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Journal of Electroanalytical Chemistry 769 (2016) 53–61

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Olive leaf extract as natural corrosion inhibitor for pure copper
in 0.5 M NaCl solution: A study by voltammetry around OCP
Chahla Rahal a, Mohamed Masmoudi a, Ridha Abdelhedi a, René Sabot b, Marc Jeannin b,
Mohamed Bouaziz a, Philippe Refait b,⁎
a
Laboratory of Electrochemistry and Environment (LEE), Sfax National Engineering School (ENIS) BPW, 3038 Sfax, University of Sfax, Tunisia
b
Laboratoire des Sciences de l'Ingénieur pour l'Environnement (LaSIE), UMR7356 CNRS — Université de La Rochelle, Bât. Marie Curie, Av. Michel Crépeau, 17042 La Rochelle cedex 01, France

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

Article history: The inhibiting action of olive leaf extract on corrosion of copper in 0.5 M NaCl solution was investigated via po-
Received 6 October 2015 tentiodynamic polarization and electrochemical impedance spectroscopy. For the highest inhibitor concentration
Received in revised form 9 March 2016 considered here the inhibition efficiency reached 90% after 24 h of immersion. Polarization curves recorded
Accepted 12 March 2016
around OCP were computer fitted with various kinetic laws to obtain detailed information on the inhibition pro-
Available online 16 March 2016
cess. This innovative procedure led to results consistent with those deduced from electrochemical impedance
Keywords:
spectroscopy and confirmed that the olive leaf extract act as a cathodic-type corrosion inhibitor mainly hindering
Olive leaf extract the transport and thus the reduction of dissolved O2. High performance liquid chromatography showed that
Oleuropein oleuropein was the major compound of the leaf extract and thus more likely the main inhibiting species.
Voltammetry © 2016 Elsevier B.V. All rights reserved.
Copper
Corrosion
HPLC
EIS

1. Introduction In the Mediterranean coastal zone, olive leaves are one of the
by-products of farming of the olive grove; they exist in high amounts
Corrosion inhibitors are commonly used in industry to reduce the in the olive oil industries (10% of the total weight of the olives). They
corrosion rate of metals and alloys. For copper protection in chloride- also accumulate during the pruning of the olive trees [23]. Olive leaves
containing media, various substances were considered [e.g. 1–8], and are a cheap raw material that can however be the source of high-
it was shown that nitrogen, sulfur and aromatic containing organic added value products, e.g. phenolic compounds. This has recently raised
compounds reduced efficiently the corrosion rate. The inhibiting action interest for their chemical composition and specific properties. It was
of these organic compounds is usually attributed to their adsorption on for instance shown that the olive leaf extract has anti-oxidative,
the metal surface, the polar functional groups playing the main role in anti-inflammatory and antimicrobial activities against bacteria and
the adsorption process [5]. In general, this process depends on the fungi. It also exhibits anti-viral activities against several species like
chemical structure of the inhibitor, the nature and surface charge of haemorrhagic septicaemia rhabdo virus [24].
the metal, the adsorption mode and the electrolyte [8]. Following the same line, the present study aimed to determine the
However, most of these compounds are synthetic chemicals which efficiency of a natural olive leaf extract as a corrosion inhibitor for
may be very expensive and hazardous to living creatures and environ- pure copper in 0.5 M NaCl solution. The organic species present in the
ments. Because of economic and environmental factors, an inhibitor extract were characterized by high performance liquid chromatogra-
must not only be efficient but also cheap, nontoxic and innocuous in phy. Electrochemistry was used to study the evolution over time of
the environment. Various parts of plants proved to contain several the inhibition efficiency during 24 h experiments, the influence of inhib-
compounds that satisfy these criteria and plants thus constitute a itor concentration and the role of temperature. Results obtained with
potential source of new corrosion inhibitors. Numerous studies were electrochemical impedance spectroscopy (EIS) were compared to
recently achieved to determine the effects of some naturally occurring those given by voltammetry. Polarization curves were recorded as
substances on the corrosion of various metals, including copper, in usual on a wide range of potential (from −0.55 V/SCE to +0.6 V/SCE)
different corrosive media [e.g. 9–22]. at the end of the experiment. Additionally, other polarization curves
were recorded before each EIS analysis. They were acquired around
⁎ Corresponding author. the open circuit potential (OCP) to limit modifications of the electrode
E-mail address: prefait@univ-lr.fr (P. Refait). surface. All these curves were analyzed via a computer fitting procedure

http://dx.doi.org/10.1016/j.jelechem.2016.03.010
1572-6657/© 2016 Elsevier B.V. All rights reserved.

