Construction and Building Materials 245 (2020) 118464

Contents lists available at ScienceDirect

Construction and Building Materials

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

Potential role of a novel green eco-friendly inhibitor in corrosion

inhibition of mild steel in HCl solution: Detailed macro/micro-scale
experimental and computational explorations
Ali Dehghani a, Ghasem Bahlakeh a,⇑, Bahram Ramezanzadeh b,⇑, Mohammad Ramezanzadeh b
a
Department of Chemical Engineering, Faculty of Engineering, Golestan University, Aliabad Katoul, Iran
b
Department of Surface Coatings and Corrosion, Institute for Color Science and Technology, P.O. Box 16765-654, Tehran, Iran

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

A novel inhibitor was applied for steel

corrosion mitigation in HCl solution.

Selected extract showed 93%
inhibition degree at 800 ppm extract
after 2.5 h.

Ziziphora leaves extract behaved as
mixed inhibitor.

Classical simulations verified the
extract compounds adsorption on the
steel.
High preotection

Deep corrosion

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

Article history: Ziziphora leaves extract was utilized as a new eco-friendly green inhibitor for acidic-induced corrosion of
Received 24 July 2019 mild steel (MS). The inhibition activity of various phytochemicals present in the Ziziphora leaves aqueous
Received in revised form 1 January 2020 extract, e.g., acacetin, chrysin, and thymonin were probed by electrochemical examinations. The influ-
Accepted 13 February 2020
ence of Ziziphora leaves extract on HCl aggressiveness reduction was inspected via several surface exper-
iments. Moreover, the structure of extract phytochemicals was characterized by Fourier transform
infrared spectroscopy (FT-IR) spectroscopy and ultraviolet–visible (UV–Vis) spectroscopy. The electro-
Keywords:
chemical impedance spectroscopy (EIS) analysis evidences that by increasing the concentration of
Mild steel
Ziziphora leaves extract
Ziziphora leaves extract (up to 800 ppm) the inhibition performance raises to 93% (after 2.5 h). The polar-
Green corrosion inhibitor ization curves reveals that through mixed inhibition control the corrosion of steel was retarded by
EIS Ziziphora leaves extract. The surface studies ensure the Ziziphora leaves extract effectiveness in MS sur-
FT-IR face damage/roughness reduction. Also, the Ziziphora leaves extract molecules adsorption on the steel
Molecular simulations surface occurs according to the Langmuir isotherm model. Alongside experimental explorations, theoret-
ical tools including classical simulations (molecular dynamics, MD connected with Mote Carlo, MC) and
quantum chemical computations (density functional theory, DFT) were chosen for obtaining basic
electronic/atomic-scale details about the extract compounds adsorption on target metal and their active

⇑ Corresponding authors.
E-mail addresses: gh.bahlakeh@gu.ac.ir (G. Bahlakeh), ramezanzadeh-bh@icrc.ac.ir, ramezanzadeh@aut.ac.ir (B. Ramezanzadeh).

https://doi.org/10.1016/j.conbuildmat.2020.118464
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464
sites. The results of molecular simulations the adsorption tendency of green extract molecules on the
steel, which supports the experimental outcomes.
1. Introduction
Nowadays, metal corrosion has become one of the biggest chal-
lenging problems in numerous industrial applications, leaving high
cost-waste in different countries. Hence, researchers are focusing
on different iron protection ways. Certainly, corrosion cannot be
controlled via 100% efficiency but by utilizing highly resistant
materials, safe industrial processes and prevention methods the
steel lifetime can be increased notably [1]. The corrosion occur-
rence can be affected by various factors (i.e., surface impurities,
pressure, temperature and solution activity) [2–4]. Generally, the
metal alloy surface is electrochemically active and can react with
the surrounding environment to reach a stable form. The iron cor-
rosion activity can be limited by the application of conversion coat-
ing, cathodic protection, and corrosion inhibitors [5]. According to
economic flexibility [6,7] and high anti-corrosion potentiality, the
usage of inhibitors is acknowledged in the present decade. Because
of hazardous environmental impacts linked with the traditional
inhibitors their usage has been limited in recent applications [8].
On the other contrary, by enhancing the ecological consciousness,
the usage of green corrosion inhibitors gained high consideration
recently [9].
Rajesh Haldhar et al. investigated the application of Saraca
ashoka extracts as steel green inhibitor in a 0.5 M H2SO4 solution.
The electrochemical, weight loss and polarization experiments
indicated high efficiency (93%) along with mixed type inhibition
mechanism [10]. In another study, Srivastava et al. selected Pisum
sativum peels extract as a steel inhibitor in HCl solution [11]. The
weight loss, polarization and EIS outcomes illustrated 91%, 87%,
and 90% efficiencies, respectively. The corrosion suppression action
of Acacia hamulosa methanolic extract in 1 M HCl solution was
investigated by Bader et al. [12]. Observed results indicated nearly
94% efficiency after dissolving 600 ppm extract in the electrolyte.
Based on the SEM micrographs a highly dense inhibitive layer
emerged on the metallic substrate. Akhil Saxena et al. understood
that the Cuscuta reflexa extract can behave as a strong inhibitor for
steel in acidic medium (H2SO4) [13]. The EIS observations clarified
that efficiency raised to 93% for the usage of 500 ppm extract. Also,
Rajesh Halder et al. found that Myristica fragrans extract possesses
suitable suppression capability (88% efficiency) against corrosive
H2SO4 solution [14]. Gopal Ji et al. assessed the inhibition impacts
of Musa paradisiac peels aqueous extract in HCl via electrochemical
methods and observed high performance (89%) for 300 ppm
extract concentration [15]. These authors also probed the inhibi-
tory action of Chlorophytum borivilianum root extract against HCl
and H2SO4 solutions. The EIS results demonstrated 90 and 85% effi-
ciency in HCl and H2SO4 electrolytes, respectively [16].
Ziziphora tenuior L. is mainly utilized for gastrointestinal disor-
ders treatment as a carminative and analgesic plant. This medicinal
plant distributed widely all over the Asia region. The phytochemi-
cal analysis indicated that major components of Ziziphora extract
consist of various active components (i.e., acacetin, chrysin, and
thymonin) with heteroatoms and p electrons which can help
inhibition property [17]. There is no report on the application of
Ziziphora extract for MS corrosion retardation capability in HCl
solution.
In the present investigation, the inhibition ability of Ziziphora
leaves aqueous extract for steel corrosion in HCl electrolyte (1 M)
was evaluated by applying several experimental and theoretical
Ó 2020 Elsevier Ltd. All rights reserved.
analyses. The steel microstructures and topographies were probed
via SEM and AFM microscopes, respectively. Moreover, the electro-
chemical features were explored through polarization and EIS
techniques. The structure of Ziziphora leaves extract molecules
was characterized via Fourier transform infrared spectroscopy
(FT-IR) and UV–Vis approach. To corroborate the electrochemical/-
surface morphological outcomes, theoretical tools including
classical simulations (a combination of MD and MC) and quantum
chemical computation (DFT) were selected so as to obtain
detailed-level (i.e., atomic and electronic) understandings
regarding the interfacial surface adsorptivity and reactivity of
chosen Ziziphora leaves extract species.
2. Experimental
2.1. Extraction and preparation
After collecting the Ziziphora leaves from jungles in Golestan-
Iran, they were dried and powdered. The specific amount (30 gr)
of powder was fluxed with highly pure water (1 lit) in a beaker.
Then, the solution was heated (70 °C) and mixed on the stirrer
for 3 h. The resulting solution was passed from the filter for elim-
inating the undissolved Ziziphora leaves particles. Afterward, the
clear solution was centrifuged for 10 min and kept in the oven
for evaporation of the solvent (water). The final solid product is
named Ziziphora leaves extract. The electrochemical combined
with morphological experiments were done on the MS (St-12).
The metal specimens were bought from Mobarakeh Co. and cut
mechanically inappropriate dimensions. The composition of the
chosen alloy is presented in Table 1. The iron surface was abraded
via 400 to 1200 silicon-carbide papers. Then, the samples were
cleaned by commercial acetone and deionized water and were kept
in humid-free packs. The electrolyte was prepared by the use of
strong HCl 37% (Merck Co.) and distilled water. Thereafter, specific
quantities of Ziziphora leaves extract was dissolved in 1 M HCl
solution.
2.2. Characterizations
The phytochemicals of Ziziphora leaves extract were recognized
via UV–Vis and FT-IR techniques. The Perkin Elmer was utilized for
the FT-IR test and the UV–Vis curve was plotted by Cecil sc9200
spectrometer. In order to record the SEM and AFM micrographs
the steel samples were papered and dipped in electrolyte for 5 h.
Subsequently, the samples were washed carefully via deionized
water. The MS surface was explored by a Philips XL30 microscope
Table 1
The mild steel chemical composition used for electro-
chemical and morphological studies.
Element Composition (%)
P 1.2
Mn 1.1
Si 1.0
Mo 1.0
Ni 1.7
Cr 0.7
Fe balance
 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464 3

