Journal of Industrial and Engineering Chemistry 58 (2018) 92–99

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Journal of Industrial and Engineering Chemistry

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

Rollinia occidentalis extract as green corrosion inhibitor for carbon steel

in HCl solution
Patricia E. Alvareza,b,**, M. Victoria Fiori-Bimbia , Adriana Neskec , Silvia A. Brandánd,
Claudio A. Gervasie,f,*
a
Cátedra Física I, Instituto de Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471,
4000 San Miguel de Tucumán, Argentina
b
INQUINOA-CONICET, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 491, T4000INI San Miguel de Tucumán,
Argentina
c
Instituto de Química Orgánica, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471,
4000 San Miguel de Tucumán, Argentina
d
Cátedra Química General, Instituto de Química Inorgánica, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471,
4000 San Miguel de Tucumán, Argentina
e
INIFTA-CONICET, Facultad de Ciencias Exactas, UNLP, Suc. 4-C.C. 16, 1900 La Plata, Argentina
f
Area Electroquímica, Facultad de Ingeniería, UNLP, 1 y 47, 1900 La Plata, Argentina

A R T I C L E I N F O A B S T R A C T

Article history:
Received 27 September 2016 An extract of Rollinia occidentalis as well as pure solutions of two acetogenins isolated from this extract,
Received in revised form 2 September 2017 namely Rolliniastatin-1 and Motrilin, were tested as corrosion inhibitors for carbon steel in acidic
Accepted 6 September 2017 solutions. Weight loss measurements were performed in the 298–328 K temperature range and the
Available online 13 September 2017 obtained data were used to calculate corrosion rate and inhibition efficiency. It was found that the extract
and the acetogenins solutions act as good corrosion inhibitors for the tested C-steel in 1 M HCl media.
Keywords: Moreover, results from potentiodynamic polarization measurements indicate that R. occidentalis and the
Rollinia occidentalis extract two tested acetogenins act as mixed-type inhibitors. Data collected from EIS studies were modeled with
Green corrosion inhibitor
an equivalent circuit containing a single time constant what can be understood in terms of a corrosion
EIS
inhibition process resulting from the geometric blocking effect of the carbon steel surface by an adsorbed
FTIR
inhibitor species. Inhibitor adsorption follows a Langmuir adsorption isotherm. The inhibition efficiency
decreases with increasing temperature and extract concentration. Spectroscopic analysis points to the
formation of a complex between metal cations and compounds present in the R. occidentalis extract. This
additional aspect is considered in the proposed inhibition mechanism of C-steel.
© 2017 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction
Different industrial batch operations and closed-loop systems
require the addition of inhibitors to the process fluids and solutions
in order to reduce the rate of metal corrosion. Corrosion inhibitors
are particularly important in connection with pickling or acid
cleaning treatments when they are applied to carbon steel
* Corresponding author at: INIFTA-CONICET, Facultad de Ciencias Exactas, UNLP,
Suc. 4-C.C. 16, 1900 La Plata, Argentina.
** Corresponding author at: Cátedra Física I, Instituto de Física, Facultad de
Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471,
4000 San Miguel de Tucumán, Argentina.
E-mail addresses: palvarez@fbqf.unt.edu.ar (P.E. Alvarez),
gervasi@inifta.unlp.edu.ar (C.A. Gervasi).
surfaces. As industrial acid cleaner and pickling acid HCl is very
often used [1]. In order to remove scales from the surface pickling
is used and is usually applied prior to hot-dip coating or
electroplating [2]. A less severe treatment than pickling like acid
cleaning is used for final finish of metal surfaces before plating,
painting, or storage. Acid solutions of 40–60 vol% hydrochloric acid
(often containing up to 1% inhibitor) are used at room temperature
for removing soil and light rust. Consequently, a large research
effort has been devoted to finding new suitable compounds to be
used as corrosion inhibitors for carbon steel in acidic solutions.
These studies showed that there is a large number of organic and
inorganic compounds which added in small amounts to the
corrosive media can effectively decrease the corrosion rate [3–5].
Many works were conducted to assess some naturally occurring
substances as corrosion inhibitors for different metals in various