The mobile phase was composed of 0. i. a time necessary for the OCP to cathodic process. purity NaCl and de-ionized water (resistivity 18. the obtained leaf extract was added to 0. composed of a vacuum degasser. The effect of temperature on the inhibition efficiency was studied to +0. with the potential range) but to obtain information on the kinetics of 12 min. The were mixed with 1 L of de-ionized water under stirring for 1 h at range of this variation of potential has however to be kept small so as 75 °C. even if a rath- er small scan rate of 0. E were computer fitted as- suming that the anodic reaction obeys Tafel's law and that the cathodic Electrochemical measurements. Rahal et al. The expression of the anodic current ja is then: performed in a classical three-electrode cell. The first series of potentiodynamic polarization around OCP and EIS where βa is the anodic Tafel coefficient. Electrochemical measurements The experimental polarization curves j vs. the measurement of the polarization resistance Rp per- (HPLC. The evolution of the system was followed with given for the various determined parameters are the average of the time during 24 h. Moreover. i. in the 25–55 °C range. no linear part could be observed on Detection and quantification were performed at 254 nm.2 mV/s was used (the variations of Ecorr should in- 2. E curve acquired around OCP even if both reactions should maximum absorption of most phenols [25]. platinum foil and saturated calomel electrode (SCE: XR110. was under mixed activation–diffusion polarization and electrochemical impedance spectroscopy (EIS) were control.54 C. For this reason. in V−1. at a scan rate dE/dt = 2. for instance ±70 mV as in the present study.2. a quaternary may be more adequate. These polarization curves were acquired on a limited range of potential around OCP to induce only a minor perturbation of the metal 2. at 25 ± 2 °C when the experiments were performed (May– immersion. pump. 50% B.5. A thermostat controlled the temperature with an Each experiment was performed at least three times and the values accuracy of ± 0. 25 min.5 M NaCl solutions in various corrosion potential Ecorr of the metal could be decreased of 200 mV amounts (see Section 3. 5% B.6 mL min− 1. were fitted using electrical equivalent circuits with EC-Lab software The solutions were not stirred during the experiments. 95% B. In a recent study days. / Journal of Electroanalytical Chemistry 769 (2016) 53–61 which provided information about the influence of the inhibitor on the experiments was performed after 1 h. Experimental surface.25% acetic acid interface.4. The pH of the filtrate was measured at 5. with the following steps: 0 min. Karlsruhe. tary method to EIS. . 17 min. based on electrochemical kinetic laws. Characterization of the olive leaf extract by HPLC crease with increasing scan rate).8 after preparation. Pure copper. The EIS measurements were carried out The work electrodes were all made with the same pure copper in each case just after the acquisition of the polarization curve. The dal voltage. the method must be considered as destructive because The quantitative analysis of olive leaf extract was carried out using the modifications of the interface can be significant and irreversible. including potentiodynamic reaction. Imped- (99.e. Each polarization curve is required. a column oven and a diode array detector (DAD).e. and the other series after 6 and 24 h. i. the difference be- in water (solvent A)/methanol (solvent B) at a flow rate of tween the experimentally determined Rp and the true Rp value increases 0. An Eclipse The method called here “voltammetry around OCP” involves a larger XDB-C18 column (250 × 4. because of O2 consumption and increase of interfacial pH.99%) rod of 6 mm in diameter. Peaks were identified by obey Tafel's law.6 mm.. Voltammetry around OCP (ΔE = ±70 mV): methodology The olive leaves were first air-dried at room temperature (~25 °C) The determination of corrosion rates by electrochemical methods for one month in the absence of light. MA) was used at room temperature (25 °C) with an injection sufficiently small to have a negligible impact on the metal/electrolyte volume of 10 μL. ja ¼ jcorr :eβaðE−EcorrÞ ð1Þ The open-circuit potential (OCP) was recorded as a function of time except during the potentiodynamic polarization and EIS experiments. The impedance spectra 98% min. after the last EIS experiment. various measurements.d. The [26]. stored in a freezer at 4 °C. Extraction solution and extract preparation 2. a polarization curve was drawn from − 0.6 V/SCE at a sweep rate dE/dt = 0. The linearity of the system was checked in varying the 0. Germany) equipped with an formed on a small potential range (typically ± 15 mV around OCP) automatic injector. if the potential range is really important.5 mV s−1. near the the log|j| vs. 5 μm particle size. 2. and then a conditioning cycle of 5 min at the same conditions for the two processes can be neglected with respect to the other at the vi- the subsequent analysis. then down to OCP-70 mV and back to OCP. range. the reduction of O2. For an Agilent Technologies series 1100 liquid chromatography system such reasons. 22 min.5 °C.55 V/SCE June). cinity of OCP. The surfaces were prepared via an ance diagrams were obtained over a frequency range of 100 kHz to abrading procedure with silicon carbide (from grade 240 to grade 10 mHz with ten points per decade using a 10 mV peak-to-peak sinusoi- 1200). This innovative approach proved a useful complemen. it was for instance observed that after cathodic polarization. in particular for the cathodic reaction (typically O2 reduction).3.2 MΩ cm). a fitting procedure of the experimental congruent retention times compared with available standards. was used during the following information on the processes really occurring at OCP. The potential was swept from the OCP to OCP + 70 mV. Electrodes and electrolytes 0. but assumed to be Milford. the mixture was filtered through a filter paper to limit modifications of the electrode/electrolyte interface and obtain and the filtrate. 60% B. none of 5% B. counter and reference electrodes. However. The influence (Bio-Logic). Agilent Technologies.1). Radiometer-Analytical) were used as working. respectively. washed with distilled water and degreased with acetone.5. Each curve was analyzed using a computer fitting proce- dure described in Section 2. various kinetic laws can be used. After cooling. 45% B.5 mV s−1..e. 27 min. reach a quasi-stationary value.1. 2. The aim is not to determine Rp (in principle. 35% B. Then. phenolic compound was quantified in comparison with its standard The main advantage with respect to the so called Tafel method usually when it was available while the other detected compounds were used on polarization curves acquired on a wider potential range is that quantified by other equivalent compounds. 7 min. of the olive leaf extract concentration was studied at room temperature Finally. Waters Co. approximately after 24 h of (RT) i. the anodic and cathodic processes occurring at OCP.5 M NaCl solution used as aggressive medium was prepared with amplitude of the ac signal applied to the sample. As a consequence. 100 g of powdered leaves generally implies to modify the potential of the metal electrode.