for capturing the SEM images. The surface topographies were
recorded by DS 95–200 instrument. In addition, the steel surface
hydrophilic nature changes were assessed by contact angle (CA)
measurements and the water droplets pictures were obtained by
a home-made type instrument. The EIS and polarization measure-
ments were conducted by Gill device. For the polarization test, the
potential was monitored between + 250 and 250 mV around OCP
(1 mV.s1 sinusoidal perturbation). Additionally, the EIS outcomes
were recoded between 1 mHz and 104 Hz (10 mV constant scan
rate).
2.3. Microscopic-scale investigations
2.3.1. Quantum chemical computations
For probing the electronic structure of green inhibitor (Ziziphora
extract) constituents the electronic scale quantum chemical com-
putations on the basis of DFT were used. The chemical structures
(neutral form) of organic constituents of Ziziphora extract are dis-
played in Fig. S1, which includes acacetin, chrysin, and thymonin.
Besides the neutrally-charged form of present molecules, their
positively-charged (i.e., protonated) state should be considered
owing to the inhibitors protonation in acidizing media [18]. The
protonation presumably takes place through oxygen atoms. For
molecular protonation, the best oxygen atom with the highest
chance of protonation was first identified via calculating the ther-
modynamic parameters namely proton affinity and basicity. Based
on the estimated amounts of these parameters the single carbonyl
O atom of all three constituents was found as the most favorable
atom for mono-protonation. The molecular structures were fully
refined under liquid medium situations by the combination of
DFT method, B3LYP/6-311G** level and SCRF/PCM formula (all pre-
sent in Gaussian 09 package). For fully refined structures the fol-
lowing features were predicted: energies/pictures of the highest
occupied and the lowest unoccupied molecular orbitals (shown
3. Results and discussion
3.1. FT-IR and UV–Vis
The FT-IR diagram of Ziziphora leaves extract was reported in
Fig. 1. As explained in previous works [18], the existence of polar
functional groups and heteroatoms is the most important object
in the adsorption of inhibitor molecules on the iron surface. Based
on Fig. 1 the O–H (3397 cm1), C–H (2930 cm1), C = O
(1707 cm1), C-O (1601 cm1), C–C (1410 cm1) and CH3
(1260 cm1) vibrations were identified in Ziziphora leaves extract
structure which can assist the adsorption of extract molecules on
MS surface, leading to their anti-corrosion potential against corro-
sion [18]. Also, the Ziziphora leaves extract possesses many het-
eroatoms (i.e., O) which can be protonated and adsorbed easily
via electrostatic interactions. The extract of Ziziphora leaves was
further characterized by the UV–Vis approach. As shown in
Fig. 1, before MS immersion in HCl two sharp peaks exist in the
UV–Vis plot. The first peak, which is located at 225 nm, pointed
to p-p* transition, depicting the C = C bond (aromatic) absorption.
The second peak (centered in 331 nm) is related to n-p* transition,
illustrating the C = O groups’ absorption ability [18]. After iron sub-
jection, the p-p* and n-p* transition humps migrated to 221 and
326 nm, respectively. These variations pointed to the successive
interaction of C = C and C = O bonds with iron cations.
3.2. Electrochemical studies
Prior to EIS and polarization tests the open circuit potential
(OCP)-immersion time plots of all samples were recorded during
1 h iron subjection to HCl medium (Fig. 2). It is obviously seen that
the OCP moved to low values rapidly at initial immersion times
a
C-H , CH2

by HOMO, EHOMO, LUMO, ELUMO and DEL-H = ELUMO- EHOMO), green

molecules charges (via ChelpG scheme), Fukui indices (FIs) and
the number of transferred charge (DN). Upon calculation of the
transferred charge, the hardness (g) and chemical electronegativity
(v) were utilized. The g and v values were instead dependent upon
2930
O-H

1260
1707

the ionization potential (I) relying on the energy of HOMO and the
electron affinity (A) relating to the LUMO energy.
1410