http://dx.doi.org/10.1016/j.jiec.2017.09.012
1226-086X/© 2017 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
 P.E. Alvarez et al. / Journal of Industrial and Engineering Chemistry 58 (2018) 92–99
Fig. 1. Molecular structures of five acetogenins present in the Rollinia occidentalis
extract.
environments [6–10] as well as crude extracts and pure
components isolated from the extracts [11–15].
Typically, effective organic inhibitors contain either N, S, or O
atoms in their structures or electronegative functional groups and
p electrons in triple or conjugated double bonds. Adsorptive
interactions between adsorbates and the metal surface explain the
inhibiting action of these organic compounds. In this regard, the
following plausible elementary processes were used as a basis to
propose an inhibition mechanism: (1) electrostatic attraction
between the charged metal and the charged inhibitor molecules,
(2) vacant d-orbitals of Fe atoms in the metal interacting with lone
pair electrons of heteroatoms (N, S or O), (3) vacant d-orbital of Fe
atoms in the metal interacting with p electrons in aromatic rings
and when possible (4), a combination of some of these three
processes.
Since many organic inhibitors are toxic and not sufficiently
cost-effective, the successful application of seed and plant extracts
as green corrosion inhibitors was pursued [16].
Rollinia occidentalis is a plant species of Annonaceae family
which is found in north-west Argentina. Molecular structures of
five acetogenins present in the tested R. occidentalis extract are
shown in Fig. 1 [17]. The aim of the present work is to assess the
feasibility of using the naturally occurring, cheap and environ-
mentally safe extract of R. occidentalis for the corrosion inhibition
of C-steel in acidic media. The use of this extract is expected to
achieve simultaneously, the economic and environmental goals.
Experimental methods
Preparation of solutions and steel samples
Weight percentage composition of the tested mild steel
specimens was as follows: 0.04% P, 0.06% Si, 0.06% Al, 0.20% Mn,
0.05% C, 0.02% S, 0.02% Cr and the remainder Fe. Surface treatment
of the specimens involved wet-grinding with emery paper grades
N
400–N
1200; rinsing with distilled water, degreasing with
acetone and finally, drying with warm air before use.
Plant material: R. occidentalis fruits were collected in the
province of Tucumán, Argentina, in March 2005. A voucher sample
(No. 604639) was deposited at the Herbarium of Instituto Lillo in
the city of Tucumán, Argentina.
93
For the present work the following acetogenins were isolated
from the methanol seeds extract: rolliniastatin-1 and motrilin.
Extraction of R. occidentalis and purification of acetogenins:
Dried and powdered seeds of R. occidentalis were percolated with
methanol. Evaporation of the solvent yielded a crude MeOH extract
which was further partitioned between CHCl3 and H2O. The CH3Cl
layer was washed with water, dried over anhydrous Na2SO4,
filtered, and evaporated in vacuum to give 9 g of a solid extract. The
residue was chromatographed on a silica gel column by using
chloroform and increasing amounts of ethyl acetate (0–100%) and
finally methanol as eluents.
Chromatographic fractions containing acetogenins (TLC detec-
tion by Kedde’s reagent) were further processed by high-
performance liquid chromatography (HPLC)using a Beckman C
18 column (25 cm  1 cm i.d., 5 mm particle size) and mixtures of
methanol and water to yield pure acetogenins.
The corrosive medium was 1 M HCl (Merck) prepared from 37%
analytical grade reagent. From a stock solution four diluted seeds
extract solutions were prepared with final concentrations: 0.1, 0.4,
0.7 and 1.0 g L1.
Weight loss measurements
Weight loss measurements were carried out in 50 ml of 1 M HCl
solution containing 0.1, 0.4, 0.7 or 1.0 g L1 of the seeds extract and
in 50 ml of 1 M HCl solution containing 0.007 g L1 of either
rolliniastatin-1 or motrilin. Steel coupons with dimensions
1.0 cm  4.0 cm  0.1 cm were immersed completely. After 3 h of
immersion each coupon was retrieved from the test solution and
immersed in 20% sodium hydroxide solution containing 200 g L1
of Zn dust as a means of cleaning the corrosion products.
Subsequently, the coupons were scrubbed several times with a
bristle brush under water to remove corrosion products, and
finally, they were dried in acetone and reweighed.
Experiments were performed in triplicate and the resulting
data showed good reproducibility (below 5% deviation from the
mean value). In each case the mean value of the weight loss has
been reported. Weight loss measurements were carried out at
temperatures 288, 298, 308 and 318 K in absence and presence of
different concentrations of the inhibitor in the test solution.
Weight loss data were used to calculate corrosion rate (CR)
expressed in units of mg cm2 s1 and inhibition efficiency in a
percentage scale h (%).
Electrochemical measurements
Steel samples for electrochemical experiments were machined
into cylindrical specimens and then embedded in polytetrafluoro-
ethylene (PTFE) with an exposed geometrical circular area of
0.16 cm2. Prior to each experiment the electrode surface was
pretreated as described above. Electrochemical experiments were
conducted in a three-electrode electrochemical cell by using a
Zahner IM6 electrochemical workstation. A platinum sheet was
used as the counter electrode, and a saturated calomel electrode
(SCE) was used as the reference electrode. All potentials in this
work are referred to the SCE (0.2412 V with respect to the standard
hydrogen electrode). Measurements were performed in naturally
aerated and unstirred solutions after 1 h of immersion at 298  1 K.
Impedance measurements (EIS) were made at the corrosion
potential (Ecorr) over a frequency range from 100 kHz to 100 mHz,
with a perturbation signal amplitude of 10 mV. Potentiodynamic
polarization (PP) curves were recorded by sweeping the applied
potential Eapp at a scan rate of 1.0 mV s1 while the current I was
recorded. Just like the gravimetric measurements, PP curves were
measured in triplicate to confirm acceptable reproducibility of
results.
94 P.E. Alvarez et al. / Journal of Industrial and Engineering Chemistry 58 (2018) 92–99

