption potential. The phenomenon
may be due to the obvious metal dissolution, which led to a
desorption of the inhibitor molecule from the electrode surface, in
this case the desorption rate of the inhibitors is higher than its
adsorption rate, so the corrosion current obviously increased with
rising potential [53]. This result shows that the inhibition effect of
this compound depends on the electrode potential.
From Table 3, it is clear that the values of jcorr values decrease
and Rp increase considerably with the increase of the concentration
of EFE, however, there is no definite trend in the shift of Ecorr values
with concentration. bc values for EFE are higher than those for
uninhibited solution. This may probably be due to a diffusion or
barrier effect [54]. The inhibition efficiencies values, h (%), calcu-
lated by both methods (potentiodynamic polarisation and LPR) are
in good agreement (Table 3). The inhibition efficiency values,
Fig. 5. Polarization curves for carbon steel in 1 M HCl containing different concen-
trations of EFE.
calculated from polarization studies, show the same trend as those
obtained from weight loss measurements and ac impedance
method previously described (Tables 2 and 3).
slope (bc)), determined from these experiments by extrapolation
method [49,50], are reported in Table 3. The jcorr was determined by
3.2. SEM study
Tafel extrapolation of only the cathodic polarization curve alone,
which usually produces a longer and better defined Tafel region
To establish whether inhibition is due to the formation of an
[51]. Table 3 also included percentage inhibition efficiency, hTafel
organic film on the metal surface, scanning electron micrographs
(%), that was calculated from the following equation [52]:
were taken. Fig. 6 shows the SEM micrograph of the carbon steel
surface before and after of the immersion in 1 M HCl with and
jcorr  jcorrðiÞ
hTafel ð%Þ ¼  100 (9) without corrosion inhibitor. Parallel features on the polished steel
jcorr surface before exposure to the corrosive solution were observed,
which are associated with polishing scratches (Fig. 6a). Fig. 6b and c
where jcorr and jcorr(i) are the corrosion current densities for steel
shows the steel surface after 6 h of immersion in 1 M HCl without
electrode in the uninhibited and inhibited solutions, respectively.
and with EFE. The resulting of the high resolution SEM micrograph
The polarisation resistance (RP) values obtained from the LPR
(Fig. 6b) shows that the steel surface was strongly damaged in the
experiment are also presented in Table 3. The LPR experiments
absence of the EFE with the increased number and depth of the pits.
were carried out in order to exclude the influence of the surface
However, there are less pits and cracks observed in the micro-
changes which may occur during polarisation at higher over-
graphsin the presence of EFE (Fig. 6c) which suggests a formation of
potentials in the case of potentiodynamic polarisation method. In
protective film on steel surface which was responsible for
this case, the inhibition efficiency, hLRP (%), is calculated from Rp
hTafel ð%Þ ¼ ðjcorr  jcorrðiÞ =jcorr Þ  100 the corrosion inhibition.
using the following equation:
Indeed, EFE has a strong tendency to adhere to the steel surface and
can be regarded as good inhibitor for steel corrosion in normal
RPðiÞ  Rp
hLRP ð%Þ ¼  100 (10) hydrochloric medium. The high inhibitive performance of this plant
RPðiÞ extract suggests a strong bonding of the EFE derivatives on the
metal surface due to presence of lone pairs from heteroatom (ox-
where Rp and Rp(i) are the polarisation resistance of carbon steel ygen) and p-orbitals, blocking the active sites and therefore
electrode in the uninhibited and inhibited solutions, respectively. decreasing the corrosion rate.
The analysis of Fig. 5 shows that the addition of EFE to 1 M HCl
solution reduces the anodic dissolution of steel and also retards the
cathodic hydrogen evolution reaction. These results indicated that 3.3. Adsorption study
this organic inhibitor exhibit cathodic and anodic inhibition effects.
Therefore, EFE can be classified as an inhibitor of relatively mixed In order to gain more information about the mode and type of
effect (anodic/cathodic inhibition) in 1 M HCl. However, for adsorption of EFE on the carbon steel surface, the experimental
data have been tested with several adsorption isotherms. Indeed,
the establishment of adsorption isotherms that describe the
Table 3 adsorption behaviour of corrosion inhibitor is important as they
Polarization parameters and the corresponding inhibition efficiency for the corro- provide important clues about the nature of metaleinhibitor
sion of carbon steel in 1 M HCl containing different concentrations of EFE at 30  C. interaction. The fractional surface coverage q can be easily deter-
Inhibitor Tafel data LPR data mined from ac impedance measurements at 30  C by the ratio h
conc. (g L1) (%)/100, if one assumes that the values of h (%) do no differ sub-
Ecorr jcorr bc hTafel Rp hLPR
vs SCE (mV) (mA cm2) (mV dec1) (%) (U cm2) (%) stantially from q (the impedance data are collected in a time in-
terval of 6 h, considered sufficient for adsorption equilibrium to be
Blank 451 717 112 e 31 e
0.6 452 97 140 86.5 270 88.5 achieved) [55].
1.2 450 95 142 86.7 280 88.9 The experimental data are most often described by the
1.8 476 80 136 88.8 321 90.3 adsorption isotherms of Langmuir, Frumkin or Temkin. In this work,
2.1 483 63 140 91.2 421 92.3 the best fit was obtained with the Langmuir adsorption isotherm
3.0 470 48 141 93.3 567 94.5
[56]:
246 A. El Bribri et al. / Materials Chemistry and Physics 141 (2013) 240e247