C=O
CH3
3397

1601

C-C

2.3.2. Classical simulations C-O

Classical atomic-level simulations namely MC and MD were
selected for exploring the interfacial adsorptivity of Ziziphora
extract constituents on the target steel metal expressed by Fe
(1 1 0) surface. The adsorption of neutrally-charged/positively-ch
b
arged green extract molecules obtained from DFT on the selected
iron surface was analyzed via the MC technique. In the case of
MD, a single extract molecule and solution layer were placed on π-π* transition
the surface. The solution layer representing the 1 M HCl contained
water (4 9 1), chloride (9) and cationic species of hydronium ion
(9). The potential energies of all prepared cells of MD were mini-
mized for at least 20,000 steps as static simulations. Thereafter,
1 ns (1000 ps) dynamics (i.e., NVT MD) simulations were continued
selecting 1 fs time step and 298 K as simulation temperature. The
running of static and dynamics simulations was done by the Mate-
rials Studio program. Classical simulations were based on COM- n-π* transition
PASS as an appropriate force field. The temperature control at
298 K was obtained via Noose-Hoover thermostat. The electro-
static interactions were described by Ewald and the vdW ones
were modeled by the atom-based cutoff. The movement of metal
atoms during classical simulations was hampered. Fig. 1. (a) FT-IR and (b) UV–Vis spectra of Ziziphora leaves extract powder.
4 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464
Fig. 2. Open circuit potential versus time for mild steel sample immersed in 1 M
HCl solution with different concentrations of Ziziphora leaves extract.
[19] due to iron oxide dissolution and galvanic cell formation on
the iron surface. Also, the potential of all samples became stable
after 20 min. This stabilization can be related to the formation of
Fe oxide/hydroxide on the MS substance in the case of the
inhibitor-free solution and the adsorption of inhibitor molecules
in the case of inhibited HCl solution [20]. Evidence revealed that
by enhancing the Ziziphora leaves extract concentration in the elec-
trolyte more negative values for OCP were achieved, indicating
suitable adsorption and high iron surface coverage of Ziziphora
leaves extract molecules.
The definition of electrochemical kinetics can be done by
polarization evaluations (Fig. 3). Observations clarified that after
Fig. 3. (a) Potentiodynamic polarization diagrams for the mild steel samples dipped
in the 1 M HCl media with different concentrations of Ziziphora leaves extract. (b)
Potentiodynamic polarization diagrams shifted to Ecorr = 0.
dissolving Ziziphora leaves extract in HCl medium the polarization
curves moved to cathodic regions (except 600 ppm sample), signi-
fying the fact that the cathodic interactions are more effective than
anodic ones against steel corrosion [5]. Further inspection of this
figure depicted that by enhancing the concentration of Ziziphora
leaves extract the corrosion current density (icorr) adopted lower
magnitudes. Also, the cathodic domains are parallel for all samples
which implied unchanged cathodic reactions mechanism [21].
However, after the addition of the Ziziphora leaves extract to elec-
trolyte the shape of anodic domains changed appreciably. In other
words, the existence of Ziziphora leaves extracts affected the iron
dissolution mechanism in acidic solution [22]. For better compar-
ison, the polarization parameters like anodic (ba) and cathodic
(bc) Tafel constants (slopes), corrosion potential (Ecorr) and icorr
were estimated and recorded in Table 2. Clearly, the Ecorr did not
vary remarkably and under the best condition, only ± 15 mV can
be observed. Such outcomes suggested that the extract of Ziziphora
leaves can control HCl aggression via mixed anodic/cathodic pro-
tection mechanisms (the Ecorr differences are below ± 85 mV)
[23]. As exhibited, the icorr was mitigated noticeably after introduc-
ing the Ziziphora leaves extract into acidic medium, reflecting the
high performance of a defensive layer in HCl solution [24]. The dif-
ferences in ba may be related to the adsorption of extract molecules
on anodic sites [25]. For better evaluation the polarization effi-
ciency was computed as follows [26–28]:
0
icorr  icorr
gð%Þ ¼ 0
ð1Þ
icorr
0
Where icorr and icorr represent the current density of un-
inhibited and inhibited samples, respectively. It is clearly noticed
that after introducing 800 ppm of Ziziphora leaves extract, the cor-
rosion activities retarded notably (91% for 5 h metal immersion),
indicating that a sufficient anti-corrosive layer constructed on
the iron substrate [29–31].
To investigate the Ziziphora leaves extract effectiveness in HCl
solution the EIS measurements were conducted in various immer-
sion times for different samples. The Nyquist and Bode plots were
recorded pictorially in Fig. 4 and S2, respectively. As displayed in
Fig. 4, the bare sample did not provide high resistance against cor-
rosion attacks and only impedance value of 40 X.cm2 was obtained
in the solution subjected to HCl solution for 5 h. However, after
enhancing the extract concentration in HCl media the resistance
raised to higher values (about 560 X.cm2 for 800 ppm sample)
reflecting the strong inhibition impact of green extract in 1 M
HCl solution. On the other side, the shape of Nyquist diagrams
did not alter even after inhibition, demonstrating a simple corro-
sion occurrence in all samples [32]. Moreover, only a semicircle
can be observed in all cases which pointed to the fact that corro-
sion is under control of the charge transfer mechanism. In general,
the deviations of semicircles indicated the surface un-uniformity,
electrode discontinuity and inhibitor adsorption on the electrode
substance. All experimental results were fitted via a one-time con-
stant equivalent circuit model. Low deviations (i.e., v2) ensure that
this model is appropriate for fitting the experimental outcomes.
The derived parameters like solution resistance (Rs), total resis-
tance (Rt = Rs + Rct), constant phase element (CPE), double layer
capacitance (Cdl) and EIS efficiency (Cdl) are tabulated in Table 3.
The increment of Rt highlights that the inhibitor molecules’ effec-
tiveness in the reduction of iron substance dissolution rate in HCl
solution [33]. The Y0 values shifted to lower amounts for the inhib-
ited sample, disclosing the replacement of inhibitor molecules of
Ziziphora leaves extract with water molecules [34]. Unlike Y0 the
phase shift deviation (n) values for the inhibited samples are much
higher than the bare sample. The ‘‘n” values are commonly in rela-
tion to the electrolyte surface homogeneity/heterogeneity. As
 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464 5

Table 2
Potentiodynamic polarization parameters after 5 h immersion of mild steel in 1 M HCl with different concentrations of Ziziphora leaves extract.

Concentration (mg.L-1) Ecorr vs. Ag/AgCl (mV) icorr (mA/cm2) -bc (mV/dec) ba (mV/dec) g (%)
0 548.1 ± 41.6 0.89 ± 0.91 110 ± 10 100 ± 9
200 550.1 ± 44.2 0.18 ± 0.05 166 ± 12 76 ± 5 79
400 563.3 ± 42.3 0.15 ± 0.04 157 ± 11 101 ± 8 83
600 542.8 ± 44.5 0.11 ± 0.02 173 ± 15 93 ± 8 87
800 557.8 ± 47.9 0.08 ± 0.01 162 ± 13 166 ± 11 91

Fig. 4. Nyquist plots for mild steel sample immersed in 1 M HCl solution with (a) 200, (b) 400, (c) 600, (d) 800 and (e) 0 ppm of Ziziphora leaves extract.
6 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464

Table 3
Impedance parameters for mild steel during 5 h immersion in 1 M HCl with different concentrations of Ziziphora leaves extract.