UV–visible and IR spectrophotometric measurements

Functional groups responsible for the inhibition were investi-

gated by using FT-IR spectra. Spectra of the solid compounds
generated on mild steel after 3 days immersion in 1 M HCl
without and with 1.0 g L1 R. occidentalis extract were measured
with the KBr pellet technique. The spectra were recorded in the
range from 4000 to 400 cm1 with a resolution of 1 cm1 and 200
scans and on a Fourier transform infrared (FT-IR) PerkinElmer
spectrophotometer that is equipped with a Globar source and a
DGTS detector.
UV–visible absorption spectrophotometric measurements
were carried out for 1 M HCl solution without and with 1.0 g L1
Rollinia extract before and after mild steel samples immersion at
298  1 K for 3 days. All spectra were recorded using a Cary 50 Scan
spectrophotometer.
Fig. 2. Corrosion rate (CR) of mild steel in 1 M HCl containing various concentrations
SEM surface analysis (C) of Rollinia at different temperatures.

Morphological studies of the mild steel samples were

conducted by using SEM examinations of surfaces exposed to
different test solutions. Micrographs were obtained with a Zeiss
Supra 55VP scanning electron microscope operating with a
tungsten filament as electron source. Mild steel specimens of
dimensions 2 cm  1 cm  0.14 cm were ground successively with
silicon carbide abrasive paper of different grades (#400–#1200).
Thereafter, the samples were polished using a cloth with 5 mm
diamond paste to obtain a near mirror-like finish of the surface.
The cleaned coupons were then immersed for 2 h in the blank
solution 1 M HCl without and with 1.0 g L1 Rollinia extract at
298  1 K, and finally, they were washed with distilled water, dried
in warm air, and submitted for SEM surface examination.
Results and discussion
Weight loss measurements
Corrosion rate and inhibition efficiency
Corrosion of mild steel in 1 M HCl containing various
concentrations of Rollinia extract or 0.007 g L1 of either roll-
iniastatin-1 or motrilin was studied by weight loss measurements,
i.e. by measuring the mass of metal turned into corrosion products
per unit of surface area per unit of time. In this case, h(%) is
calculated by applying the following equations:
Wb  Wa
CR ¼
At
Rollinia increases up to 0.4 g L1 and beyond this concentration the
decrease becomes less noticeable. This indicates that Rollinia acts
as an inhibitor that effectively reduces the attack by the corrosive
solution. Further inspection of Fig. 2 reveals that corrosion rate of
mildsteel in the absence and presence of the inhibitor increases
with an increase in temperature.
Fig. 3 shows h (%) plotted as a function of the inhibitor
concentration, at different temperatures. Examination of the plots
reveals an initial rapid increase in h(%) for increasing Rollinia
concentration up to 0.4 g L1, but the inhibition efficiency increases
only marginally with further increase in concentration of the
inhibitor. This indicates that Rollinia acts as an effective inhibitor
even at low concentrations. Moreover, inhibition efficiency
decreases with increasing temperature. The fact that the inhibition
efficiency decreases as the temperature increases can be under-
stood in terms of the metal dissolution process being enhanced
while the rate of desorption of inhibitor molecules is larger at
higher temperature [18,19].
Inspection of data shown in Figs. 2 and 3 reveals that corrosion
rate increases with increasing temperature both in uninhibited and
inhibited conditions.
Weight loss measurements carried out at 298  1 K in 1 M HCl
solutions with a concentration of 0.007 g L1 of either of the two
isolated acetogenins allowed to determine inhibition efficiencies
h(%) of 71.6% for Rolliniastatin-1 and 68.9% for motrilin (Table 1).
ð1Þ