Fig. 6. SEM micrographs of the carbon steel surface: (a) metallic surface after being polished, (b) metallic surface after 6 h immersion in 1 M HCl and (c) metallic surface after 6 h
immersion in 1 M HCl with 3 g L1 of EFE.

q electrostaticeadsorption (ionic) [61]. This conclusion is in agree-

¼ Kads Cinh (11) ment with the findings of other workers [34,36,62]. It was reported
1q
that the surface charge of steel at Ecorr in 1 M HCl solution is ex-
Rearranging this equation gives: pected to be positive [46]. Accordingly, the adsorption of Cl anions
first occurs and the surface becomes negatively charged. Due to the
Cinh 1
¼ þ Cinh (12) electrostatic attraction, the cationic forms of inhibitor (EFEHþ) are
q Kads adsorbed through electrostatic interactions (physical adsorption)
between positively charged oxygen atoms and negatively charged
where Cinh is the inhibitor concentration in the electrolyte and Kads
carbon steel surface [63].
is the equilibrium constant of the adsorption process which is
Finally, the good inhibition properties of E. falcata extract (EFE)
related to the standard Gibbs energy of adsorption, DGoads, according
on the corrosion carbon steel in 1 M HCl (93% at 3 g L1) may be due
to [52]:
to the presence of several heteroatoms (oxygen), aromatic rings
  (benzoate in compounds 2, 3 and 4) and alkyl chain in their
1 DGpads
Kads ¼ exp (13) structures (Fig. 1), therefore there may be a synergism between the
CH2 O RT main constituents, present in EFE. The large size of constituent’s
molecule (diterpenes) which cover wide areas on the metal surface,
where R is the universal gas constant, T the thermodynamic tem-
and thus retarding the steel corrosion, can also explain the high
perature and the concentration of water in the solution is
inhibitive performance of EFE.
1000 g L1. To calculate the adsorption parameters, least-squares
linear optimisation procedure was applied. The experimental
(points) and calculated isotherms (lines) are plotted in Fig. 7. A very
good fit is observed with the regression coefficient up to 0.99,
which suggests that the experimental data are well described by
Langmuir isotherm. From the intercept of the straight line Cinh/q-
axis, the Kads value can be calculated Kads ¼ 13.32 L g1. The
calculated DGoads value, using Eq. (11), is 23.92 kJ mol1. The large
negative values of DGoads ensure the spontaneity of the adsorption
process and the stability of the adsorbed layer on the carbon steel
surface [57,58] as well as a strong interaction between the EFE
molecules and the metal surface [59]. Generally, absolute values of
DGoads up to 20 kJ mol1 are consistent with physisorption, while
those around 40 kJ mol1 or higher are associated with chemi-
sorption as a result of the sharing or transfer of electrons from
organic molecules to the metal surface to form a coordinate type of
metal bonds [60]. Here, the calculated DGoads value
is 23.92 kJ mol1, indicating that the adsorption mechanism of
EFE on carbon steel in 1 M HCl solution at 30  C is mainly due to Fig. 7. Langmuir adsorption plot for carbon steel in 1 M HCl containing EFE at 30  C.
 A. El Bribri et al. / Materials Chemistry and Physics 141 (2013) 240e247 247

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