Concentration (ppm) Immersion time (h) Rs (O.cm2) Rct (O.cm2) CPE Cdl (lF/cm2) g (%) v2
-6 2 n2
Y0(10 S cm S ) n
0 0.5 2.1 ± 0.21 32.7 ± 4.2 135 ± 11.2 0.86 334.94 0.00421
2.5 2.3 ± 0.19 36.4 ± 5.1 155 ± 13.6 0.87 369.44 0.00352
5 2.4 ± 0.15 42.6 ± 7.2 200 ± 18.9 0.86 541.19 0.00415
200 0.5 1.4 ± 0.08 281.9 ± 18.9 59 ± 4.8 0.85 62.55 88 0.00385
2.5 1.4 ± 0.09 306.3 ± 25.6 46 ± 5.1 0.88 48.12 88 0.00364
5 1.8 ± 0.11 330.6 ± 28.1 47 ± 5.6 0.88 50.88 87 0.00388
400 0.5 1.3 ± 0.06 219.8 ± 19.5 57 ± 4.9 0.90 58.64 85 0.00442
2.5 1.4 ± 0.07 382.4 ± 31.2 59 ± 5.5 0.88 61.73 90 0.00398
5 1.6 ± 0.05 336.9 ± 30.6 71 ± 6.1 0.86 76.58 87 0.00469
600 0.5 1.5 ± 0.03 313.4 ± 25.7 48 ± 3.5 0.92 49.70 89 0.00401
2.5 1.5 ± 0.06 436.8 ± 38.2 61 ± 5.3 0.89 64.10 91 0.00418
5 1.4 ± 0.06 419.6 ± 35.9 70 ± 6.3 0.88 73.25 90 0.00421
800 0.5 1.8 ± 0.09 401.2 ± 29.7 34 ± 2.1 0.90 36.27 92 0.00438
2.5 1.8 ± 0.10 485.0 ± 39.1 47 ± 3.6 0.89 50.51 93 0.00410
5 1.5 ± 0.09 554.8 ± 41.6 58 ± 4.8 0.91 60.35 92 0.00399

could be observed the value of this parameter is low for the blank
sample which directly explains the high coverage of Fe oxide/hy-
droxide on the iron substance. However, after increasing the
amounts of Ziziphora leaves extract in acidic solution the value of
this quantity improved significantly, indicating good prevention
against corrosive HCl and the corrosion products movement from
the MS substrate. The behavior of Cdl values is different from Y0
ones as its values are much lower for the inhibited samples than
a bare one. This observation is directly devoted to the electrical
constant reduction and/or high double layer thickness. In addition,
the calculated values of efficiency percentage were listed in Table 3.
It is evident that by increasing the extract concentration a better
performance was reached, which is assigned to more metallic sur-
face coverage by inhibitor molecules. In the best condition the effi-
ciency value of approximately 93% was gained after 5 h steel
exposure to the electrolyte.
3.3. Adsorption isotherm
The inhibition performance is directly associated with the
adsorption of inhibitor molecules on the metal sheet. For the anal-
ysis of the type of adsorption of Ziziphora leaves extract compo-
nents on target adsorbent different adsorption modes were
considered. Herein, the experimental results were fitted by Lang-
muir, Frumkin, Temkin and Freundlich isotherms and the fitting
results were portrayed in Fig. 5. As illustrated, the experimental
results were excellently fitted with Langmuir isotherm
(R2 = 0.99). Hence, it can be inferred that the Ziziphora leaves
extract protected the MS substrate through a mono inhibitor layer.
The adsorption parameters were listed in Table 4. The summarized
data in this table demonstrated high standard adsorption equilib-
rium constant (Kads) values, an observation clarifying spontaneous
adsorption of Ziziphora leaves extract on the steel substance. Fur-
thermore, it was found that the standard Gibes free energy
 of the suitable protection of Ziziphora leaves extracts barrier
ðDGads Þ values changed between 33 and 35 kJ.mol1. According
 against corrosion attacks. The parameters relevant for AFM analy-
to previous works, if the DGads is higher than 20 kJ.mol1 the
adsorption takes place physically and its values of less than 40 kJ.-
mol1 demonstrate the occurrence of adsorption via chemical
interactions [18]. Accordingly, the Ziziphora leaves extract mole-
cules adsorbed by chemical/physical interactions (electrostatic
and charge sharing).
sented in Fig. 6. As shown, the angle droplet obeyed simple
patterns and intensified with the enhancement in the concentra-
tion of Ziziphora leaves extract. The increment is rationalized by
inhibitor (Ziziphora leaves extract) molecules adsorption on the
surface of MS. It is also observed that the angle related to the bare
sample is not large enough, declaring the high hydrophilic charac-
ter of the sample [18]. This can be devoted to the un-uniform sur-
face and high coverage of corrosion products on the MS surface.
The existence of corrosion products (i.e., Fe oxide/hydroxide) can
accelerate the formation of hydrogen bonds between the corrosive
ions and iron substrate, giving rise to high aggression [18]. After
adsorption of the molecules of Ziziphora leaves extract on MS sur-
face the surface hydrophilicity degree decreased, proposing the
lower hydrogen bonds emergence among corrosive ions and iron
surface [18].
The MS surface was additionally explored by means of SEM
analysis and final micrographs are portrayed in Fig. 7. Evidence
showed that the substance of the bare sample was covered by cor-
rosion products, which indicates the occurrence of deep corrosion
on the MS surface. However, a highly defensive layer was formed
on the MS surface after increasing the Ziziphora leaves extract con-
centration in the electrolyte. In the best case (i.e., 800 ppm concen-
tration) the corrosion products were removed from the iron
surface and an inhibitive barrier layer covering the whole electrode
area. These observations reflected suitable inhibition impact of
Ziziphora leaves extract in HCl solution on MS surface.
The derived AFM images are presented in Fig. 8. Based on the
plotted results, it is apparent that the blank sample yielded higher
variations in comparison with the 800 ppm sample. This experi-
mental observation points to deep iron corrosion happening on
the MS surface. In addition, the high amounts of height mountains
may be related to the presence of iron oxide/hydroxide particles on
metal [18]. By dissolving 800 ppm extract of Ziziphora leaves the
height variations diminished considerably, which is an implication
sis are listed in Table 5. As proved in this table, all parameters for
the inhibited sample are too low in comparison with the bare sam-
ple which supports the outcomes from AFM micrographs.
3.5. Corrosion prevention mechanism

3.4. Surface studies On the basis of the aforementioned discussions, the inhibitor
molecules can be adsorbed on the MS substance chemically, phys-
To assess the steel surface hydrophilicity degree CA measure- ically or through both mechanisms. Adsorption of inhibitor mole-
ment was executed and the recorded water contact angles are pre- cules is dependent on their molecular structure, MS active sites
 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464 7

Fig. 5. (a) Langmuir, (b) Frumkin, (c) Temkin and (d) Freundlich adsorption isotherm for mild steel in 1 M HCl solution with different concentrations of Ziziphora leaves
extract.

Table 4
Langmuir isotherm parameters for different concentrations of Ziziphora leaves extract
in 1 M HCl solution.