C RðblankÞ  C RðinhÞ
h ð%Þ ¼  100 ð2Þ
C RðblankÞ

where Wb and Wa are the coupon weights measured before and

after immersion in the test solutions, A is the exposed area and
t = 3 h is the exposure time. CR is the corrosion rate of mild steel and
the subscripts (blank) and (inh) indicate the absence and presence
of the inhibitor in the hydrochloric solution, respectively.
Experimental results obtained from weight loss measurements
for mild steel in 1 M HCl solution without and with different
concentrations of Rollinia extract are presented in Figs. 2 and 3.
Fig. 2 shows plots of the corrosion rate (CR) as a function of the
inhibitor concentration (C), at different temperatures. These plots
show that the corrosion rate decreased in response to the additions
of increasing amounts of Rollinia to the corrosive medium.
Specifically, the corrosion rate of the steel coupons after the Fig. 3. Corrosion inhibition efficiency in percentage h(%) of mild steel as a function
addition of Rollinia markedly decreases as the concentration of of Rollinia concentration C in 1 M HCl at different temperatures.
 P.E. Alvarez et al. / Journal of Industrial and Engineering Chemistry 58 (2018) 92–99 95

Table 1 Electrochemical measurements

Calculated activation energy Ea values for mild steel
corrosion rate in 1 M HCl in the absence and the
presence of different concentrations of Rollinia Potentiodynamic polarization (PP) curves
occidentalis extract. PP curves shown in Fig. 5 were measured for mild steel in 1 M
HCl blank solution and in the same solution containing different
C (g L1) Ea (kJ mol1)
concentrations of R. occidentalis extract.
0.0 (Blank) 41.9
Each increase in the extract concentration results in smaller
0.1 50.6
0.4 52.3
current densities both for the anodic and the cathodic branches of
0.7 54.6 the PP curves. However Tafel slopes and the corrosion potential
1.0 54.7 remain practically unchanged. Clearly, R. occidentalis extract acts as
a mixed-type inhibitor decreasing simultaneously the anodic
contribution (metal dissolution) and the cathodic contribution
Effect of temperature
(hydrogen evolution) to the corrosion process. These results are
In order to calculate the activation energy for the corrosion
compatible with an inhibition mode characterized by the
reaction, the Arrhenius equation (3) was used:
geometric blocking of the metal surface by the adsorbed inhibiting
 