/ Journal of Electroanalytical Chemistry 769 (2016) 53–61 55 The expression of the cathodic current jc. Fig. −e−βc ðE−Ecorr Þ : þ j lim jcorr j lim In region (I) an apparent Tafel behavior is observed and the current density increases up to jmax when the potential increases. In region (III). E is then: O2 þ 2H2 O þ 4e− →4OH− ð5Þ βa ðE−Ecorr Þ 1 j ¼ ja þ jc ¼ jcorr :e þ   ð3Þ 1 1 1 The anodic part of the curve shows three main regions of potential. 8: oleuropein. 6: apigenin 7.2. The HPLC chromatogram (Fig. 7: verbascoside and 8: oleuropein. RT (~25 °C). This effect is in- (HPLC) using a solution obtained with 100 g of powdered leaves creased when the inhibitor concentration is increased and reaches a mixed with 1 L of distilled water.55 and +0. The first step leads to the for- βa and βc and limiting cathodic current density jlim were obtained via mation of CuCl adsorbed on the metal surface according to the following the computer fitting of the potentiodynamic polarization curves. is: 3. 1. 4: pcoumaric acid. The dissolution of the film and/or metal is then 3.31].5 M NaCl solution in the 2: tyrosol. In region (II).1. Results and discussion potential increases again before to stabilize when it reaches a limiting current density. 1: hydroxytyrosol. 5: luteolin 7-glucoside. In the potential range considered here. 4: pcoumaric acid. Phenolic compounds contents of the studied olive leaf extract controlled by the diffusion of CuCl−2 [31].29]. 1) maximum for the largest considered concentration C1. the cathodic reaction is The experimental function used for the mathematical modeling of mainly the reduction of dissolved oxygen: the potentiodynamic polarization curve j vs. the Tafel coefficients a two-step reaction mechanism [30. E dissolution process of copper in the presence of Cl− ions proceeds via curve while the corrosion current density (jcorr).1. absence (blank) and presence of different concentrations (C1–C3) of olive leaf extract at glucoside. 2: tyrosol: 3: caffeic acid. Effect of olive leaf extract concentration Koutecky–Levich equation. the current density decreases from jmax to jmin due to the formation of a CuCl film [30]. Rahal et al. as it was also reported by several authors [28. HPLC chromatogram at 254 nm of the obtained olive leaf extract. C. For this study the solution C1 was di- luted two and five times which led to the solutions C2 (1. which confirms that this extract has a stronger influ- hydroxytyrosol. the shows several peaks corresponding to phenolic compounds. C3.42 mmol L−1 (C1). The Ecorr values measured for the blank. The The corrosion potential (Ecorr) was directly read on the log| j| vs. They are compared to the curve obtained in similar conditions in a 0. derived from the 3. where βc is the cathodic Tafel coefficient. Polarization curves of copper obtained after 24 h in 0. 5: luteolin ence on oxygen cathodic reduction than on copper oxidation reaction. Eight phe. and to a lesser extent. of the anodic branch.27–29]. the cathodic part of the log|j| vs.48 mmol L−1). 3: caffeic acid. 7: verbascoside. E curve was linear. The most abundant compound was oleuropein.21 mmol L−1) and C3 (0. Potentiodynamic polarization between −0. reaction: In some cases. in V−1. only the part of the curve corresponding to the In region (I). the 3. current density. namely. mixed charge transfer and mass transport controlling negative-going scan from OCP + 70 mV down to OCP − 70 mV was kinetics are usually assumed and thus the Tafel behavior of the curve computer fitted.5 M NaCl solution without olive leaf extract. 2. The experimental function used for the mathematical modeling of the curve is in this case: Copper dissolution occurs in the second step via the formation of CuCl− 2 complex: h i j ¼ ja þ jc ¼ jcorr eβa ðE−Ecorr Þ −eβc ðE−Ecorr Þ ð4Þ − CuCl þ Cl →CuCl2 − ð7Þ In each case. 7-glucoside. E curve was then achieved using Tafel's law for both anodic and cathodic currents. C2 and C1 solutions are in agreement with previous works [25. As a result. corrosion potentials shifted to more negative values in presence of nolic compounds are identified in the olive leaf extract. 6: apigenin 7-glucoside. 2 shows the polarization curves obtained on a large potential jc ¼   ð2Þ 1 1 1 range at the end of the 24 h of immersion in the various olive leaf extract −e−βc ðE−Ecorr Þ : þ j lim jcorr j lim concentrations C1–C3. and jlim the limiting solution referred to as “blank”. The quantitative study led to an estimated concentration of oleuropein of 2. . − Cu þ Cl →CuCl þ e− ð6Þ The computer fitting of the j vs. is only “apparent”. The presence of olive leaf extract results in a marked shift of the ca- The determination of phenolic compounds contents of the olive leaf thodic branch of the polarization curve towards smaller current density extract was carried out by high performance liquid chromatography values.2. 1: olive leaf extract.6 V/SCE 1 Fig. Fig.