Concentration (ppm) Immersion time (h) Kads (M1) DG°ads (kJ mol1)
200 0.5 36,666 35.9
2.5 36,666 35.9
5 33,461 35.7
400 0.5 14,166 33.6
2.5 22,500 34.7
4
5 16,730 34.0
600 0.5 13,484 33.5
2.5 16,851 34.0
5 15,000 33.7
800 0.5 14,375 33.6
2.5 16,607 34.0
5 14,375 33.6

Fig. 6. Contact angle measurements for mild steel after 5 h immersion in 1 M HCl
solution with (a) 0, (b) 200, (c) 400, (d) 600, (e) 800 ppm of Ziziphora leaves extract.

and charge density [18]. In order to construct a barrier, the inhibi-

tor molecules should be adsorbed on the MS sites. For physical the chloride ions with negative charge can be adsorbed on the
adsorption, the protonated inhibitor molecules interact with the MS surface. The protonated forms of Ziziphora leaves extract mole-
adsorbed chloride ions, as graphically shown in Fig. 9 [35]. Actu- cules (i.e., acacetin, chrysin, and thymonin), which carry a net pos-
ally, the iron surface charges positively in HCl solution and thus itive electronic charge, are able to electrostatically interact with
8 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464
Fig. 7. SEM images of mild steel surface after 5 h immersion in 1 M HCl solution with (a) 0, (b) 200, (c) 400, (d) 600 and (e) 800 ppm of Ziziphora leaves extract.
adsorbed chloride ions [36]. Besides the electrostatic interactions,
the acacetin, chrysin, and thymonin molecules interact with metal
ions (cations) by sharing the electrons in the heteroatoms (i.e., O)
with Fe empty orbitals (called as chemisorption) [18]. Within this
mechanism, the other electron-rich site of acacetin, chrysin and
thymonin electron, i.e., aromatic rings can donate p electrons to
iron cations containing unfilled atomic orbitals.
3.6. Novelty aspects and industrial applications
The selection of a specific steel corrosion inhibitor relies on
some important factors which include inhibition performance,
inhibitor availability, and cost-effectiveness. Besides these key
parameters, the environmental and human health negative effects
should be considered. By taking into consideration of such impor-
tant factors, the usage of commonly utilized inhibitors (i.e., phos-
phoric and chromatic base) was forbidden nowadays. Moreover,
synthetic inhibitors lead to economic loss and environmental pol-
lution. The difficulty in the production of these types of inhibitors
is also another parameter that can limit their usage in large-scale
industrial applications. For these reasons, intensive research efforts
have recently done to find potential replacements like green corro-
sion inhibitors. Green inhibitors can be classified as biopolymers,
ionic liquids, and extracts. Because of the lower economic effi-
ciency of biopolymers and ionic liquids, the extracts become very
popular in industrial applications. However, the utilization of
extracts has restrictions such as availability limit, production diffi-
culty, low solubility and insufficient performance in short and long
intervals. According to literature, the extraction procedure mostly
happens with the aid of methanol and ethanol solvents. Although
these solvents have low environmental risks, their cost is not flex-
ible for industrial procedures (7–8$ per lit). The economic aspects
are not an important issue for lab scales but in industrial applica-
tions is the most important topic (Table 6).
According to Table S1, the production procedure for green inhi-
bitors requires more than 10$ per kg. Although the extraction pro-
cess of the fruits and flowers can affect the extraction cost notably
the leaves extracts are very cost-effective even in high amounts
 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464 9

Fig. 8. AFM images of mild steel surface after 5 h immersion in 1 M HCl solution with (a) 0 and (b) 800 ppm of Ziziphora leaves extract.

Table 5
AFM parameters after 5 h immersion of mild steel in 1 M HCl with different concentrations of Ziziphora leaves extract.

Concentration (ppm) Sy1 (nm) S2z (nm) S3a (nm) Sq4 (nm)
0 812 752 99 125
800 550 595 62 85
1
Maximum height 2Ten point height 3Arithmetic mean square deviation
4
Root mean square deviation

Fig. 9. Schematic corrosion inhibition mechanism of mild steel by Ziziphora leaves extract inhibitor against 1 M HCl solution.

(e.g., Ziziphora leaves extract and Eucalyptus leaf extract). The sol-
ubility parameter is another object which should be considered.
Low solubility gives rise to time and energy waste for producing
a homogenous solution (e.g., Borage flower extract and Mustard
seed extract). Furthermore, the performance at longer immersion
times is the most important issue. As displayed, the protection is
not sufficient for most green extracts (below 90% during 0.5 h steel
immersion). On the other side, the defensive behavior of the anti-
corrosive layer lowered after 5 h MS subjection, revealing that a
weak protective layer covered the metallic substrate. However,
by applying the Ziziphora leaves extract significant protection
achieved within short and long time periods, reflecting suitable
protection against corrosion attacks.
The salt deposition in heaters and boilers tubes can affect the
equipment efficiency and for this reason, strong acids such as
HCl can be applied for descaling processes. However, strong HCl
results in deep corrosion and to prevent this unwanted process
the corrosion inhibitors are applicable. It should be noticed that
10 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464

Table 6
Comparison of Ziziphora leaves extract with other inhibitors.

Corrosion inhibitor Hazardous Cost per Kg of Concentration Efficiency Availability Extraction Hazardous Reference
impacts inhibitor (%) environment procedure
Ziziphora leaves extract Very low 6–8 800 ppm 93 Very high Water Very low Present
work
Maize gluten meal extract Very low 1–6 1000 ppm 85 High Water-Ethanol- Low [37]
Acetone
Schinopsis lorentzii extract Very low 20–40 2000 ppm 86 Low Water Very low [38]
Polysaccharide Very low 500–1000 100 ppm 96 Lab Various solvents High [39]
product
Alginate Very low 20–30 1000 ppm 82 Lab Various solvents High [40]
product
1-benzyl-4-phenyl-1H-1,2,3- High – 7 mM 95 Lab Various solvents High [41]
triazole product
(N-(quinolin-8-yl) quinoline-2- High – 100 ppm 94 Lab Various solvents Very high [42]
carboxamide) product