Ea species. The geometric blocking effect basically leads to a reduction
C R ¼ A exp  ð3Þ in the reaction area.
RT
Mansfeld [21,22] proposed a precise procedure of analysis to
where CR is the corrosion rate, R the gas constant, T the absolute determine polarization resistance Rp and Tafel slopes from
temperature, A the pre-exponential factor. polarization data (Eapp vs. I) measured within a small potential
The activation energy (Ea) at different concentrations of R. window around Ecorr. Firstly, Rp was derived as usual, in the pre-
occidentalis extract in the hydrochloric solution was determined by Tafel regions of the polarization curve, from the slope of the
linear regression of ln CR vs. 1/T data (Fig. 4) and the results are tangent at Ecorr. Secondly, by using Mansfeld’s approach, anodic
shown in Table 1. (ba) and cathodic (bc) Tafel slopes were calculated through
Linear regression coefficients are close to 1, indicating that steel nonlinear least-squares fitting of polarization data in the form
corrosion in 1 M HCl acid can be explained by using the kinetic 2.3IRp vs. (Eapp  Ecorr) to the corresponding theoretical expression,
molecular theory. Inspection of Table 1 shows that the values of Ea within the (Ecorr  30 mV) potential window. Table 2 contains the
determined in 1 M HCl containing different concentrations of R. results of this polarization data analysis together with values for
occidentalis extract are larger than the value obtained for the Ecorr and the corrosion current density jcorr.
uninhibited blank solution. Fig. 6 shows PP curves measured for mild steel in 1 M HCl blank
A decrease in inhibition efficiency with increasing temperature solution and in the presence of 0.007 g L1 of either of the two
combined with a lower activation energy for the corrosion rate in tested acetogenins isolated from the seeds extract (rolliniastatin-
the blank solution than in the inhibited solution might be related 1 and motrilin).
to a physical adsorption between the iron surface and the inhibitor Addition of any of both acetogenins to the HCl blank solution
[20]. results in smaller current densities both for the anodic and the
cathodic branches of the PP curves as compared with the curve for
the uninhibited solution. Tafel slopes and the corrosion potential
remain practically unchanged. Both acetogenins, like the R.
occidentalis extract, act as a mixed-type inhibitors decreasing
simultaneously the anodic and cathodic contributions to the
corrosion process.
Table 3 contains the results derived from the polarization data
analysis together with values for Ecorr and the corrosion current
density jcorr.
Inhibition efficiencies by the acetogenins as pure species are
comparable with the value obtained using the R. occidentalis
extract at its lowest tested concentration. These data suggest that

Fig. 4. Arrhenius plots for the corrosion rate of steel in 1 M HCl in the absence and
presence of Rollinia occidentalis extract at different concentrations.

Table 2
Corrosion data derived from potentiodynamic polarization curves analysis (see
text) for carbon steel in 1 M HCl with different concentrations of Rollinia occidentalis
extract at 298  1 K.

C (g L1) Ecorr jcorr bc ba Rp h%

(mV vs. SCE) (mA cm2) (mV/dec) (mV/dec) (Vcm2)
0.0 563 920 166 146 36.7 –
0.1 574 419 165 137 77.4 52.5
0.4 576 193 163 136 166.5 77.9
0.7 571 148 163 128 210.5 82.6 Fig. 5. Polarization curves for steel recorded after 1 h of immersion, at 298  1 K in
1.0 571 119 144 138 257.3 85.7 1 M HCl containing different concentrations of Rollinia occidentalis extract.
96 P.E. Alvarez et al. / Journal of Industrial and Engineering Chemistry 58 (2018) 92–99

Fig. 6. Polarization curves recorded after 1 h of immersion for mild steel, at

298  1 K in 1 M HCl blank solution and 1 M HCl solution containing 0.007 g L1
rolliniastatin-1 or 0.007 g L1 motrilin.
Fig. 8. Bode plots for steel in 1 M HCl solution containing 0.7 g L1 of the Rollinia
occidentalis extract. Experiment (*) and fitting (—).

Table 3 elucidate the operative form of the inhibition mechanism. Fig. 7

Corrosion data derived from PP curves analysis for carbon steel in 1 M HCl solution shows Nyquist plots of the impedance spectra obtained for mild
containing 0.007 g L1 rolliniastatin-1 or 0.007 g L1 motrilin at 298  1 K.
steel in the absence and presence of different concentrations of R.
Acetogenin Ecorr jcorr bc ba Rp h% occidentalis extract. Typically, a single depressed capacitive
(mV vs. SCE) (mA cm2) (mV/ (mV/ (Vcm2) semicircle characterizes Nyquist plots for the blank solution and
dec) dec)
for the inhibitor-containing solutions, over the studied frequency
Rolliniastatin- 0.580 429.8 163 136 74.9 51 range. When the faradaic impedance Zf of the system is given solely
1
by a charge transfer resistance, like the spectra shown in Fig. 7
Motrilin 0.564 491.5 163 136 65.5 44
containing a single capacitive loop, inhibition was shown to be
associated with a geometric blocking effect that achieves high
efficiency [23]. Therefore, the total impedance is described by a
the strong inhibitory action performed by the extract is mainly due parallel connection between the polarization resistance (here
to the presence of these compounds. equal to the charge transfer resistance) and the double layer
capacitance (Cdl) while these two impedance elements are
Electrochemical impedance spectroscopy measurements connected in series with the electrolyte resistance.Theoretical
For the sake of comparison corrosion rates were also deter- and experimental impedance spectra for mild steel in 1 M HCl
mined through EIS measurements for the uninhibited as well as for containing 0.7 g L1 of the R. occidentalis extract are shown in Fig. 8.
the inhibited system. EIS experiments are particularly suitable Experimental data are in good agreement with the impedance of
when they are used to obtain corrosion rates in a rapid and the selected equivalent circuit.
accurate way. In addition, the impedance response can help to Taking into account the frequency dispersion effect present in
depressed semicircles of the complex plane representations of the
experimental impedances, double layer capacitance was evaluated
according to Eq. (4) [24]
00
1
C dl ¼ 2 p f m Rp ð4Þ
00
where fmis the frequency at which the imaginary component of
the interfacial impedance is at a maximum.
Polarization resistance values were calculated from the Nyquist
diagrams measured at Ecorr taking into consideration the following
definition