Some computer fittings of the polarization curves obtained in the The cathodic Tafel coefficient βc was determined at − 26 ± 5 V− 1 in blank required the use of a mixed activation–diffusion controlled kinetic the blank solution but it decreases from − 18 ± 5 V−1 to − 33 ± for oxygen reduction while others were achieved using Tafel's law for 2 V−1 with the increase of the olive leaf extract concentration. more likely oleuropein (OLE). Solution jcorr βa βc jlim CR η The beneficial effect of the inhibitor on the substrate is also (μA cm−2) (V−1) (V−1) (μA cm−2) (mm year−1) (%) illustrated by the shape of the curves in region (III). 3) at RT (~25 °C). For con- centration C3.0–3. the computer fitting of the ηð%Þ ¼  100 ð8Þ j0 corr polarization curves acquired around OCP showed that the kinetic of ox- ygen reduction was whether partially controlled by diffusion or mainly where j0corr and jcorr are the corrosion current densities in the absence controlled by charge transfer but was never totally controlled by diffu- and presence of inhibitor. Experimental polarization curve around OCP of copper obtained after 24 h in 0. 3.041 ± 0. it appears that the limiting cathodic ciency (η).3 60 ± 8 when E increases. the shape of the diagram in the high frequency region differs and appears to involve two overlapping semi-circles.3 had to be used. the current density remains stable at j = jmin C3 1. sion (in this last case jcorr = jlim). − 0.3 ± 1. − 222.4).017 ± 0.3 – concentrations C1 and C2. the corrosion rate (CR) and the inhibition effi. The method may not be sufficiently accurate in in the blank solution and with the smallest inhibitor concentration C3 some cases.3 65 ± 14 −24 ± 7 −6. given in Table 1. This gives another example of the found for copper static electrodes in aerated neutral 3. So the Table 1 Ecorr shift reaches 85 mV for the highest concentration (C1).3 38 ± 13 −26 ± 5 –a 0. First of all. In only 1 case the curve had to be fitted with ca- thodic reaction under mixed control. So even after 1 h it seems that the system has reached stationary conditions. in the case of cies acting as a corrosion inhibitor.5 M NaCl solution without and with various concentrations of olive leaf extract at 25 °C. the NaCl solution (blank) and computed curve. The kinetic of the cathodic reaction creases strongly with the increasing olive leaf extract concentration. This value corresponds to a Tafel slope controlled by diffusion at OCP (i.3 70 ± 2 −18 ± 5 – 0.e.009 V decade− 1.5 M NaCl solution and the com. The inhibition efficiency (η) is then calculated according to the Looking back to the polarization curves acquired on a large range of following equation: potential (Fig. It could be linked to a non-stationarity of the system.1 0.e.02 ± 0.2 86 ± 5 the formation of the CuCl− 2 adsorbed species (reaction 3) preventing a the dissolution of the CuCl film and/or favoring its formation. The second semi-circle may correspond to the film of corrosion products.2 V/SCE).2. Voltammetry around OCP (ΔE = ±70 mV) The polarization curves obtained after 24 h of immersion in the could be fitted in most cases with activation controlled cathodic various solutions on a limited potential range (ΔE = ± 70 mV) were reaction (i. decreases the cathodic reaction rate. it may be partially ba equal to 0. i. However.5 V/SCE). For concentrations C2 and C1.6 ± 0. a slight inductive behavior is observed at low frequency. This clearly shows that the inhibitor hinders oxygen puted curve. until jlim is finally reached tion considered here. 3. For the two largest Blank 4. However. a value Electrochemical kinetic parameters and inhibition efficiency obtained from potentiody- namic polarization curves (ΔE = ±70 mV.3 59 ± 6 C2 1. in agreement with the values controlled by charge transfer. one must recall that the re- The values obtained for the various determined parameters are sults obtained by voltammetry around OCP relate to the kinetics at OCP.05 ± 1.007 ± 0. using Eq.5% g L− 1 relevance of voltammetry around OCP.5 V/SCE does not necessarily means that the kinetic is mainly average value of 59 ± 15 V−1. Electrochemical impedance spectroscopy (EIS) Fig. a mixed activation–diffusion control. may be partially controlled by charge transfer at OCP and totally con- which definitively confirms that this extract contains at least one spe. The adsorption of the inhibitor more likely hinders C1 0. it can be seen that O2 reduction is completely con- trolled by diffusion in any solution (even in blank) for the more cathodic j0 corr −jcorr potentials (around −0. 2). Actually. This inductive behavior was neglected. Fig.2 47 ± 2 −33 ± 2 −2.e. Consequently.8 ± 0.045 and 0. In contrast.7 0. for strongly cathodic potentials. i.e. are increasing when the potential decreases.e.5 ± 0. O2 reduction was under mixed computer fitted as described in Section 2. / Journal of Electroanalytical Chemistry 769 (2016) 53–61 respectively equal to − 210. Moreover.2. see Fig. It is probable that the impact of diffusion was may be related to the fact that the inhibitor mainly influences the ca. which the cathodic process. i. trolled by diffusion at more cathodic potentials. which are those of main interest. 