sufficient protection in short immersion times is the most impor-
tant topic. According to literature, most of the inhibitors cannot
provide high protection in short immersion times and significant
protection observed in long time periods. The descaling and acid
washing processes are not long-term approaches and thus most
of the corrosion inhibitors are not suitable for this objective. How-
ever, the Ziziphora leaves extract can prevent corrosion even in
short intervals (0.5 h), proposing its potency for the aforemen-
tioned applications.
3.7. Classical simulation results
The affinity of selected neutral as well as charged Ziziphora
extract constituents on the steel (i.e., iron (1 1 0)) adsorbent was
evaluated by conducting a combination of MC and MD. The top
views of MC cells possessing the lowest potential energy were
visualized in Fig. 10. The visualized configurations indicate that
the acacetin, chrysin and thymonin compounds of Ziziphora extract
are able to adsorb onto the target substrate (steel). The careful
evaluation of the visualized surface clarifies that the adsorbed
geometries (i.e., aromatic backbone) of acacetin, chrysin, and thy-
monin (neutral and charged) arranged parallel relative to substrate
of steel or iron. The planar molecular arrangement leads to maxi-
mized contact area (or surface coverage) of corrosion-inhibitive
species over the target metallic adsorbent which results in mini-
mized availability of substrate against unwanted corrosive attacks
of chlorine anions in acidic solution. Therefore, the electron-rich
sources of surface-adsorbed components (for instance heterocyclic
rings and heteroatoms) are able to effectively give lone pair and p
electrons to a potential charge acceptor, i.e., metal atoms bearing
empty orbitals. Such charge sharing between extract molecules
and the metallic surface gives rise to the formation of coordination
bonds. This electron sharing could also take place oppositely, i.e.,
from the metal surface to positively-charged inhibitive species
leading to their antibonding interactions. The emergence of such
chemical metal/inhibitor interactions gives rise to a stable and
compact film of extract molecules over the surface. The quantita-
tive results including the adsorption energy related to each certain
non-charged and charged molecule are listed in Table 7. The ener-
gies with negative magnitude observed for all Ziziphora extract
constituents are an indicator of spontaneous green molecules
adsorption. It is visible from the listed energies that the absolute
values of derived adsorption energies for both neutral and charged
states changed in the sequence of thymonin > acacetin > chrysin
reflecting the most intensified surface attachment capacity of thy-
monin molecule amongst considered green molecules. The liquid
phase MD simulation snapshots obtained after 1 ns are recorded
in Fig. 10. The side views of final MD configurations confirm that
the investigated molecules preserved their adsorption propensity
when the metal surface is in contact with solvent molecules. The
adsorption energies (in kcal/mol) of 202.38, 164.37 and
231.85 were respectively estimated for neutral acacetin, chrysin,
and thymonin. Additionally, the mono-protonated acacetin, chry-
sin and thymonin adsorption were quantified by energies of
250.12, 238.37 and 274.63 kcal/mol, respectively. The trend
of these energies is the same as that observed in MC modeling,
which again points to the strongest adsorption and the best inhibi-
tion level of thymonin agent. The visualized simulation snapshots
in connection with the adsorption energies of the negative sign
are an implication of adsorption layer formation of the Ziziphora
extract constituents which can act as a suitable barrier for target
metal corrosion.
3.8. Quantum chemical calculation results
The atoms/sites in green inhibiting molecules which are helpful
in adsorption on steel were basically probed by electronic-
structure analyses using DFT. Through DFT the donor–acceptor
chemisorption mechanism of extract species was explored. Within
this type of adsorption, the electron-rich parts of adsorbing mole-
cules and electron-deficient centers of metal substrate share/trans-
fer charges at solution/metal interface. The analysis of electron-
donating and withdrawing ability was executed via graphical
examination and quantification of HOMO/LUMO of each molecule.
The fully refined geometries and corresponding HOMO/LUMO
plots in neutral/charged acacetin, chrysin and thymonin are gath-
ered in Fig. 11. According to the plotted results, the phenyl rings,
central ring double bond, and oxygen atoms (ether, carbonyl, and
hydroxyl) in neutral components contributed in the distribution
of HOMO electron density isosurface. The HOMO of charged acace-
tin and chrysin mostly resembles that of neutral species. However,
in the case of charged thymonin the whole aromatic skeleton
appeared as HOMO places. As a consequence, the above-
mentioned sites of neutral and charged extract components have
the highest capability of offering their electrons towards an appro-
priate electrophile such as unfilled orbitals of iron centers. On the
other side, the LUMO isosurfaces of non-charged and charged aca-
cetin, chrysin and thymonin located overall backbone carbon sites
and also the oxygen atoms directly attached to ring. Hence, the
entire backbone of all three molecules could take charges supplied
by nucleophiles (filled metal atoms orbital) and thereby involve in
donor–acceptor based chemisorption.
In addition to graphical inspection, the molecular orbitals were
quantitatively explored through the analysis of corresponding
energies. The eigenvalues and respective gap of orbitals are tabu-
lated in Table 8. The summarized data clarify that the neutral thy-
 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464 11

Acacetin Chrysin Thymonin

MC (neutral)
MC (charged)
MD (neutral)
MD (charged)

Fig. 10. The final snapshots of neutral and charged acacetin, chrysin, and thymonin compounds over Fe (1 1 0) surface obtained from MC and MD simulations.

Table 7
The energetic outputs and descriptors (all in kcal/mol) obtained from MC simulations of non-protonated and mono-protonated compounds over the Fe (1 1 0) substrate. The data
in parentheses are for mono-protonated molecules.

Compound Total energy Adsorption energy Rigid adsorption energy Deformation energy dEads/dNi
Acacetin 692.94(636.81) 169.39(178.94) 158.12(163.90) 11.27(15.03) 169.39(178.94)
Chrysin 678.14(598.30) 151.27(166.42) 139.86(146.34) 11.40(20.08) 151.27(166.42)
Thymonin 291.77(230.68) 216.68(220.33) 198.00(203.67) 18.68(16.65) 216.68(220.33)

monin owned the greatest EHOMO amount amongst studied com-
pounds which signifies its strongest affinity against electron dona-
tion. Moreover, this molecule possessed the least value of the
energetic gap (DEL-H) displaying its best corrosion controlling
action. The sequence of these quantities in case of charged mole-
cules is the same as that in non-charged species, highlighting the
most effective inhibition behavior of charged thymonin. By means
of a series of chemical descriptors the magnitude of charge moved
from extract inhibitor to metal atoms or vice versa (i.e., DN) was
assessed. The simulated values listed in Table 8 demonstrate that
the DN of all non-charged molecules is positive ensuring the trans-
fer of charge from green molecules to metal surface. The negative
DN value in the case of some charged molecules implies the charge
migration from metal to corresponding charged molecules. The
neutral and mono-protonated thymonin yielded the highest DN
further proposing its most intensified chemisorption.
Further evaluation of electronic structure was done by the anal-
ysis of local reactivity in terms of Fukui indices. These indices are
an indicator of electrophilic and nucleophilic natures of corrosion
resisting molecules. The DFT obtained results of FIs are displayed
in Fig. 12. The depicted graphics illustrate that in the neutral aca-
cetin, chrysin and thymonin some aromatic cycles, single ring
ethylene bond together with atomic oxygen centers emerged as
electrophilic places, implying the sharing of charges from these
local regions with electrophiles attacking the inhibitors. The local
sites of charged or protonated acacetin, chrysin, and thymonin
which are most susceptible to electrophilic attacks include C atoms
in the ring and the neighboring heteroatoms directly attached to
12 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464

Acacetin Chrysin Thymonin

Equilibrated
(neutral)
Equilibrated
(charged)
HOMO (neutral)
HOMO (charged)
LUMO (neutral)
LUMO (charged)

Fig. 11. The equilibrated geometry and HOMO/LUMO of neutral and charged compounds.

Table 8
The HOMO and LUMO energies (eV), ELUMO – EHOMO energy gap (DEL-H), electron affinity (A), ionization potential (I), electronegativity (v), hardness (g), and fraction of electrons
transferred (DN) for non-protonated and mono-protonated compounds.

adsorbate EHOMO ELUMO DEL-H A I v g DN

Non-protonated molecules
Acacetin 6.211 2.100 4.111 2.100 6.211 4.155 2.055 0.1618
Chrysin 6.404 2.199 4.205 2.199 6.404 4.301 2.102 0.1234
Thymonin 5.828 2.095 3.733 2.095 5.828 3.961 1.866 0.2301
Mono-protonated molecules
Acacetin 6.619 3.072 3.547 3.072 6.619 4.845 1.773 0.0070
Chrysin 7.025 3.324 3.701 3.324 7.025 5.174 1.850 0.0956
Thymonin 6.359 3.094 3.265 3.094 6.359 4.726 1.632 0.0287