Rp ¼ lim ReðZ f Þ ð5Þ

v!0

where Re(Zf) is the real part of the faradaic impedance Zf and v is

the sinusoidal perturbation signal (v = 2pf).
Addition of increasing amounts of R. occidentalis extract to the
blank electrolyte results in increasing polarization resistance
values.
Polarization resistance and double layer capacitance data are
assembled in Table 4 for different concentrations of the inhibitor in
the HCl solution. Rp values confirm the inhibitory action of R.
occidentalis extract. Moreover, the double layer capacitance (Cdl)
decreases with increasing concentration of the inhibitor, some-
Fig. 7. Nyquist diagrams for steel in 1 M HCl blank solution and solutions containing
thing that can be understood in terms of a reduction of the active
additionally different concentrations of Rollinia occidentalis extract.
 P.E. Alvarez et al. / Journal of Industrial and Engineering Chemistry 58 (2018) 92–99 97

Table 4 Table 5
Impedance elements derived from spectra recorded for steel in 1 M HCl with Impedance elements derived from spectra recorded for steel in 1 M HCl containing
varying concentrations of Rollinia occidentalis extract at 298  1 K. 0.007 g L1 of either rolliniastatin-1 or motrilin at 298  1 K.

C (g L1) Rp (V cm2) Cdl (mF cm2) h% Test solution Rp (V cm2) Cdl (mF cm2) h%
1
0.0 54.8 184.0 – Rolliastatin-1 0.007 g L 193.1 52 72
0.1 90.8 110.9 39.6 Motrilin 0.007 g L1 132.7 76 59
0.4 167.1 75.6 67.2 Blank 54.8 184 –
0.7 212.7 59.4 74.2
1.0 269.9 68.0 79.7
occidentalis extract, namely, rolliniastatin-1 and motrilin present in
the HCl solution. Rp values confirm the inhibitory action of the
metal surface due to the blocking effect brought about by the acetogenins and yield inhibition efficiencies comparable to those
adsorbed inhibitor.At this point it is worth mentioning that Cdl calculated from gravimetric data.
values in Table 4 are referred to the apparent sample area.
Cdl allows to calculate the “relative coverage” (m) according to
the following equation: Corrosion inhibition mechanism