3.060 V decade− 1 [2]. tion increases.56 C. such a behavior may rather be due to adsorp- tion phenomena and thus may point out the adsorption of the inhibitor Fig. it appears clearly that the corrosion rate de. and Eq. In contrast. − 278 and − 295 mV/SCE. So the observation of a plateau (j = jlim) The anodic Tafel coefficient βa is approximately constant around an at − 0. the OCP was stable after less than 15 min. The Nyquist diagrams obtained without inhibitor (blank) and with the small inhibitor concentration C3 shows a depressed semicircle in the high frequency region. the evolution of OCP was followed with time (results not shown) and it was observed that in any case. the limiting effects of diffusion The inhibition efficiency η reaches 86 ± 5% for the highest concentra. 3 shows as an example the experimental polarization current jlim decreases (in absolute value) when the inhibitor concentra- curve of copper obtained after 24 h in 0.5 to determine the corrosion activation–diffusion control for the larger C2 and C1 concentrations current density (jcorr). too small to be detected by voltammetry around OCP while EIS revealed thodic reaction. reduction. The obtained jlim value was −28 μA cm−2. This high frequency semicircle is mainly due to the charge transfer and double-layer capacitance [33]. 4 shows the Nyquist diagrams obtained after 24 h of immersion in 0. Rahal et al. respectively. sufficiently high to classify the olive leaf extract as a cathodic inhibitor rather than a mixed inhibitor [32].3. data corresponding to the lowest frequencies of this peculiar impedance .5 M on the copper surface. It is also interesting to note that the curves obtained the diffusional process. Four experiments were performed.9 ± 0. NaCl solutions that range between 0.2. and more particularly for C1.

In contrast. it was deduced that O2 reduction was under mixed ac. . Actually. 5. temperature. are fractional parameters describing the ΔE = ±70 mV. C. 5b and c). departure of the electrode from an ideal surface: for n = 1 the CPE tivation–diffusion control for the larger C1 and C2 concentrations and describes an ideal capacitor. / Journal of Electroanalytical Chemistry 769 (2016) 53–61 57 In accordance with this preliminary description of the EIS results. 5c in- cludes Warburg impedance and was used for concentrations C2 and diagram were excluded for the modeling. That of Fig. Equivalent circuits used to fit the EIS experimental data. etc. The parameters n1 and n2. For these two presented in Fig. 5a proved suitable for the Nyquist plot of copper in the blank solu- tion. the equivalent circuits used for copper in solutions containing olive leaf extract include a contribution of the film of corrosion products via the resistance Rf and the element Qf (Figs. 4. 5b does not include Warburg impedance and was used for concentration C3. with or without adsorption inhibitors [30. 6. which may be related to a The values obtained after the computer fitting of the Nyquist diffusion phenomenon. 6. Circles and squares (phase): experimental curves. Fig. 5. inhibitor adsorption. Nyquist plots for copper electrode immersion in 0. This shows that the contribution of the film of corro- sion products formed on the metal surface is negligible. porous layer formation. From the diagrams are listed in Table 2. semicircular shape at low frequency.5 M HCl solutions without to surface roughness. respectively. The model shows a good agreement with the concentrations and for the blank as well. Rp is the sum of Rf and Rct. In each experiments. This indicates that the corro. The EIS results according to: are therefore clearly consistent with those given by voltammetry. 24 h. These models were used in various studies to describe the behavior of copper or copper alloys in chloride containing solutions. Experimental Bode and Nyquist plots and their mathematical fitting: Example of copper in 0. (blank) and with various concentrations (C1–C3) of olive leaf extract at RT (~25 °C) for that leads to a distribution of time constants on the electrode surface. both situations were met and the Nyquist Rp −R0p plot shown here corresponds to a case where the cathodic reaction was ηð%Þ ¼  100 ð9Þ Rp partially controlled by diffusion. Rct is the charge transfer resistance. The equivalent circuit of Fig.5 M NaCl solution with inhibitor concentration C2 after 24 h at room Fig. In this model. Rahal et al. case. Finally. Rs is the solution resistance. the curves deviate from their experimental results for both Nyquist and Bode plots. In the case of the blank solution.33–36]. lines: computed curves. The equivalent circuit of Fig. Q dl corresponds to the capacitance of the double layer and W is the Warburg impedance related to the diffusion processes in the low frequency region. A typical example of the results given by the computer fittings is stronger effect at the higher concentrations C1 and C2. the analysis of impedance data were performed with the various equivalent circuits presented in Fig. Actually it is masked by a C1. where R0p and Rp are total polarization resistance of copper in the sion rate decreases due to the inhibitor in agreement with voltammetry solution in the absence and presence of inhibitor. These deviations arise from the inhomogeneous nature of the electrode due Fig. Q dl and Qf represent constant phase elements (CPE) used in place of capacitors to compensate for deviations from ideal dielectric behavior. associated analysis of the potentiodynamic polarization curves obtained with with Q f and Q dl respectively. it is clearly visible that the diameter of the curve grows with increasing olive leaf extract concentration. more likely that of dissolved O2. The inhibition efficiency η was computed mainly under activation control at concentration C3.