ring. Furthermore, in both neutral and charged species most back-
bone atoms (i.e., C and O) especially the atoms of carbonyl moiety
(C = O) are most vulnerable to nucleophilic type interactions and
thus presumably take electronic charges which can be offered by
occupied (i.e., filled) orbitals of metal atoms.
4. Conclusion
In the present research the inhibition impact of Ziziphora leaves
extract was investigated via various electrochemical and morpho-
logical examinations and combined MC, MD and DFT approach. EIS
outcomes proved that after dissolving 800 ppm of Ziziphora leaves
extract in the electrolyte the MS corrosion was notably mitigated
and 93% efficiency value was achieved after 2.5 h iron immersion.
Also, polarization graphs revealed that the Ziziphora leaves extract
can control the corrosion phenomenon by a mixed type mecha-
nism. Surface studies demonstrated that by enhancing the Zizi-
phora leaves extract concentration the steel heterogeneity and
hydrophilicity decreased significantly. Additionally, the adsorption
followed Langmuir isotherm, depicting a mono inhibitor layer
 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464
Acacetin
electrophilic
(neutral)
electrophilic
(charged)
nucleophilic
(neutral)
nucleophilic
(charged)
Fig. 12. The Fukui indices of neutral and charged acacetin, chrysin, and thymonin compounds.
adsorption on a steel substrate. The combination of MC and MD
based classical simulations verified the adsorption ability of each
extract molecule over the target metal. Moreover, the DFT results
reflected that the active electron-rich regions of organic extract
molecules are the main sites in their adsorption.
CRediT authorship contribution statement
Ali Dehghani: Writing - review & editing. Ghasem Bahlakeh:
Writing - review & editing. Bahram Ramezanzadeh: Writing -
review & editing. Mohammad Ramezanzadeh: Writing - review
& editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
The present study was supported by Golestan University, Gor-
gan, Iran. Authors gratefully thank the use of the School of Com-
puter Science, Institute for Research in Fundamental Science
(IPM) as the computations were done there.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.conbuildmat.2020.118464.
13
Chrysin Thymonin
References
[1] M. Mehdipour, B. Ramezanzadeh, S.Y. Arman, Application of electrochemical
noise to investigate corrosion inhibition properties of some azole compounds
on aluminum in 0.25 M HCl, Progress in Color, Colorants and Coatings 8 (2014)
69–86.
[2] H. Lgaz, R. Salghi, K.S. Bhat, A. Chaouiki, S. Jodeh, Correlated experimental and
theoretical study on inhibition behavior of novel quinoline derivatives for the
corrosion of mild steel in hydrochloric acid solution, J. Mol. Liq. 244 (2017)
154–168.
[3] H. Lgaz, K.S. Bhat, R. Salghi, S. Jodeh, M. Algarra, B. Hammouti, I.H. Ali, A.
Essamri, Insights into corrosion inhibition behavior of three chalcone
derivatives for mild steel in hydrochloric acid solution, J. Mol. Liq. 238
(2017) 71–83.
[4] H. Lgaz, R. Salghi, S. Jodeh, B. Hammouti, Effect of clozapine on inhibition of
mild steel corrosion in 1.0 M HCl medium, J. Mol. Liq. 225 (2017) 271–280.
[5] M.T. Saeed, M. Saleem, S. Usmani, I.A. Malik, F.A. Al-Shammari, K.M. Deen,
Corrosion inhibition of mild steel in 1 M HCl by sweet melon peel extract, J.
King Saud Univ.-Sci. (2019).
[6] T. Gholami, M. Salavati-Niasari, M. Sabet, Novel green synthesis of ZnAl2O4
and ZnAl2O4/graphene nanocomposite and comparison of electrochemical
hydrogen storage and Coulombic efficiency, J. Cleaner Prod. 178 (2018) 14–21.
[7] M. Goudarzi, M. Salavati-Niasari, F. Yazdian, M. Amiri, Sonochemical assisted
thermal decomposition method for green synthesis of CuCo2O4/CuO ceramic
nanocomposite using Dactylopius Coccus for anti-tumor investigations, J.
Alloy. Compd. 788 (2019) 944–953.
[8] P. Dohare, M. Quraishi, C. Verma, H. Lgaz, R. Salghi, E. Ebenso, Ultrasound
induced green synthesis of pyrazolo-pyridines as novel corrosion inhibitors
useful for industrial pickling process: experimental and theoretical approach,
Results Phys. 102344 (2019).
[9] A. Rostami-Vartooni, M. Nasrollahzadeh, M. Salavati-Niasari, M. Atarod,
Photocatalytic degradation of azo dyes by titanium dioxide supported silver
nanoparticles prepared by a green method using Carpobrotus acinaciformis
extract, J. Alloy. Compd. 689 (2016) 15–20.
[10] R. Haldhar, D. Prasad, A. Saxena, P. Singh, Valeriana wallichii root extract as a
green & sustainable corrosion inhibitor for mild steel in acidic environments:
experimental and theoretical study, Mater. Chem. Front. 2 (6) (2018) 1225–
1237.
[11] M. Srivastava, P. Tiwari, S. Srivastava, A. Kumar, G. Ji, R. Prakash, Low cost
aqueous extract of Pisum sativum peels for inhibition of mild steel corrosion, J.
Mol. Liq. 254 (2018) 357–368.
[12] A. Bader, U. Shaheen, M. Aborehab, Y. El Ouadi, A. Bouyanzer, B. Hammouti, T.
B. Hadda, Inhibitory effect of Acacia hamulosa methanolic extract on the
14 A. Dehghani et al. / Construction and Building Materials 245 (2020) 118464
corrosion of mild steel in 1 M hydrochloric acid, Bull. Chem. Soc. Ethiop. 32 (2)
(2018) 323–335.
[13] A. Saxena, D. Prasad, R. Haldhar, Investigation of corrosion inhibition effect and
adsorption activities of Cuscuta reflexa extract for mild steel in 0.5 M H2SO4,
Bioelectrochemistry 124 (2018) 156–164.
[14] R. Haldhar, D. Prasad, A. Saxena, Myristica fragrans extract as an eco-friendly
corrosion inhibitor for mild steel in 0.5 M H2SO4 solution, J. Environ Chem.
Eng. 6 (2) (2018) 2290–2301.
[15] G. Ji, S. Anjum, S. Sundaram, R. Prakash, Musa paradisica peel extract as green
corrosion inhibitor for mild steel in HCl solution, Corros. Sci. 90 (2015) 107–
117.
[16] G. Ji, P. Dwivedi, S. Sundaram, R. Prakash, Inhibitive effect of chlorophytum
borivilianum root extract on mild steel corrosion in HCl and H2SO4 solutions,
Ind. Eng. Chem. Res. 52 (31) (2013) 10673–10681.
[17] A. Raoofi, A. Amini, R.M. Farahani, The Synergistic Effect of Curcumin and