C inh The above studies have shown that the Rollinia extract exhibits
m¼1 dl
ð6Þ
an inhibition effect which might result from the formation of
C blank
dl
complexes. In order to gain an insight into the possibility of the
where C inh blank
dl and C dl represent the double layer capacitance at the occurrence of a complexation reaction, infrared and UV–visible
interface of the electrode with the inhibited solution and with the spectroscopic measurements were performed. Fig. 11 shows the IR
blank solution, respectively. spectrum of a solid sample of Rollinia extract together with the IR
Likewise, inhibition efficiency h can be calculated by using Rp spectrum corresponding to solid surface products generated on
values in the following way: mild steel in 1 M HCl with 1.0 g L1 Rollinia extract after 3 days of
immersion in the acid solution at 298 K. The most intense bands
Rblank observed in the IR spectrum of the Rollinia extract can be easily
h¼1 p
ð7Þ
Rinh
p
assigned by comparison with the assignments reported by Breda
et al. [25] for 2(5H)-furanone because this species is the main
where Rinh
p and Rp
blank
represent the polarization resistance for the structure recognizable in the acetogenins depicted in Fig. 1.
electrode in the inhibited solution and in the blank solution, Various modifications are observed in the IR spectrum
respectively. measured after steel immersion in the hydrochloric solution of
Cdl values in Table 4 were used to calculate m which was plotted R. occidentalis. For instance, the broad band at 3404 cm1 in the
against h obtained from Rp values in Table 2 [23]. The resulting plot initial IR spectrum assigned to the OH stretching shifts toward
of m vs h exhibits an acceptable linear trend followed by a straight higher wavenumbers (3435 cm1) after the immersion and
line passing through the origin, in agreement with the proposed simultaneously increases its intensity relative to the other bands
geometric blocking effect. [26]. Hence, the shortening of the O H bond lengths could be
Fig. 9 shows Nyquist plots of experimental impedance data that attributed to the presence of coordinated O atoms. The group of
were obtained for mild steel in the blank solution and in the 1 M intense bands between 2922 and 2856 cm1 associated to CH2
HCl solution containing 0.007 g L1 of either rolliniastatin-1 or stretching modes decrease in intensity, as can be seen after
motrilin. comparison of both spectra in Fig. 10. Therefore, restrictions of
Polarization resistance and double layer capacitance data are those modes are also expected for the conditions of the spectrum
assembled in Table 5 for the two acetogenins isolated from the R. in Fig. 10b. Also note that the band at 1510 cm1 assigned to the CH2
deformation modes disappear in the spectrum of Fig. 10b what
supports the hypothesis of restriction of those groups. On the other
hand, the broad bands between 1712 and 1597 cm1 in the initial IR
spectrum, easily assigned to C¼O and C¼C stretching modes,
undergo a notable decrease in their intensities for the conditions of

Fig. 9. Nyquist diagrams for steel in 1 M HCl and in 1 M HCl containing 0.007 g L1 of Fig. 10. Experimental infrared spectra corresponding to a sample in solid state of (a)
one of the two acetogenins isolated from the Rollinia occidentalis extract, namely, Rollinia occidentalis extract; (b) surface products generated on mild steel after 3 days
rolliniastatin-1 and motrilin. immersion in 1 M HCl with 1.0 g L1 Rollinia occidentalis extract.
98 P.E. Alvarez et al. / Journal of Industrial and Engineering Chemistry 58 (2018) 92–99

Fig. 10b. Here, the O atoms belonging to the C¼O bonds of the increases. Another fact worthy of mention is that a slight change in
furanone rings present in the acetogenins of the R. occidentalis the intensity of the band at 275 nm is also noticeable. The p ! p*
extract are possibly coordinated to the Fe2+ ions forming and n ! p* interactions as expected from the presence of C¼C and
complexes in the experimental conditions described for Fig. 10b C¼O groups, might explain the occurrence of the bands at 215 nm
[27–29]. and 275 nm, respectively, while the new band could be justified by
A simulation performed by using B3LYP/LanL2DZ calculations the formation of a complex of Fe, as reported by Ehrt and Möncke
of a complex between four furanone molecules and one Fe2+ cation for the Fe2+ charge transfer bands with a maximum at 220 nm [32].
generate an infrared spectrum with eight defined bands in the Here, the formation of new products after immersion of the steel
1693–1603 cm1 region where the four most intense bands are sample in the solution is evident.The differences among the three
attributed to the C¼O stretching modes and the other four bands spectra are clearly observed in Fig. 11 and are indicative of the
are associated with the C¼C stretching modes [30]. Moreover, the characteristic pattern of complex formation between R. occiden-
IR spectrum of the simulated complex also presents bands in the talis and Fe2+ ions released during the corrosion reaction.
600–400 cm1 region that can be easily attributed to FeO
stretching modes. On the other hand, in the region of lower Surface morphological examination
wavenumbers we observe an expansion and shifting of the bands
associated to the C¼O rocking and out-of-plane deformation The surface morphology of mild steel surfaces unexposed and
modes and to the formation of new Fe O bonds (671 and exposed to 1 M HCl solutions in the absence and presence of
492 cm1). Hence, complexes formed between metal cations and 1.0 g L1 R. occidentalis extract were examined by using SEM.
the O atoms of both C¼O and OH groups of the compounds in the Analysis of the micrographs in Fig. 12 reveal that the mild steel
inhibitor participate in the corrosion inhibitory action. Addition-
ally, these complexes can exhibit a restrictive effect on the side
chains and, as a consequence, on the vibration modes of the CH2
groups.
UV–visible spectroscopic measurements were undertaken
since it has been reported that a change in position of the
absorbance maximum and a change in the value of absorbance
indicate that a complex between two species in solution is
probably formed [31]. Fig. 11 shows UV–visible absorption
spectra measured for 1 M HCl solution without and with 1.0 g L1
R. occidentalis extract, before and after immersion of mild steel
samples for 3 days at 298 K. The solution resulting from mild steel
immersion in 1 M HCl yields a spectrum with two bands, one with
low intensity at ca. 252 nm and the other with an intense
absorption maximum at ca. 205 nm, while the spectrum for 1 M
HCl containing the inhibitor shows an intense band at ca. 215 and
230 nm and a shoulder at ca. 275 nm. On the other hand, in the
spectrum of the solution resulting after 3 days of immersion of
mild steel in 1 M HCl with added inhibitor we observed two
differences in comparison with the spectrum for 1 M HCl
containing the inhibitor but in absence of Fe2+ ions, namely, after
immersion of the steel samples: (i) an intense and new band
appear at ca. 220 nm and (ii) the intensity of the band at 230 nm