The growing film around OCP (Table 1). In contrast.89 ± 0.74 ± 0. blocks the cathod. frequency. the cathodic sites of the copper surface. significant changes of the electrode surface. e. 7 shows the potentiodynamic polarization curves of copper in Another time constant appears in the low-frequency region related to 0.3. favoring its stability and increasing its protective ability. It can be noted first that the Rct value obtained for the blank so- copper electrode in NaCl solution.07 ± 0.e. which indicates that the mechanism of the cess.e. In contrast.607 ± 0.3. As the inhibitor.01 0.3. The results obtained proved consistent with those of the main the measured charge-transfer resistance in Ω. Only the larger inhibitor cess is partially controlled by diffusion in both solutions. is with voltammetry around OCP applied only at the end of the 24 h of im- multiplied by 10: Rct = Rmes ct × S = 10 (Rmes ct × S / 10). / Journal of Electroanalytical Chemistry 769 (2016) 53–61 Table 2 Electrochemical impedance parameters for copper electrodes after 24 h in 0.02 W (Ω−1 cm−2 s0. ic sites so that only the small proportion of the surface not covered by The values of η are then 73 ± 10%.01 n1 0. imately constant. ter varies. In agreement.000 Ω cm2.1 μA cm− 2 after 1 h. and Rmes ct × S / 10 is in series of experiments. In contrast. there is no clear trend in the blank solution.2. i. i. Rf also increases. This once again con. after 1 h. and therefore jcorr (and also jlim) Note finally that all the experiments were performed once again. it can then be used as a itor. i. 6 h and 24 h. Rahal et al. More precisely. expressed in Ω cm2. However. 5). then Icorr is divided by 10. expressed using the overall surface S. This result is consistent with what was observed on the polariza- tion curves acquired in a large potential range (Fig. Actually.87 ± 0.5 M NaCl so- tentials. − 19 μA cm−2 vs. Note that Qdl decreases while Rct increases.03 0.90 ± 0. Moreover. 8 shows the Nyquist plots obtained for copper in 0. by adsorbing on the metal surface.02 0. Rf / (Rf + Rct) = 12% of the Nyquist diagram does not change with increasing time. Voltammetry around OCP (ΔE = ±70 mV) transfer. They are gathered in for the blank solution and 5c for inhibitor concentration C1 (see Table 3. It can be seen that in any case the corrosion current density of Fig. of Rp is mainly due to the increase of Rct with the inhibitor concentra.58 C.2. the impedance diagrams of copper in the Finally. Solution Blank C3 C2 C1 Rs (Ω cm2) 8.e.5) 216 ± 18 – 378 ± 100 334 ± 100 η% – 47 ± 2 65 ± 4 90 ± 4 As it was already visible from the Nyquist plots.5 M NaCl solution without and with olive leaf extract obtained after mass transport. the other to the contribution of the film formed on the surface. the increase than those determined with inhibitor concentration C1. The anodic coefficient βa is not that the film of corrosion products does not influence the corrosion pro- changed by the inhibitor. This shows that the method did not lead to i. In contrast Rct.2 by computer The impedance data could be modeled using equivalent circuits 5a fitting of the curves using Eq. that it has a poor protective ability. The kinetic parameters were ob. with the results given by voltammetry for this series of experiments.5 ± 2. the inhibition tion.011 8±3 6±1 Rct (Ω cm2) 2500 ± 800 4465 ± 100 6250 ± 1000 22. values the inhibitor remains active. SIE indicates that the pro- (a) 1 h. This is consistent with the assumption immersion is higher than the others.01 Rf (Ω cm2) – 275 ± 125 1150 ± 200 3000 ± 500 Qf 10−6 (Ω−1 cm−2 sn2) – 39 ± 5 23 ± 3 13. which explains why the shape of the values computed for jlim are significantly higher (in absolute value) curves changes with the inhibitor concentration. but is then also divided by 10.5 ± 3 7. As shown by the increase of Rf. activation–diffusion control. more likely O2 diffusion. one corresponding to charge 3. the shape of the there is also a slight contribution (i. efficiency could also be computed using |jlim | instead of jcorr in Eq.e. The resistance experiment were fitted in any case with O2 reduction under mixed Rf of the film of corrosion products also increases with the inhibitor con. Schematically. Fig. where voltammetry around OCP was applied first approximate equal to the Rct value measured without inhibitor. Rct clearly increases over time for the firms that the inhibitor behaves as a barrier hindering the access of O2 to inhibitor concentration C1. tained from these curves as explained in Section 3. This shows once again that the not blocked.5 M NaCl solutions with or without olive leaf extract at RT (~25 °C). The inhibitor.09 ± 0. (b) 6 h and (c) 24 h of immersion. if only 10% of the surface is similar to those computed from jcorr. describes the behavior of the metal surface not covered by the inhib. It can however be seen in Table 3 that the centration up to 3000 Ω cm2. in agreement concentration C1 was considered here. 6 and 24 h). of corrosion products has not a significant influence on the corrosion process for such small immersion times.5 n2 – 0. Rct increases with The curves obtained in the blank solution for this series of the inhibitor concentration from 2500 to 22. The current density is still inhibitor influences the rate of O2 reduction. This loop relates to the charge-transfer process of copper dis- ical modeling of the potentiodynamic polarization curves recorded solution occurring at the metal/electrolyte interface.73 ± 0.03 0.