Ziziphora Extract Due to Their Anti-inflammatory and Antioxidant Properties
on Ovarian Tissue Follicles, J. Pharmaceutical Res. Int. (2018) 1–11.
[18] A. Dehghani, G. Bahlakeh, B. Ramezanzadeh, M. Ramezanzadeh, Electronic/
atomic level fundamental theoretical evaluations combined with
electrochemical/surface examinations of Tamarindus indiaca aqueous extract
as a new green inhibitor for mild steel in acidic solution (HCl 1 M), J. Taiwan
Inst. Chem. Eng. 102 (2019) 349–377.
[19] A.A. Farag, M. Migahed, E. Badr, Thiazole ionic liquid as corrosion inhibitor of
steel in 1 m hcl solution: gravimetrical, electrochemical, and theoretical
studies, J. Bio-and Tribo-Corrosion 5 (3) (2019) 53.
[20] I. Benmahammed, T. Douadi, S. Issaadi, M. Al-Noaimi, S. Chafaa, Heterocyclic
Schiff bases as corrosion inhibitors for carbon steel in 1 M HCl solution:
hydrodynamic and synergetic effect, J. Dispersion Sci. Technol. (2019) 1–20.
[21] M. Chevalier, M. Lebrini, F. Robert, S. Sutour, F. Tomi, C. Jama, F. Bentiss, C.
Roos, Investigation of Corrosion Inhibition Efficiency of Amazonian Tree
Alkaloids Extract for C38 steel in 1M Hydrochloric Media, Int. J. Electrochem.
Sci. 14 (1) (2019) 1208–1223.
[22] M. Sohail, A.D. Chandio, M. Sheikh, High temperature effectiveness of ginger
extract as green inhibitor for corrosion in mild steel, NUST Journal of
Engineering Sciences 11 (1) (2019).
[23] R. Farahati, A. Ghaffarinejad, S.M. Mousavi-Khoshdel, J. Rezania, H. Behzadi, A.
Shockravi, Synthesis and potential applications of some thiazoles as corrosion
inhibitor of copper in 1 M HCl: Experimental and theoretical studies, Prog. Org.
Coat. 132 (2019) 417–428.
[24] G. Karthik, M. Sundaravadivelu, Sodium 2-Oxo-3-(3-oxo-1-phenylbutyl)-2H-
chromen-4-olate as Green Corrosion Inhibitor for Mild Steel in 1 M HCl
Medium: A Combined Experimental and Theoretical Study, J. Bio-and Tribo-
Corrosion 5 (2) (2019) 33.
[25] M. El Faydy, M. Rbaa, L. Lakhrissi, B. Lakhrissi, I. Warad, A. Zarrouk, I.B. Obot,
Corrosion protection of carbon steel by two newly synthesized benzimidazol-
2-ones substituted 8-hydroxyquinoline derivatives in 1 M HCl: Experimental
and theoretical study, Surf. Interfaces 14 (2019) 222–237.
[26] R. Haldhar, D. Prasad, A. Saxena, R. Kumar, Experimental and theoretical
studies of Ficus religiosa as green corrosion inhibitor for mild steel in 0.5 M
H2SO4 solution, Sustainable Chem. Pharm. 9 (2018) 95–105.
[27] S. Jayakumar, T. Nandakumar, M. Vadivel, C. Thinaharan, R.P. George, J. Philip,
Corrosion inhibition of mild steel in 1 M HCl using Tamarindus indica extract:
electrochemical, surface and spectroscopic studies, J. Adhes. Sci. Technol.
(2019) 1–31.
[28] R. Haldhar, D. Prasad, N. Bhardwaj, Extraction and experimental studies of
Citrus aurantifolia as an economical and green corrosion inhibitor for mild
steel in acidic media, J. Adhes. Sci. Technol. 33 (11) (2019) 1169–1183.
[29] A. Saxena, D. Prasad, R. Haldhar, G. Singh, A. Kumar, Use of Saraca ashoka
extract as green corrosion inhibitor for mild steel in 0.5 M H2SO4, J. Mol. Liq.
258 (2018) 89–97.
[30] A. Saxena, D. Prasad, R. Haldhar, G. Singh, A. Kumar, Use of Sida cordifolia
extract as green corrosion inhibitor for mild steel in 0.5 M H2SO4, J. Environ.
Chem. Eng. 6 (1) (2018) 694–700.
[31] R. Haldhar, D. Prasad, A. Saxena, Myristica fragrans extract as an eco-friendly
corrosion inhibitor for mild steel in 0.5 M H2SO4 solution, Journal of
Environmental, Chem. Eng. 6 (2) (2018) 2290–2301.
[32] R.S. Erami, M. Amirnasr, S. Meghdadi, M. Talebian, H. Farrokhpour, K. Raeissi,
Carboxamide derivatives as new corrosion inhibitors for mild steel protection
in hydrochloric acid solution, Corros. Sci. 151 (2019) 190–197.
[33] M.M. Bouraoui, S. Chettouh, T. Chouchane, N. Khellaf, Inhibition efficiency of
cinnamon oil as a green corrosion inhibitor, J. Bio-and Tribo-Corrosion 5 (1)
(2019) 28.
[34] S. Cao, D. Liu, H. Ding, J. Wang, H. Lu, J. Gui, Task-specific Ionic Liquids as
Corrosion Inhibitors on Carbon Steel in 0.5 M HCl Solution: An Experimental
and Theoretical Study, Corros. Sci. (2019).
[35] O. Dagdag, A. El Harfi, O. Cherkaoui, Z. Safi, N. Wazzan, L. Guo, E. Akpan, C.
Verma, E. Ebenso, R.T. Jalgham, Rheological, electrochemical, surface, DFT and
molecular dynamics simulation studies on the anticorrosive properties of new
epoxy monomer compound for steel in 1 M HCl solution, RSC Adv. 9 (8) (2019)
4454–4462.
[36] N. Hassan, S.M. Ali, A. Ebrahim, H. El-Adwy, Performance evaluation and
optimization of Camellia sinensis extract as green corrosion inhibitor for mild
steel in acidic medium, Mater. Rese. Express 6 (8) (2019) 0865c7.
[37] Z. Zhang, H. Ba, Z. Wu, Y. Zhu, The inhibition mechanism of maize gluten meal
extract as green inhibitor for steel in concrete via experimental and theoretical
elucidation, Constr. Build. Mater. 198 (2019) 288–298.
[38] H. Gerengi, H.I. Sahin, Schinopsis lorentzii extract as a green corrosion
inhibitor for low carbon steel in 1 M HCl solution, Ind. Eng. Chem. Res. 51 (2)
(2011) 780–787.
[39] S. Banerjee, V. Srivastava, M. Singh, Chemically modified natural
polysaccharide as green corrosion inhibitor for mild steel in acidic medium,
Corros. Sci. 59 (2012) 35–41.
[40] A. Jmiai, B. El Ibrahimi, A. Tara, S. El Issami, O. Jbara, L. Bazzi, Alginate
biopolymer as green corrosion inhibitor for copper in 1 M hydrochloric acid:
experimental and theoretical approaches, J. Mol. Struct. 1157 (2018) 408–417.
[41] C.M. Fernandes, L.X. Alvarez, N.E. dos Santos, A.C.M. Barrios, E.A. Ponzio, Green
synthesis of 1-benzyl-4-phenyl-1H-1, 2, 3-triazole, its application as corrosion
inhibitor for mild steel in acidic medium and new approach of classical
electrochemical analyses, Corros. Sci. 149 (2019) 185–194.
[42] R. Sadeghi Erami, M. Amirnasr, S. Meghdadi, M. Talebian, H. Farrokhpour, K.
Raeissi, Carboxamide derivatives as new corrosion inhibitors for mild steel
protection in hydrochloric acid solution, Corros. Sci. 151 (2019) 190–197.