Fig. 11. UV–visible spectra of (i) 1 M HCl with 1.0 g L1 Rollinia occidentalis extract
(—); (ii) 1 M HCl with 1.0 g L1 Rollinia occidentalis extract after mild steel immersion Fig. 12. SEM images for (a) unexposed mild steel; (b) mild steel exposed to the
for 3 days at 298 K (—); (iii) 1 M HCl after mild steel immersion for 3 days at 298 K blank solution, and (c) mild steel exposed to1 M HCl containing 1.0 g L1 Rollinia
(—). occidentalis extract for 3 h at 298 K.
 P.E. Alvarez et al. / Journal of Industrial and Engineering Chemistry 58 (2018) 92–99
specimens exhibit a very rough surface in the absence of the
inhibitor (Fig. 12b) arising from the corrosive attack by the acid
solution. The attack was quite uniform, however the occurrence of
a slight selective corrosion cannot be ruled out (compare Fig. 12b
with Fig. 12a for the unexposed steel sample). In Fig. 12c, even with
a larger magnification, the surface of the sample immersed in the
inhibited solution looks comparatively smoother than the sample
immersed in the uninhibited solution what confirms the inhibiting
action of R. occidentalis.
Conclusions
This work gives a proof of concept for the use of R. occidentalis
extract as a green corrosion inhibitor for mild steel corrosion. This
advance, i.e. its potential application, is provided by this work for
the first time in the literature. Moreover, the action of two pure
components present in the extract, namely, the acetogenins
rolliniastatin-1 and motrilin, were also successfully tested.
(1) R. occidentalis extract can be used without further addition of
other compounds as an efficient inhibitor for mild steel
corrosion, even at very low concentrations. An increase in
temperature causes a decrease in the inhibition efficiency.
(2) Corrosion inhibition is mainly achieved through physical
adsorption of different compounds in the extract onto the
mild steel surface.
(3) The extract of R. occidentalis can be considered a mixed-type
inhibitor since it affects both the anodic and cathodic reactions.
Moreover, this behaviour can be understood in terms of an
inhibition mode resulting from the geometric blocking of the
metallic surface by the adsorbed inhibitive species.
(4) Spectroscopic analyses by using the IR and UV spectra support
the coordination of O atoms to the Fe2+ ions forming complexes
that become adsorbed on the steel surface.
Acknowledgements
C.A. Gervasi gratefully acknowledges the Comisión de Inves-
tigaciones Científicas y Técnicas Buenos Aires (CICBA) for his
position as a member of the Carrera del Investigador Científico. The
authors gratefully acknowledge the Consejo de Investigaciones de
la Universidad Nacional de Tucumán (CIUNT).
99
This work was supported by the Agencia Nacional de Promoción
Científica y Tecnológica with grants PICT N
2008-1902 and PICT-
2014-1785.
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