(6) or Eq. 62 ± 10% and 90 ± 4%. Fig.09 ± 0. Actually. Electrochemical impedance spectroscopy the inhibitor on the CuCl film limits its dissolution at strongly anodic po.01 0.g. the Nyquist dia- 3. it clearly increases with time in the presence of the sion products that have formed on parts of the metal not protected by inhibitor. where Rmes ct is mersion. it is also clear from the curves rate determined by voltammetry around OCP (Table 3) remains approx- of Fig.15 ± 0. already noted in Section 3. Only its diame- inhibiting effect) coming from the adsorption of the molecules on corro. So.01 0. The determined values of the various parameters are given in copper in the presence of olive leaf extract is lower than that of the Table 4. which shows that both beneficial effects .(8). − 5.73 ± 0. the corrosion anodic process is not modified.000 ± 5000 Qdl 10−3 (Ω−1 cm−2 sn1) 0.55 ± 0.07 0. The value of η (86 ± 5%) reached after 24 h of persion of the measurements). Actually.12 0. it can be seen that the values of η determined from EIS spec. the inhibitor also adsorbs on the film non-destructive technique to follow the evolution of a system over time. Effect of immersion time grams obtained with inhibitor concentration C1 clearly reveal the pres- ence of two overlapping capacitive loops.e. the values of η are lution does not vary significantly over time (taking into account the dis- all higher than 70%. 7 that only the cathodic reaction is inhibited. of corrosion products.(7). 2): the adsorption of 3. even if the 90% efficiency of olive leaf extract is mainly due lution without (a) and with (b) inhibitor concentration C1 at different to the adsorption of organic molecules directly on the metal surface immersion times (1.2. In both solutions.1. blank solution show only one capacitive flattened loop at high tra (Table 2) are very similar to those determined from the mathemat.

2 47 ± 2 −33 ± 2 −2. the cathodic reaction could only be modeled by the kinetic law corresponding to a mixed activation– Fig.3 ± 1. Nyquist plots for copper at different times (a) in 0. the highest inhibition efficiency is observed after 24 h.85 ± 0.9 ± 0.5 ± 0. once again.5 M NaCl solution without inhibitor (blank) or with the largest inhibitor concentration in C1 at different times: (a) 1 h.6 ± 0. at RT (~25 °C). which explains why the organic molecules finally adsorb on this film. 9. The results obtained in 0.3 73 ± 9 Immersion time = 24 h Blank −263 ± 50 4.35 ± 0. Solution Ecorr jcorr βa βc jlim η (h) (mV) (μA cm−2) (V−1) (V−1) (μA cm−2) (%) Immersion time = 1 h Blank −245 ± 35 3. It can be noted first that. In conclusion. the inhibition efficiency increases with time and is only around 60–70% at the beginning of the corrosion process (at least during 6 h). of the inhibitor increase over time.1 ± 1. .3 ± 1. Accordingly. 7. (b) 6 h and (c) 24 h.4. This is in fact consistent with the observed effect of the inhib- Fig.3 38 ± 13 −26 ± 5 −28 – C1 −258 ± 8 0.15 65 ± 2 −48 ± 8 −5.5 M NaCl solution with inhibitor formed on some parts of the steel surface while the inhibition efficiency concentration C1.6 50 ± 10 −28 ± 8 −19 – C1 −238 ± 6 0. C.9 ± 0.7 – C1 −233 ± 15 0. Polarization curves around OCP of copper in 0.55 75 ± 5 −35 ± 5 −9.3 75 ± 4 Immersion time = 6 h Blank −221 ± 25 3. 3.5 M NaCl solution with inhibitor concentration C1 are shown in Fig. The film of corrosion product was mainly inhibitor (blank) at different times and (b) in 0. It reaches 90% only after a longer immersion time (but be- fore 24 h). The kinetic parameters determined by computer fitting are listed in Table 5.7 86 ± 5 was still moderate. Effect of temperature The effect of temperature on the inhibition efficiency was investigat- ed by voltammetry around OCP (ΔE = ± 70 mV) in the temperature range 298–328 K. / Journal of Electroanalytical Chemistry 769 (2016) 53–61 59 Table 3 Electrochemical kinetic parameters and inhibition efficiency at RT (~25 °C) obtained from potentiodynamic polarization curves (ΔE = ±70 mV) for concentration C1 compared to those obtained without inhibitor (blank) at different times.3 64 ± 3 −52 ± 18 −3. 8.4 ± 0.5 M NaCl solution without itor on the corrosion products. Rahal et al.

53 ± 0. The obtained Arrhenius plot Ln jcorr vs. and approximately to a straight line and the Ea value can be determined reached 90% for the largest considered inhibitor concentration. the This value is significantly higher than that of 17. associated with a decrease in inhibition efficiency with increasing −2. 9 that increasing the can be quantified by computing the inhibition efficiency at each temperature increased the current density of the potentiodynamic po.27 ± 0.02 334 ± 100 90 ± 4 diffusion control.03 110 ± 50 72 ± 8 24 6±1 22. 2 and 7). Table 5 Electrochemical kinetic parameters and inhibition efficiency obtained from potentiody- namic polarization curves (ΔE = ±70 mV) for concentration C1 at different temperatures. This is more clearly illustrated in Table 5 by the when the temperature increases.01 0. T Ecorr jcorr βa βc jlim η (K) (mV) (μA cm−2) (V−1) (V−1) (μA cm−2) (%) 298 −258 0. which explains why the variations process. this means that η could be increased using a larger inhibitor concentration. corresponds to an increase in inhibition efficiency with temperature The dependence of the corrosion rate on temperature can be and a lower activation energy in the presence of the inhibitor [39–40]. but is characterized by a loss in inhibition efficiency at elevated temperatures.6 ± 1 1000 ± 500 16 ± 4 0. 4. The decrease of the inhibition efficiency with the temperature and the value obtained for the apparent activation energy of the corrosion process indicate a predominant physisorption mechanism.90 ± 0.7 ± 3 0.15 ± 0. Similarly. it can be seen from Fig.5 M NaCl solution 4. for instance the values of jcorr are more pronounced in the presence of the inhibitor. Experi- from the slope of this line. 9. variations of jcorr with temperature.14 ± 0. given in Table 5. Such type of inhibitors is efficient at ambient temperature. In this last case. see Table 1). The inhibition efficiency was found to increase The experimental curve obtained with the olive leaf extract corresponds with time during the 24 h experiments performed in this study. it has been proposed that physisorbed molecules are Ea bound to the metal at cathodic sites and mainly inhibit the corrosion jcorr ¼ A exp − ð11Þ RT process by hindering the cathodic reaction.2 8940 ± 30 0. after 24 h. from itor.2 13. which provided information on the inhibition corresponding line in Fig. T is the rate (see Figs. This is due to the temperature. Effect of temperature on the polarization curves around OCP of copper in 0.60 ± 0.11 ± 0. show that η decreases larization curves. a chemisorption mechanism the increase of temperature.4 34 −41 −14 65 Fig.88 ± 0.314 J mol− 1 K− 1).9 kJ mol−1 given in previous work [37] and the corrosion current density obtained at The olive leaf extract was found to be an effective green inhibitor of 25 °C in our experimental conditions (i.05 – – – 230 ± 80 – 24 8.4 ± 0.e.5 M NaCl 328 −344 3.55 ± 0.9 86 308 −234 1 75 −42 −6 82 318 −286 2.3 μA cm−2. voltammetry around OCP (ΔE = ± 70 mV).e.9 kJ mol−1 obtained polarization curves were computer fitted using various kinetic laws previously for copper without inhibitor (and used for drawing the for the cathodic reaction.03 650 ± 500 9. 10.74 ± 0. From an applied point of view.07 – – – 216 ± 18 – With inhibitor concentration C1 1 8. the limiting current jlim An increase of the corrosion activation energy in the presence of inhib- increases (in absolute value) significantly with temperature. i.9 μA cm−2 at 298 K to −127 μA cm−2 at 328 K. 9) [37]. expressed by the Arrhenius equation: Our results suggest a predominant physisorption of the inhibiting   species.94 ± 0.5 M NaCl. absolute temperature and R the universal gas constant (8. from 86% at 298 K to 63% at 328 K. Conversely. is frequently interpreted as due to the formation of an ad- fact that diffusion is a thermally activated process with a higher effect sorption film of physical nature.05 0. This is consistent with the voltammetry analysis that shows that the decrease of the corrosion where jcorr is the corrosion current density. 1/T is given in Fig. Two electrochemical methods were used.5 0.5) (%) Blank 1 6. involving electrostatic interactions on the reaction rate than the decrease of O2 concentration linked to with the metal surface [36.13 0. Actually. Rahal et al. EIS and corrosion process with inhibitor.8 ± 1.38]. A is the frequency factor. copper in 0.300 ± 2400 0.5 ± 3.05 – – – 478 ± 47 – 6 9.60 C.9 ± 0.02 0.01 3000 ± 500 13.12 0.61 ± 0. It is compared to that of copper in 0.5 ± 2.6 47 −33 −2.5 ± 3 2500 ± 800 0.02 434 ± 50 73 ± 2 6 7.5 3300 ± 300 0.000 ± 5000 0. The fitting of this curve with a straight line ments over longer times are to be performed to specify if the efficiency gave a value of 47 ± 6 kJ mol− 1 for the activation energy Ea of the can further increase. The inhibiting species present in the olive leaf extract act as a cathodic inhibitor adsorbed on the metal surface. / Journal of Electroanalytical Chemistry 769 (2016) 53–61 Table 4 Electrochemical impedance parameters at RT (~25 °C) obtained for concentration C1 after various times compared to those obtained without inhibitor. Ea current density was mainly due to a decrease of the cathodic reaction is the activation energy of the copper corrosion reaction. Secondly. . drawn using the Ea value of 17.12 ± 0. This effect of η = 90 ± 4% (EIS) and 86 ± 5% (voltammetry) after 24 h for the largest inhibitor concentration considered in this study. Both methods led to consistent results. The results. temperature. Time Rs Rct Qdl 10−3 n1 Rf Qf 10−6 n2 W η (h) (Ω cm2) (Ω cm2) (Ω−1 cm−2 sn1) (Ω cm2) (Ω−1 cm−2 sn2) (Ω−1 cm−2 s0.3 2600 ± 600 0.07 ± 0. Conclusions without inhibitor.02 0.1 20 −21 −127 63 solutions with inhibitor concentration C1.

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